CN100513427C - Production of carrageenan and carrageenan products - Google Patents
Production of carrageenan and carrageenan products Download PDFInfo
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- CN100513427C CN100513427C CNB01820516XA CN01820516A CN100513427C CN 100513427 C CN100513427 C CN 100513427C CN B01820516X A CNB01820516X A CN B01820516XA CN 01820516 A CN01820516 A CN 01820516A CN 100513427 C CN100513427 C CN 100513427C
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Abstract
The methods of the present invention prepare carrageenan products from processed seaweed material having a solids content of less than 25% by weight solids, using shear stress treatment. The carrageenan products comprise at least about 60% by weight of carrageenan and at least about 2% by weight of acid insoluble material. The carrageenan products of the present invention are useful as components in food products, such as, dairy products, meats, and dessert gels as well as non-food products, such as, toothpaste formulations, cosmetics, paints, films and delivery capsules.
Description
Related application
The application is filed in the further part that be entitled as the U. S. application sequence number 09/798,012 of " manufacturing of carrageenan and carrageenan product " March 2 calendar year 2001.
TECHNICAL FIELD OF THE INVENTION
The present invention relates to the method for carrageenan product, this carrageenan product of preparation and contain the prescription of carrageenan product according to the present invention.
The background of invention
Carrageenan is to comprise 1,3 complex mixture through the sulfated polysaccharides of bonding type α-D-galactose units and 1,4 bonding type α-D-galactose units linear polymer, and general formula is;
→3α)A(1→4β)B(1→3α)A(1→4β)B(1→3α)A(1→4β)B(1→
Wherein A and B representative is from two on the same group galactose residues not.
Carrageenan extracts the primary structure from red algae and formation marine alga.It is arranged in the cell walls and the cell matrix of plant tissue.The carrageenan composition of commercially available seaweeds usually based on the marine alga dry weight between 30% and 80%.
Carrageenan is widely used as food composition and works in food as milk-product, water dessert frozen glue, meat product, candy, beverage, seasonings and other this series products.Carrageenan also is used for non-foodstuff products, as makeup, toothpaste and other personal-care supplies.The molecular wt of typical commercial carrageenan product is from about 100,000 to 1,000,000 dalton.Carrageenan has the unique ability that at room temperature forms unlimited variety almost, the glue of various jellying points and fusing point is arranged.These glue need not refrigerate, can by freeze repeatedly-thaw cycles becomes stable.Carrageenan solution can make particulate, colloidal dispersion and water/oil-emulsion thickening, suspension, stable.Can be thinning during solution shear, make their easy pumpings.Solution also recovers viscosity and suspending power rapidly when leaving standstill.According to being applied to food, being present in carrageenan several or still less percentage point weight provides gelation, thickening and constraint, also assists to give foodstuff products suitable mouthfeel.Because these character, carrageenan are special ideal fat-replacers in the low fat food.
Carrageenan generally is dissolved in warm water, forms viscous soln therein.It is insoluble to most of organic solvent, typically forms complex body with protein.The main type called after of carrageenan κ, ι, λ, ν and μ.These are distinguished according to being included in the carrageenan repeating galactose unit character.Polymer chain can rupture by acid treatment hydrolytic depolymerization or hydrogen peroxide treatment oxidation depolymerization in the carrageenan.After cutting polymer chain, can obtain the carrageenan product of optimum gelling characteristic and viscosity.
In producing the canonical process of pure carrageenan, natural seaweed at first with cold wash to remove sand and other particle that may after the marine alga results, exist.Carrageenan is swelling not when cold wash usually, main because carrageenan and marine alga constituent in the marine alga, and normally Mierocrystalline cellulose is continuous.The difference that depends on the marine alga kind, the hot water extraction process generally is that the carrageenan that extracts uses alkali lye in pyroprocessing after the cold wash.Usually, the alkali of use is oxyhydroxide for example NaOH, the Ca (OH) of alkali or alkaline-earth metal
2Or KOH.This high temperature alkaline solution modification forms 3,6 dehydration bondings in the polysaccharide galactose units of carrageenan.Behind the alkali modification, filter heat extraction substrate,, add acid for adjusting pH to 9 or lower as Mierocrystalline cellulose, hemicellulose and other particle to remove insolubles.Filtrate can be concentrated into about 4% carrageenan and is used for later processing then.Extracting back selectable process step comprises centrifugal and bleaching.Pure carrageenan generally by with KCl or as the alcohol precipitation of Virahol from the extract acquisition of the aqueous solution.
Commercial size prepares the expense costliness of pure carrageenan, because viscosity and the so machinable speed of carrageenan product of gelling characteristic restriction.Behind the extraction step, hot water flow part only contains the lower concentration carrageenan usually, and generally about at the most 4%.When the concentration of carrageenan was higher, the aqueous phase stream thickness that partly becomes too can't effectively be handled.Therefore, water is handled the carrageenan that stream part per unit volume obtains relatively low ratio.
The method of seeking semi-refined carrageenan of more economical preparation and other products is as than conventional carrageenan substitute more cheaply.Half refining carrageenan (SRC) product be those seldom or do not have the marine alga constituent, mainly be the product that Mierocrystalline cellulose is removed.In preparation SRC process, salt such as KCl or NaCl usually when alkali modification and alkali add together.The existence of q.s salt prevents that the marine alga structure from disintegrating and suppress to extract carrageenan from marine alga.Alcohol as Virahol, also can be used for suppressing the extraction in the high temperature alkali modification step.After the alkali modification step, the marine alga structure is still complete, and the marine alga mixture of handling is dried usually to obtain SRC.If marine alga is Eucheuma family a member, the SRC that obtains is called processing processing Eucheuma marine alga (PES).
United States Patent (USP) 5,502,179 processes at initial (feed) material of marine alga and alkali and the insoluble solvent of carrageenan.With the mixture of this alkaline purification of solution washing, make shear-stress subsequently and handle (as extrusion or use shear mixer).Shear-stress is handled at least on the marine alga material of solids component 25%, and temperature was carried out between 100 to 175 ℃ about 10 to 200 seconds.Carrageenan material after shear-stress is handled can be dry and be pulverized, grinds or mill to obtain granular size at 0.05 powder in the 0.5mm scope.
Conventional carrageenan has some advantages with respect to the SRC that obtains usually from same marine alga.One of advantage is that they generally begin hydration under the temperature lower than SRC, and just they begin swelling and dissolving.For example, from the hydration at room temperature of traditional ι carrageenan, expansion and the dissolving of Eucheuma spinosum.Yet, just can hydration, swelling and dissolving derived from the PES (about more than 60 ℃) of Eucheuma spinosum up to being heated to earlier.Another advantage is that the glue that SRC forms is low with respect to the transparency of the glue of pure carrageenan because SRC contains cellulose substances and other material that conventional carrageenan does not have.Therefore, the use of SRC product is limited to foodstuff products does not need limpid and can and dissolve in the application of required high temperature preparation in the carrageenan hydration.Yet,, need and need not high temperature agglomerative SRC is provided many application.SRC have acceptable color and outward appearance be suitable for being used in human consumption's product also very important, for example, cream, ice-creams, other milk-product and beverage and non-food product, for example, makeup, toothpaste and other personal care product.
Therefore, need the low-cost process of the carrageenan product of production hydration characteristic raising, keep acceptable color and outward appearance to be applicable in the food simultaneously.
Summary of the invention
The invention provides the method for preparing the carrageenan product, comprise that preparing step that contains carrageenan marine alga material and shear-stress that the marine alga solids component is less than 25% weight handles this marine alga material.Before extruding, selectively contain carrageenan marine alga material with alkaline purification.
In one embodiment, containing the step that the preparation process of carrageenan marine alga material comprises has: wash marine alga with water to make the marine alga of washing; With the water rinse marine alga to make the marine alga of rinsing; The marine alga of water or this rinsing of solution washing contains carrageenan marine alga material to make.
In another embodiment, method of the present invention comprises and washes marine alga with water; Arriving about 65 ℃ temperature at about 25 ℃ uses the alkaline purification marine alga to form the marine alga of alkali modification; Marine alga with the water rinse alkali modification; Marine alga with a kind of this alkali modification of aqueous solution rinsing of salt; Marine alga with this alkali modification of water rinse forms finished marine alga, and wherein finished marine alga comprises and is less than 25% solid; Push this finished marine alga and form the extruding marine alga; Dry extruding marine alga forms the carrageenan product.
In another embodiment, salt brine solution concentration is lower than about 40%.Preferable salt brine solution concentration is lower than about 15%.Better salt brine solution concentration is between about 2% and about 15%.
The present invention also comprises the carrageenan product, preferable at least 60% weight carrageenan and at least 2% weight acid non-soluble substance matter of comprising, and hydration is in about beginning below 50 ℃.In a preferable embodiment, the carrageenan product contains the kind of ι-carrageenan from Eucheuma spinosum or other.In another preferable embodiment, the carrageenan product further comprises about 2% salt to about 15% weight.Preferable salt is sodium-chlor.
The present invention also comprises the food and the other products of the product that contains the carrageenan product or produced by preceding method.Preferable carrageenan product comprises at least 60% weight carrageenan and at least 2%, the insoluble material of weight acid.To such carrageenan product that originates from Eucheuma cottonii, hydration can begin being low to moderate under about 50 ℃.To originating from the carrageenan product of Eucheuma spinosum, hydration can begin being low to moderate under about 30 ℃.
Other products comprises the formulation of tooth-paste that contains tackiness agent, wetting agent, abrasive and water, and wherein tackiness agent is according to carrageenan product of the present invention.Preferable binder concn is that about 0.5 of formulation of tooth-paste arrives about 1.5% weight.
The present invention more comprises the method that obtains to contain the one or more carrageenan goods of being produced by the inventive method.In one embodiment, heating comprises that the present invention contains the solution of carrageenan product, and the solution that at least a portion heated is handled to be transformed into barrier substance with condition for validity.For example, form film by solution being dropped into the refrigerative rotating cylinder.Containing the carrageenan film optionally is added to formation in the backwards rotation punch die, cuts the capsules every different sizes with filling by a series of cylinders.
The general introduction of accompanying drawing
Fig. 1 shows the Brabender line chart that changes with the different in moisture level.
Detailed Description Of The Invention
The present invention relates to shear stress contains the carrageenan product from finished marine alga preparation process. Representing the marine alga kind comprises from Eucheuma, Gigartina and Irideae family. Better kind comprises Eucheuma spinosum, Eucheuma cottonii and Gigartina radula.
Finished marine alga can be by obtaining if required then neutralization with the alkali treatment marine alga. The alkali modification of natural seaweed is optionally and can be with alkali such as NaOH, KOH or Ca (OH) in the situation of salt such as NaCl or KCl existence2Carry out. The marine alga of subsequently water rinse modification can obtain salt. The product that obtains when as used in this, term " salt " refers to hydrogen atom when metal replacement acid. In the present invention, salt can be used in the form of the aqueous solution. If salt is used for rinsing, the same salt of using in use and the alkali modification process is better. Use sodium salt rather than sylvite, final shear stress product water dissolubility improves usually.
Drying is carried out in the carrageenan charging that contains that obtains before shear stress is processed, or partial desiccation or humidity and solid constituent are less than 25%. As used in this, term " solid constituent " is weight poor of humidity or water content in gross weight and the marine alga material blends. The water content of marine alga material comprises the water (as hydrate water) that may be incorporated into the marine alga material before the extruding, or adds the water of marine alga material.
In some cases, for example, obtain dry when containing the carrageenan charging, usually need to add water to the marine alga material of drying before extruding, to recover moisture.
Observe when marine alga material feeding stream solid constituent be 25% or when higher shear stress process and usually cause the unacceptable colour-darkening of material. The color that contains the carrageenan product is generally very important for the end user. When the end user prepares human consumption, for example, usually select not secretly in cream-coloured SRC product, cheap, the darker product of color is usually used in color important product not like this.
Perhaps, the difference of observing with the incoming flow that surpasses 25% solid although do not fully understand, is because the effect of the heat that water produces when being subjected to shear stress for incoming flow. Water can be gone out the heat dissipation from the marine alga material that produces in the extruding, reduces the degree that heat makes sugar fusing zoom in the raw material, and caramelization deepens end product. Therefore, when more moisture heat radiation is arranged, generate the lighter product of color.
The change color that produces during shear stress is processed can be monitored with human eye or suitable measurement mechanism. According to better embodiment of the present invention, darkening during shear stress is processed is characterized as the dry powder measurement of at least 99% powder by 100 mesh sieves with Macbeth ColorEye 3000 colorimeters and granular size and is equivalent to less than about 4.0L* unit.
For keeping carrageenan product and the prescription color and the unified appearance that contain this series products, containing carrageenan marine alga material should flow into extruder as rarer incoming flow. Such dilution incoming flow brings end product more attractive in appearance (thinking the result of carrageenan optimum hydration in the marine alga) usually. In addition, water generally needn't be removed from the algal product that contains carrageenan before flowing into extruder, makes the process of preparation carrageenan product more economical because marine alga is more effective at such condition down cut. The marine alga of wet processing can fragment form, about 2cm is better to 5cm.
Extrude is that shear-stress is handled more convenient method.The extrusion equipment of different designs can be used for extruding the marine alga of wet processing.The embodiment of extrusion machine includes, but not limited to twin-screw extruder such as Clextrall ModelBC45 (Clextral company limited, the Tampa, the Florida) and Werner-Pfliederer Model ZSK-30 (Werner-Pfliederer company, Ramsey, New Jersey).Selecting suitable device and extrusion condition is simple with regard to embodiment described below to the people who is good in this respect.
In one embodiment of the invention, use Clextrall Model BC45 twin-screw extruder.This extrusion machine has 8 buckets, and each internal diameter is that 50mm and length are 200mm.The long 1600mm of screw rod, center-distance is 45mm.The marine alga of wet processing can flow into first barrel open top by weightless twin screw feeder.With pump more water is joined first barrel adjusting solids component.All the other barreleds are joined induction heating coil and water cycle with controlled temperature.Also can provide exhaust to select to make steam to discharge, it is preferable to be contained in the 7th bucket.
In another embodiment of the invention, contain the carrageenan raw material be added to one with single-screw extrusion machine that a twin-screw extruder links to each other in.Single-screw extrusion machine can be, for example, Wenger Model X-85, twin-screw extruder can be, for example, and Wenger Model TX-57 (all can buy Sabetha, Kansas from Wenger Manufacturing Co., Ltd).Usually, the single-screw extrusion machine outlet links to each other with the twin-screw extruder inlet, for example, and with a heat insulation flexible conduit.
Although be not to want restriction, think to flow in the extruder system of twin-screw extruder that the heat that single-screw extrusion machine produces is the marine alga material that the twin-screw extruder of more shearing force prepares to contain carrageenan at single-screw extrusion machine.This heat is thought to make the carrageenan in the marine alga raw material to give aquation or is begun dissolving.Other produces this hot method and can be used for the marine alga material that heat prepares to contain carrageenan, for example, and high-shear mixer and/or high solid mixing tank.
The solids component that adds the wet finished marine alga of extrusion machine is generally less than 25% weight.The solids component of finished marine alga can, for example, about 24%.In one embodiment, marine alga material or the finished marine alga that contains carrageenan comprises about 23% solid.In another embodiment, finished marine alga comprises about 22% solid.In an embodiment in addition, finished marine alga comprises about 21% solid.In other embodiment, finished marine alga comprises about 20% solid.In also having an embodiment, finished marine alga comprises about 18% solid.In yet another embodiment, finished marine alga comprises about 16% solid.In a preferable embodiment, the solids component that contains the marine alga material of carrageenan arrives between about 20% weight about 10%.In another preferable embodiment, the solids component that contains the marine alga material of carrageenan arrives between about 17% weight about 13%.
The extruder screw configuration design becomes can provide the shearing that is enough to destroy the plain structure level of seaweed fiber.Typical screw rod comprises 5 high shear zone of being made up of delivery element, mixing pieces, and the reversing element is used for wherein 3 high shear zone.Delivery element transmits finished marine alga along extrusion machine.The reversing element is increased in the residence time in the mixing pieces that takes place to shear.First and second only contains delivery element with seven barrels.One screwed cap is guaranteed mouth template from extruder outlet, stays less relatively clearance.The clearance can be regulated to reach the required enough back pressures of suitable shearing.For example, Clextral Model BC45, the clearance of using 1.75mm.At this, mouth template has 3 holes, each bore dia 6mm.
For suitable shearing is provided, screw speed needs about 200rpm at least.Screw speed is preferable at least about 500rpm, and is better at least about 600rpm.
Extrusion temperature can be regulated to obtain best and effectively to extrude.The extrusion temperature that improves can assist to destroy the marine alga structure, thereby discharges carrageenan from the marine alga constituent.
Preferably, the extrusion machine interior condition can make what is called " steam explosion " take place.Steam explosion is owing to the extrusion machine internal vapor pressure, rapid h substance from extruder die.Particularly, operate extrusion machine under high enough temp and pressure, steam pressurizes in extrusion machine, and the marine alga material that the result contains carrageenan is discharged into barometric point rapidly by the extruder outlet die head.The steam of staying in the material that has been extruded is considered to cause emitting physical form and change in the expansion of the die head shape of the mouth as one speaks.Usually, emitting material extrudes the line material from solid and becomes the particle of getting very thin, high level expansion, open architecture.The granule surface area that such particle forms during with respect to no steam explosion increases.
Promoting that the operation extrusion machine has several advantages under the steam explosion condition.An advantage is that the surface-area that the granular marine alga material that contains carrageenan increases makes the product cooling faster.The product of heat usually clings each other, and cold product is not sticking usually.Therefore, when amassing the increase mass treatment, product surface is improved.The surface-area that " steam explosion " particle increases also makes particle drying faster and hydration is faster.
In another embodiment of the invention, contain carrageenan the marine alga raw material can with hydrocolloid and/or other additive fusion or co-processing with by reducing cost or broadened application is come enhancement function and/or reduced cost.For example, if the carrageenan product is intended for use toothpaste, contain carrageenan raw material (as finished marine alga or the marine alga washed) can with fibrinous material of food grade such as Mierocrystalline cellulose, Microcrystalline Cellulose (MCC) and/or chemically-modified cellulose such as carboxymethyl cellulose (CMC), methylcellulose gum (MC), Natvosol (HEC), hydroxypropylcellulose (HPC) and Vltra tears (HPMC), and and wetting agent, buffer reagent, tensio-active agent, emulsifying agent, sequestrant, other SYNTHETIC OPTICAL WHITNER or staining agent, reodorant and similar substance mix or co-processing.Similarly, finished Euchema cottonii, finished Euchema spinosum and Euchema Mare Humorum algae raw material can with following one or more fusion or co-processing (i) Mierocrystalline cellulose, MCC and/or chemically-modified cellulose; (ii) other Seaweed Extract such as Furcellaria gum, agar and comprise their salt and/or the alginate of chemically modified derivative, for example propanediol alginate; (iii) natural Oak Tree glue and rubber tree juice, as Sudan Gum-arabic and karayagum, many mannosanss such as Viscogum BE, guar gum and konjac, plant milk extract such as pectin and amidated pectins; (iv) biosynthesizing natural gum is as xanthan gum, jelling agent and dextran; (v) protein such as gelatin and chitin; (vi) synthetic hydrocolloid such as polyvinylpyrrolidone (PVP), carboxy vinyl polymer (for example Carbopol product), methylvinylether/MALEIC ANHYDRIDE MIN 99.5 polymkeric substance (for example Gantrez AN product) and ethylene oxide polymer (for example Polyox product); (vii) starch, treated starch, dextrin, glucose, sugar, tensio-active agent, emulsifying agent and salt; And/or other additive, for example microgrid shape albumen, Microcrystalline Starch and analogue.Additive can be selected to contain the product of carrageenan and food and other use and contain the enhanced function that needs in the product of carrageenan product and comprise dispersion, hydration, solvability and other characteristic to be provided at the present invention.Such additive, function and characteristic are known, and for example, as U.S. Patent number 5,502,179 5 row 21 row and following etc. the description.Additive can be before shearing manipulation, in or introduce afterwards or add from containing the carrageenan product after shearing.Additive also can with contain carrageenan marine alga raw material before shearing manipulation or as a part of co-processing, or can with from containing carrageenan product co-processing after shearing." co-processing " or similar terms, as used in this, meaning forms with simple adulterant or stirs the correlated mixture of thing, and for example, as U.S. Patent number 5,441,753 at 5 row, 32 row and following etc. described.
Wet finished marine alga through-put rate can be different.For example, when using 1, during the Clextral Model BC45 of 75mm air gap, wet finished marine alga through-put rate usually from about 40 pounds per hour be up to about 200 pounds per hour.Generally, to special extrusion machine, along with through-put rate improves, the finished marine alga residence time reduces in the extrusion machine.As, to the Clextral extrusion machine, through-put rate is about per hour 80 pounds about 50 seconds of the wet finished marine alga residence time.The finished marine alga solvability of extruding is generally better when hanging down through-put rate, probably increases because of the finished marine alga residence time in the extrusion machine.Residence time increase makes the interior shearing of mixing pieces more.Accordingly, if the residence time also increases, under higher temperature, can obtain the wet finished marine alga that solubleness improves.The residence time increases and can reach by increasing extrusion machine length or improving the reversing component number.More be full of for following barrel in the high material through-rate equally, further strengthen the shearing in mixing pieces.
The cold cut of the finished marine alga of pushing from Euchema spinosum is separated temperature and influenced by the product salts contg.Usually, to the lesser temps solvability, preferable salt is NaCl.Effective salt concentration generally is less than about 25% weight, and it is preferable to be less than about 15% weight.Salt concn is better between about 2% to 15% weight.Required salt concn can obtain by water or the finished marine alga material of salt brine solution rinsing before extruding.From the finished marine alga of Euchema spinosum marine alga, salt concn is about 25%, and the highest swelling temperature is about 92 ℃ usually.Depend on extrusion condition and salt concn that the inventive method is used, the highest swelling temperature can be low to moderate about 10 ℃ to about 70 ℃.For example, the finished Euchema spinosum marine alga material of extruding sodium chloride concentration about 10% makes the highest swelling temperature low to about 25 ℃.
Carrageenan product of the present invention comprises carrageenan and acid non-soluble substance matter, is more preferably the hydration starting temperature about below 50 ℃.Carrageenan product of the present invention more preferably comprises at least 70% weight carrageenan and at least 2% acid non-soluble substance matter.In one embodiment of the invention, hydration is initial below 35 ℃.In another embodiment, hydration is initial below 25 ℃.In a preferable embodiment, carrageenan product of the present invention is from the Euchema spinosum that the ι carrageenan is provided.Acid non-soluble substance matter comprises the constituent of marine alga, mainly is fibrinous material.
Carrageenan product of the present invention comprises the highest about 20% weight water usually, and about 10% weight is more suitable.In a preferable embodiment, the carrageenan product further comprises about 2% salt to about 20% weight, and sodium-chlor is better.The carrageenan product comprises that about 2% is better to about 5% salt.
Carrageenan product particle size of the present invention arrives in about 200 micrometer ranges preferable at about 50 microns.Required granular size depends on special application.For example, some application need point-device granular size so that the carrageenan product can pass through entry needle as meat, therefore, generally use the product of mean particle size at this scope lower limit.In other are used, toothpaste for example, carrageenan product particle size is so unimportant, the therefore general product that uses mean particle size in this range limit.
Hydration starting point according to carrageenan product of the present invention determines by measuring its solution viscosity, and is preferable with the Brabender viscometer.Measure with the Brabender viscometer, the hydration starting point is the point of the slope of a curve as time and temperature function mapping soltion viscosity when changing.Use the Brabender viscometer to measure hydration starting point, setup test solution.Test soln is made of preferable in water the carrageenan product, for example mix the 10.0g product in the 490.0g deionized water.The cup speed of Brabender viscometer is made as 75rpm.Test soln is formed better by the prescription of using at the representative specialty products of carrageenan product.For example, can use following prescription:
Sorbitol Powder/glycerine toothpaste elixir-8.0g sample, 2.0g soluble saccharin, 2.5g tetrasodium pyrophosphate, 11.0g one sodium phosphate, 170.0g Sorbitol Powder, 100.0g glycerine, 220.0g deionized water.
Glycerine toothpaste elixir-8.8g sample, 2.2g soluble saccharin, 2.8g tetrasodium pyrophosphate, 8.4g one sodium phosphate, 242.0g glycerine, 236.0g deionized water.
Meat salt solution-7.5g sample, 7.5g tripoly phosphate sodium STPP, 33.8g glucose, 22.5g sodium-chlor, 429.0g deionized water.
Elixir-4.9g sample, 1.2g terra alba, 12.2g propylene glycol, 482.0g deionized water are wiped in buffing.
In case test soln is ready to, it is initial to determine hydration that the Brabender viscometer is made temperature profile.Above-mentioned prescription preferred temperature line chart is as follows:
Attention: all Brabender viscometers are distributed in 75rpm to carry out.
Carrageenan product of the present invention shows the formation gel property of raising.For example, when 2%SRC solution that foundation the inventive method is prepared be heated to about 50 ℃ and after form gel, the breaking tenacity of glue is about 100 and arrives about 250g.By comparison, 2% finished marine alga solution is heated to 50 ℃ and does not form gel and when being heated to 72 ℃, only form the fragile gel that breaking tenacity is about 90g.Compare therewith, the 2% carrageenan product solution that in 120 ℃ of Clextral extrusion machines, prepares, output per hour 80 pounds and salt concn is about 10%NaCl, is heated to 50 ℃, forms the gel that breaking tenacity is about 150g.
Carrageenan product of the present invention more has multiple application.Such application comprises human consumption's product for example meat, salad dressing, soy sauce, and milk-product are cream, ice-creams and nutrition and pharmaceutical capsule for example, also has non-food product Industrial products for example toothpaste, makeup, paint, oily wellbore fluid and aircraft deicing liquid.Discovery can be prepared into the finished product in any of these product application, wherein pure carrageenan extract can extensively be used according to carrageenan product of the present invention and replace.
For example, carrageenan product of the present invention can be used as the use of formulation of tooth-paste tackiness agent.Formulation of tooth-paste of the present invention comprises tackiness agent, wetting agent, abrasive and water, and wherein tackiness agent is the carrageenan product.Preferable binder concn is about 1.5% weight less than formulation of tooth-paste.
In addition, can be used for (separately or with other composition such as weighting material, plasticizer and/or tackiness agent) according to carrageenan product of the present invention and form film and other type barrier substance.According to barrier substance of the present invention is to separate the material of two or more substances of interest, for example, controls and/or limit their interactional degree.Embodiment according to barrier substance of the present invention comprises film, capsule and pearl, as gel microballon and analogue.
Can form by deposition one deck on substrate or the carrageenan layer that contains according to the carrageenan film that contains of the present invention more.Such film can, for example,, and can simultaneously or use or adhere to substrate subsequently with the form of sheet or net.According to of the present invention contain carrageenan film and other type barrier substance can be used for around and protection different substances such as nutrition, antioxidant, sanitas and analogue.Will appreciate that, can be placed on multiple other types of materials or following formation multilayered structure according to the carrageenan barrier substance matter that contains of the present invention.
According to carrageenan capsule of the present invention can be hard or soft gel capsule and also can be used to discharge the activeconstituents of finished product dosage form, for example, is used to ingest or the medical compounds of topical application.This capsule also is used in the process of the critical stage of producing the finished product and transmits composition.Can use the embodiment of the soft gel capsule of making according to carrageenan product of the present invention can be at U.S. Patent number 6,214,376 and international publishing WO01/03677A1 find, the both lists reference at this.Use when carrageenan product of the present invention is used for the hard gel capsule, the quality that contains the carrageenan capsule wall can be by becoming component selections control, as be good in this respect the people recognized.Transmit the gel beads of composition in process of production, for example immobilized enzyme is used for non-water enzymic catalytic reaction, at U.S. Patent number 6,268, describes in 191 and 5,662,840, and the both lists reference at this.
The carrageenan of producing according to the present invention can be used for multiple production process to form release system, for example above-mentioned carrageenan capsule and the gel beads of containing.This release system is to make, as with the front has been produced, flexible contains the carrageenan bar and ties, contain the coating (two nozzle method) of carrageenan uniformly or contain the carrageenan system in liquid component outside curtain coating to begin to form film/wall then as spouting of liquid.Being good at many other that people in this respect knows is used for capsule/film/barrier substance formation method and comprises within the scope of the invention.
Can be used for fragrance in conjunction with tinting material, flavouring agent and volatile compound according to hamper of the present invention discharges, shelters or neutralizes.Generally include this additional material to modify the aggregate performance of the dosage form of giving the user.The ratio of additional substances and carrageenan product of the present invention also can be used to control/structural integrity, characteristic and the function of film, barrier substance, capsule, pearl or capsule sheet that modification is finished.For example, can obtain different decomposition rates, then allow regularly to discharge heterogeneity.The embodiment that can be used for the additional substances of modification carrageenan structure is: starch (natural, modification and/or control minimizing molecular weight, crystallite and analogue), polyol, hydrocolloid, protein (natural, polypeptide, amino acid, enzyme and its combination), the fiber disposition material of multiple source, size and crystallite, sugar (list and poly) and analogue.
The following examples are illustrated the present invention and are not limited similar.In specification sheets and claims, unless stated otherwise, all parts and per-cent are according to weight, all temperature be with degree centigrade, all pressure are with mmhg.
Embodiment
Comparing embodiment 1-3: the influence that water content is extruded raw material
Material: the main raw material that embodiment 1-3 uses is a cottonii marine alga that wet, alkali modification.Material is made the food grade standard, comprising: (1) removes plastic tape (2) bleaching marine alga to remove color from marine alga before processing.Obtain two groups of raw materials that moisture content is different, one group of moisture about 85% and about 77% humidity of another group moisture.In addition, moisture content about 27% washed, minces with exsiccant cottonii and also use.According to processing of the present invention with about 86%, about 79% and the raw material of about 74% moisture content carry out, obtain by these three kinds of cottonii raw materials of fusion.Use small-sized ribbon blender (to estimate about 8-10ft
3Capacity) these three kinds of cottonii raw materials and required extra water are mixed.Material mixing 10-15 minute with balance.
Extrusion system: the extrusion system of use is as follows:
Feeder/feeding rate-AccuRate board apparatus is from AccuRate, Whitewater, and the Wisconsin is commercial to be bought, and is calibrated to the material that uses 77% moisture, 54 kilograms/hour of speed;
Single-screw extrusion machine-Wenger X-20 is at 500rpm, temperature out 95-100 ℃ of operation;
Twin-screw extruder-Wenger TX-52 is at 454rpm, temperature out 120-180 ℃ of operation;
The single 4mm diametric hole of twin screw outlet mouth template;
Twin screw top hole pressure manual adjustment mouth mould throttling valve is to keep maximum top hole pressure and bucket compactedness (residence time).
Embodiment 1
Extrude the high moisture content raw material
Handle: extrusion machine conditional stability and TX-52 exit condition are easy to keep.
Moisture content: the final measurement usefulness moisture equilibrium of raw material humidity percentage composition such as Denver instrument IR200 or Mettler LJ16 or air oven method are determined.Typical air oven method is at about 60 ℃ of dried overnight samples and uses based on the simple computation of the difference of dried wet stock weight and determine percent water content.These two kinds of methods have been observed a little difference.As shown in the table, because difference and standard deviation are very little, all follow-up discussion will be based on average data.
Moisture content of raw material %
| | IR200 | 60 ℃ of baking ovens | On average | Standard deviation | |
| A | 86.11 | 86.42 | 86.27 | 0.22 |
Brabender hydration line chart: the raw water sum velocity of moisture content about 86% determines with the special testing method that United States Patent (USP) 5,502,179 is described that on Brabender viscograph E for example, the 4th is listed as in the patent, and 17-23 is capable described.The result as shown in Figure 1.Arbitrary hydration peak temperature as the raw material function does not have noticeable change.The raw material of moisture content about 86% is observed the peak viscosity (Fig. 1) of 148-160BU.
Brabender hydration peak
Maximum gained viscosity unit on the BU=Brabender instrument
Embodiment 2
The low moisture content raw material
Handle: test the result who relatively uses the raw material of moisture content to obtain less than foundation the present invention with moisture content.These three kinds of Cottonii stock yards are not observed significant processing difference.All three kinds of product extrusion machine conditional stabilitys and TX-52 exit condition are easy to keep.Produce drying products than the low moisture raw material in outlet.Improve in the twin screw temperature out than the low moisture raw material.
Moisture content: moisture % finally measures and shows between IR200 and air oven method that a little difference is arranged in the raw material.Because difference and standard deviation are very little, all follow-up discussion will be based on average data.
Moisture content of raw material %
| | IR200 | 60 ℃ of baking ovens | On average | Standard deviation | |
| B | 78.85 | 79.60 | 79.23 | 0.53 | |
| C | 73.58 | 74.47 | 74.03 | 0.63 |
Brabender hydration line chart: moisture content about 79% and 74% raw produce hydration rate determine with the special testing method that United States Patent (USP) 5,502,179 is described on Rrahender viscograph E, for example, the 4th row in the patent, 17-23 is capable described.Obviously the hydration performance does not have noticeable change.Arbitrary hydration peak temperature as the raw material function does not have considerable change.Yet peak viscosity descends along with raw material moisture decline and shows because the high-shear effect viscosity of process of the present invention reduces.It is 148-160BU that the raw material of moisture content about 86% is observed peak viscosity, and moisture content about 79% and 74% raw material are observed peak viscosity and be respectively 102-104BU and 52-68BU (Fig. 1).The minimizing of functionality shows that process configuration optimum handling moisture content of raw material of the present invention is greater than 80%.
Brabender hydration peak
Maximum gained viscosity unit on the BU=Brabender instrument
Embodiment 3
Moisture content of raw material is to the effect of color
The powder color is measured being ground on 99.5% the material by 100 orders (150 microns) with Macbeth ColorEye 3000 colourimeters.The powder color is reported with L* unit; L* is low more, and powder is dark more.Usually product index L* is greater than 74-75.Product powder color observation as the moisture content of raw material function arrives noticeable change.Moisture content of raw material is reduced at about 80% o'clock from about 85% and observes the obvious deepening of product colour.As shown in the table, it is 79.5 that moisture content of raw material about 86% makes product L* (powder color).The powder color is that the human consumer accepts the carrageenan product and is used for the important aesthetic character of food; The light colour product is preferable.1
1/2The variation of-2L* unit is enough to be noticed by deconditioned eyes.The variation that the discernable L* of knowledgeable final user is littler.
Embodiment 4
The Chondrus raw material that soaked alkali also is used to test the effect of high-shear extrusion system to different marine algas.This Chondrus raw material is washed marine alga by following method manufacturing (1) in fresh water; (2) mince marine alga to the needs size; (3) dry in 60 ℃ of air ovens; (4) regulate moisture content to about 30% by spraying 0.2N NaOH solution.Chondrus moisture content of raw material water is adjusted to about 29.9% (measurement).The moisture content that (during shipment) measures before regulating moisture is for being 22%.Material can't evenly add AccuRate too greatly, therefore uses a Fitz pulverizer to mince material to about 1/4-1/2 " sheet.(estimate about 8-10ft with small-sized ribbon blender
3Capacity) preparation raw material; Material mixing 10-15 minute with balance.About 29.94% (the actual humidity %) of Chondrus material moisture content.Actual humidity % measures water balance and is located at 150 ℃ with Denver instrument IR200.
Extrusion system: the extrusion system of use is as follows:
Feeder/feed rate-AccuRate board apparatus is from AccuRate, Whitewater, and the Wisconsin is commercial to be bought, and is calibrated to 54 kilograms/hour that use 77% moisture material;
Single-screw extrusion machine-Wenger X-20 is at 500rpm, temperature out 95-100 ℃ of operation;
Twin-screw extruder-Wenger TX-52 is at 454rpm, temperature out 120-180 ℃ of operation;
Twin screw outlet mouth template-single 4mm diametric hole;
Twin screw top hole pressure manual adjustment mouth mould throttling valve is to keep maximum top hole pressure and bucket compactedness (residence time).
Handle: in the carrageenan leaching process, the X-20 screw element is the maximum shear configuration, therefore, can not transmit the horizontal Chondrus material of high solid and pass through extrusion machine.Form very fine and close, solid material plug at the X-20 proximal end, and stop up all and flow.This stopper explanation is from extrusion machine heat-coking that the mechanical energy input causes and the autocatalysis acid hydrolysis of decomposing from carrageenan.Walk around single-screw extrusion machine, raw material flows directly into TX-52.Although twin-screw extruder can transmit raw material, the product that machine comes out by coking (temperature out is up to 180 ℃).Screw speed and barrel temperature all reduce to 170RPM and 100-130 ℃ respectively, and a last bucket has water coolant so that coking minimizes.Yet, infer the still too violent degraded that consequently can not prevent carrageenan fully of extrusion condition.
Brabender hydration line chart: the carrageenan that Brabender hydration line chart confirmation Chondrus material contains is being extruded middle destruction.Produce typical B rabender viscosity peak although the Chondrus raw material shows, the Chondrus material that is extruded completely loses viscosity.Further do not test.
These presentation of results process of the present invention is the feed that high shear process is only applicable to high moisture content.The pattern of process shows that the high-moisture level helps (1) lower material density; (2) carrageenan is partially hydrated in single-screw extrusion machine; (3) increase in screw rod-feed contact interface lubrication; (4) heat absorption increases; (5) temperature condition that the carrageenan degraded is minimized.As if need all of these factors taken together so that the operational process success.
Prove as embodiment 1-3, the Cottonii product from humidity raw material between 75-85% and under constant processing conditions, extrude generally very similar.Yet, by two important functionality differences.At first, product viscosity takes place below 80% obviously to reduce along with moisture content of raw material drops to.Usually be not accepted the SRC that is used for as thickening material than low production viscosity.Secondly, product powder color is along with moisture content of raw material drops to significantly deepening below 80%.For maintaining the SRC that uses in the almost colourless or white food in color, darker powder color is not accepted.
In addition, the high solid raw material, for example the Chondrus of 30% moisture generally is not suitable for process of the present invention.The high-shear extrusion condition does not have under the proper lubrication effect situation of water too violent in raw material.In the low moisture raw material, the carrageenan in the marine alga is degraded fully in this process.
Embodiment 5
Extrude the Eucheuma cottonii raw material of alkaline purification with list and twin-screw extruder:
Parent material:
1. handle Eucheuma cottonii material modification and draining by standard P ES.
2. the Eucheuma cottonii raw material 30 minutes and the draining of washing modification in cold water.Repeat.
3. at 0.17%Ca (Ocl)
2Middle bleaching 30 minutes and draining.
4. in cold water, washed 30 minutes and draining.
The moisture content of parent material is 86-87%.KCl content is 0.5-3.0%.Cottonii minces into 1/2 before bleaching " sheet.
Pre-paste producing: the cottonii that minces is added in the Wenger X-85 single-screw extrusion machine with the metering of Accu-rate feeder.With steam through 8 single extruder temperatures of independent cycle control so that the material outlet temperature reaches 95 ℃.The cottonii that handled heats in single screw rod and mixes and stick with paste smooth to destroy the marine alga structure up to marine alga.Subsequently marine alga by make the sealing transfer system 1.5 " diameter tube delivers to twin-screw extruder.
Extrude: after pre-paste producing, the commentaries on classics of eight barrels of Wenger TX-57 corotations, intersection, twin-screw extruder are gone in the cottonii materials flow of handling.It is proprietary that the high-shear screw configuration that is used for this sample belongs to Wenger.Temperature control is divided into 5 districts.Last 4 bucket district steam heating.
Extrude outlet: a valve control back pressure before the 1 aperture mould of twin screw outlet 4mm goes out machine with the finished cottonii material steam explosion of guaranteeing to extrude.Similar crumb when the cottonii that extrudes goes out extrusion machine.
Sample: when leaving extrusion machine, sample transfers to collection box with pneumatic conveyor.Product roll and cooling stick together preventing.Dry in three grades of belt dryers of Wenger series VII then.
Process is provided with and reading:
147 kilograms/hour of Accu-rate feeder input speeds
95 ℃ of single screw rod temperature outs
Screw speed 600rpm
1 minute residence time
Motor load 22% full load
Twin screw barrel temperature district (℃) 46,125,129,140,140
116 ℃ of temperature outs
Screw speed 605rpm
147 kilograms/hour of velocity of discharge
1.5 minutes residence time
Motor load 6% full load
Test: dry sample be ground at least 95% by 100 orders be used for the test.Table 1 is listed the general aspects test that the cottonii that extrudes compares with parent material, is presented at the carrageenan degraded not to take place in extruding.Table 2 shows the deliquescent raising of the relative parent material of 2% ottonii that extrudes in the Brabender line chart in water.The deliquescent raising of the relative parent material of cottonii that table 3 explanation is extruded in meat salt solution elixir Brabender line chart.
Table 1
The general aspects test
Test
Finished PES cottonii parent material
The PES that extrudes
cottonii
Moisture content (%) 86-87 85.96
Viscosity (cP) 85 91
pH 9.00-9.60 9.03
KCl(％) 0.5-3.0 2.80
Screening (by 100 purpose %) 90-100〉95
Table 2
The test-2% of Brabender analysis-solvability is in water
The initial material of finished PES cottonii
The PES cottonii that extrudes
Material
Beginning swelling: C 68 48
BU 2 3
The first secondary peak C does not have peak 52
BU does not have peak 89
The second secondary peak C 77 65
BU 12 35
Last 82 ℃ keep BU 8 29
Table 3
Brabender analysis-solvability test-meat salt solution elixir
Finished PES cottonii parent material
The PES cottonii that extrudes
Beginning swelling: C 71 66
BU 19 2
The first secondary peak C does not have peak 68
BU does not have peak 19
Second secondary peak (71 ℃) BU 35 17
Last 71 ℃ keep BU 35 15
Embodiment 6
Extrude the Eucheuma cottonii raw material of alkaline purification with twin-screw extruder
Parent material: finished cottonii parent material by Eucheuma cottonii marine alga through standard P ES handle, mince cottonii to 1/2 inch sheet of PES, drying is ground to 100 mesh sieves then and prepares.
Extrude: chippy finished cottonii adds 12 barrels of Werner-PfleidererZSK-30 corotations commentaries on classics, intersection, twin-screw extruder from hopper.Total length is 37.Water and finished cottonii are added to the mixture that feed zone produces 80% moisture.It is proprietary that the high-shear screw configuration that is used for this sample belongs to Werner-Pfleiderer.In bucket 4 to 10, control heating and cooling by electrically heated and water cooling.
Extrude outlet: there is not a mouthful mould to be placed in the screw rod outlet.The discharging outward appearance is elasticity, grinds, small pieces uniformly.
Sample: sample is spread cooling out in dish, then dried overnight in 60 ℃ of baking ovens.
Processing is provided with and reading:
9 kilograms/hour of feeder feed rates
The twin screw barrel temperature (℃) 25,82,90,90,89,89,90,90,90,90
90 ℃ of temperature outs
Screw speed 500rpm
9 kilograms/hour of velocity of discharge
Test: dry sample be ground to 91% by 100 orders be used for the test.Table 4 is listed the general aspects test that the finished cottonii that extrudes compares with parent material, is presented at the carrageenan degraded not to take place in extruding.The table 5 explanation 2% deliquescent raising of the relative parent material of finished cottonii of in water, extruding in the Brabender line chart.
Table 4
The general aspects test
Test
Finished PES cottonii parent material.
Extrude PES cottonii
Moisture content (%) 6 is not measured
Viscosity (cP) 160 55
101 gels (gms disruptive force) 491 435
KCl(％) 1.5 1.4
Screening (by 100 purpose %) 90-100 91
Table 5
The test-2% of Brabender analysis-solvability is in water
Finished PES cottonii parent material
Extrude PES cottonii
Beginning swelling: C 59 56
BU 12 12
The first secondary peak C does not have peak 59
BU does not have peak 24
The second secondary peak C 78 75
At 82 ℃ of BU 59 27
Embodiment 7
Extrude the Eucheuma spinosumi raw material of alkaline purification with list and twin-screw extruder:
Parent material: PES spinosum parent material prepares through following process by Eucheuma spinosum marine alga:
1. marine alga was soaked in 25%NaCl 1 hour and draining.
2. modification 2 hours and draining in 7.9%NaCl, 2.86%NaOH.
3. in 9% NaCl, washed 30 minutes and draining.
4. bleaching 30 minutes and draining in 0.25%NaOCl.
5. in 6% NaCl, washed 30 minutes and draining.
6. in cold water, wash and draining.
The moisture content of PES spinosum parent material is 78-82%.NaCl content is 11-15%.Spinosum minces into 1/2 before bleaching " sheet.
Pre-paste producing: the PES spinosum that minces is added in the Wenger X-85 single-screw extrusion machine with the metering of Accu-rate feeder.With steam through 8 independent head circulations with vapo(u)r blasting controls single extruder temperature so that the material outlet temperature reaches 100 ℃.PES spinosum heats in single screw rod and mixes and stick with paste smooth to destroy the marine alga structure and to become to stick with paste up to marine alga.Subsequently material by make the sealing transfer system 1.5 " diameter tube delivers to twin-screw extruder.
Extrude: along with PES spinosum comes out from single screw rod, it is added into the commentaries on classics of one eight barrels Wenger TX-57 corotations, intersection, twin-screw extruder.It is proprietary that the high-shear screw configuration that is used for this sample belongs to Wenger.Temperature control is divided into 5 districts.Last 4 bucket district steam heating.
Extrude outlet: a valve control back pressure before twin screw goes out the 1 aperture mould of 4mm goes out machine with the PES spinosum material steam explosion of guaranteeing to extrude.Similar crumb when the spinosum that extrudes goes out extrusion machine.
Sample: when leaving extrusion machine, sample transfers to collection box with pneumatic conveyor.Product roll and cooling stick together preventing.Dry in three grades of formula moisture eliminators of Wenger series VII then.
Process is provided with and reading:
144 kilograms/hour of Accu-rate feeder feed rates
100 ℃ of single screw rod temperature outs
Screw speed 600rpm
Motor load 17% full load
Twin screw barrel temperature district (℃) 48,124,128,138,136
107 ℃ of temperature outs
Screw speed 600rpm
144 kilograms/hour of velocity of discharge
Motor load 5% full load
Test: dry sample be ground at least 95% by 100 orders be used for the test.Table 6 is listed the general aspects test that the PESspinosum that extrudes compares with parent material, is presented at the carrageenan degraded not to take place in extruding.The deliquescent height of the table 7 explanation relative parent material of 2% PESspinosum that in water, extrudes in the Brabender line chart.
Table 6
The general aspects test
Test
Finished PES spinosum parent material
The PES spinosum that extrudes
Moisture content (%) 78-82 81
Viscosity (cP) 30 38
pH 8.30-8.90 8.73
NaCl(％) 11-15 11.72
Screening (by 100 purpose %) 90-100〉95
Table 7
The test-2% of Brabender analysis-solvability is in water
Finished PES spinosum parent material
The PES that extrudes
spinosum
25 ℃ of maintenances
Beginning: BU does not have peak 184
Finish BU and do not have peak 177
Add thermal spike: C 65 no peaks
BU 26 no peaks
Last 82 ℃ keep BU 26 26
Embodiment 8
Extrude Eucheuma spinosumi raw material that washed, no alkaline purification with list and twin-screw extruder:
Parent material: the spinosum parent material of washing prepares through following mode by Eucheuma spinosum marine alga:
1. in cold water, soaked 30 minutes and draining.
2. in cold 1.5%NaCl, soak and draining.
3. in the Wilmes squeezing machine, extrude superfluous water.
The moisture content of the spinosum parent material of washing is 85-86%.NaCl content is 8%.The spinosum that washed minces into 1/2 before bleaching " sheet.
Pre-paste producing: the spinosum that minces, washed is added in the Wenger X-20 single-screw extrusion machine with Accu-rate feeder half amount.With steam through 8 single extruder temperatures of independent cycle control so that the material outlet temperature reaches 95 ℃.The spinosum that washed heats in single screw rod and mixes to destroy marine alga structure and part to become to stick with paste.The spinosum that washed that preformation is stuck with paste is more smooth, but some remaining marine alga small pieces are arranged.Material is by 1.5 subsequently " the diameter instlated tubular delivers to twin-screw extruder.
Extrude: along with the spinosum that washed sticks with paste to come out from single screw rod, it is added into eight barrels of WengerTX-52 corotations commentaries on classics, intersection, twin-screw extruder.It is proprietary that the high-shear screw configuration that is used for this sample belongs to Wenger.Heating of extruder barrel 4 to 6 usefulness circulating hot oils and steam inject bucket 3 and 4.
Extrude outlet: a valve control back pressure before the 3 aperture moulds of twin-screw extruder outlet 4mm goes out machine with the spinosum material steam explosion of guaranteeing to extrude, washed.The spinosum that extrudes, washed is wet granular and sticky mixture when coming out.
Sample: during the spinosum material extruded in collection, washed carefully to guarantee that sample does not stick together.Sample pushes away in dish before 60 ℃ of oven dryings spend the night and cools off.
Process is provided with and reading:
33 kilograms/hour of Accu-rate feeder feed rates
96 ℃ of single screw rod temperature outs
Screw speed 100rpm
Motor load 11% full load
The twin screw barrel temperature (℃) 73,73,95,119,119,120,120,120
135 ℃ of temperature outs
Screw speed 472rpm
33 kilograms/hour of velocity of discharge
Motor load 9% full load
Test: dry sample be ground to 91% by 100 orders be used for the test.Table 8 is listed the general aspects test that the spinosum that extrudes, washed compares with parent material, is presented at the carrageenan degraded not to take place in extruding.Table 9 is presented at the deliquescent raising of the relative parent material of spinosum that extrude, that washed in 65 ℃ of Sorbitol Powders/glycerine toothpaste elixir Brabender line chart.The relative parent material solvability of table 10 explanation spinosum that extrude, that washed in 71 ℃ of glycerine toothpaste elixir Brabender line charts improves.
Table 8
The general aspects test
Test
The spinosum parent material of washing
The spinosum that washed that extrudes
Moisture content (%) 85-86 85.9
Viscosity (cP) 50-60 41
pH 7.5-8.5 7.8
NaCl(％) 6-10 6.2
Screening (by 100 order %) 90-100 91
Table 9
Brabender analysis-solvability test-65% Sorbitol Powder/glycerine toothpaste elixir
The spinosum parent material of washing
The spinosum that washed that extrudes
Beginning swelling: C 62 44
BU 30 45
Last 65 ℃ keep BU 44 122
Cooling: C 25 25
BU 540 850
Brabender analysis-solvability test-71% glycerine toothpaste elixir
The spinosum parent material of washing
The spinosum that washed that extrudes
Beginning swelling: C 66 37
BU 23 40
Last 71 ℃ keep BU 81 89
Cooling: C 26 37
BU 695 651
Embodiment 9
Extrude the Eucheuma spinosumi raw material of alkaline purification with twin-screw extruder:
Parent material: PES spinosum parent material prepares through following process by Eucheuma spinosum marine alga:
1.45 ℃ modification 6 hours and draining in 1.0M NaOH, 3.1M NaCl.
2. twice cold, 5%NaCI rinsing in 30 minutes after the modification.
3. in the rinsing for the first time and pH.
4. this sample soaks 30 minutes cold water in addition in testing before extruding.
The moisture content of PES spinosum parent material is 83%.PES spinosum minces into 1/2 " sheet.
Extrude: the PES spinosum that minces is added to the commentaries on classics of one nine barrels Clextral BC-45 corotations, intersection, twin-screw extruder from the metering of constant volume glassware.It is proprietary that the high-shear screw configuration that is used for this sample belongs to Clextral.Last 8 barrels of heating and cooling are by ruhmkorff coil and cooling water control.
Extrude outlet: temperature out is measured before the 3 hole cooling vent templates of 3mm.The PES spinosum that extrudes is three strands of material opaque, sticking, that can be coated with out when coming out.
Sample: sample transmits about 15 seconds on tape with cooling before collecting in dish.Even tend to connect together during the cooling of sticking material, therefore it must be broken into small pieces by hand before 60 ℃ of oven dryings spend the night.
Process is provided with and reading:
54 kilograms/hour of Accu-rate feeder feed rates
The twin screw barrel temperature (℃) 25,128,189,175,140,142,124,99,79
81 ℃ of temperature outs
Screw speed 550rpm
54 kilograms/hour of velocity of discharge
2.0 minutes residence time
Motor load 11amps
Test: dry sample be ground to 94% by 100 orders be used for the test.Table 11 is listed the general aspects test that the PESspinosum that extrudes compares with parent material, is presented at the carrageenan degraded not to take place in extruding.Table 12 explanation improves in the relative parent material solvability of the 2% PES spinosum that extrudes in the Brabender line chart in water.
Table 11
The general aspects test
Test
PES spinosum parent material
The PES spinosum that extrudes
Moisture content (%) 83 82.5
Viscosity (cP) 28 32
pH 9.90 9.10
NaCl (%) does not measure 7.47
Screening (by 100 purpose %) 90-100 97
Table 12
The test-2% of Brabender analysis-solvability is in water
PES spinosum parent material
The pressure PES spinosum that extrudes
25 ℃ of maintenances
Beginning: BU 8 35
Finish BU 9 122
First peak: C 30 30
BU 9 65
BU 27 27
Last 82 ℃ keep BU 59 13
Embodiment 10 and 11
Embodiment 10 and 11 has illustrated that carrageenan product of the present invention can be used as the formulation of toothpaste composition.Particularly, formulation of tooth-paste of the present invention is assessed as the effect of carrageenan tackiness agent in the toothpaste according to the carrageenan product.The effect of carrageenan tackiness agent is determined by measuring formulation of tooth-paste intensity, stability and quality in formulation of tooth-paste.The method of traditional measurement intensity, stability and quality is to use Cuba's rating system, and wherein toothpaste line material is extruded on Cuba's frame.The ability that chain keeps hanging between the beam that big or small one-level one-level increases determines toothpaste 1 to 12 grade.Measuring needs 9 time-of-weeks usually.More definite, 1 day, 1 week, 3 weeks, 6 weeks and 9 week the back measure for about 25 ℃ and 50 ℃ at storage temperature, to determine toothpaste intensity, stability, quality and " thermal shocking " degree.Strength Changes when thermal shocking is defined as toothpaste and is stored in 50 ℃ (increase or reduce).Change and think unfavorable above 3 Cuba's grades.The shortcoming of Cuba's test is that need 9 time-of-weeks must be prepared and measure to toothpaste to determine special carrageenan properties of samples.
Use Brabender viscograph test-based examination carrageenan solvability according to formulation of tooth-paste of the present invention, wherein toothpaste " elixir " is used for detecting carrageenan solvability when having other toothpaste component.Toothpaste " elixir " prescription contains the composition of the same ratio of general formulation of tooth-paste, except " elixir " lacks weighting agent, whipping agent and sesame oil.The Brabender temperature profile concentrates on carrageenan solvability condition usually.Brabender toothpaste " elixir " test is determined and can shows in formulation of tooth-paste by fabulous prediction carrageenan product of the present invention.The advantage that Brabender test is used in the present invention with respect to traditional Cuba hierarchical system, is that the Brabender test is done function character and determined that required time is from reduced to several hours in 9 weeks.
In the following example, toothpaste " elixir " is analyzed to detect the carrageenan solvability with the Brabender viscograph when having toothpaste component.Toothpaste elixir prescription contains the composition of the same ratio of general toothpaste system, except the elixir prescription does not have weighting agent, foaming agent and sesame oil.The Brabender temperature profile concentrates on carrageenan solvability condition usually to understand the dissolving power of carrageenan under the special applications processing conditions.For use the Brabender toothpaste elixir prescription that develop and temperature profile to be designed for carrageenan product solvability in the toothpaste system that tracking concentrates on the toothpaste processing conditions in this discussion work.
Embodiment 10
The toothpaste elixir
In this example, toothpaste elixir test is all carried out 65 ℃ of process temperatures and 71 ℃.
The intensity of the ready toothpaste of toothpaste Cuba level measurement.The thermal shocking degree is by the variation decision of toothpaste intensity after storing 3 days under 50 ℃.Brabender toothpaste elixir test provides about making the extra information of toothpaste process: when dissolve generations (when and temperature), whether hydration complete, the processing medium viscosity contribute and viscosity to the contribution of the finished product,
Slope and viscosity when table 13 and 14 compares the toothpaste elixir solubility curve temperature that Cuba's change of rank is high in keeping than the actual toothpaste storage.
Spinosum, the spinosum that washed that extrudes and toothpaste that table 13 was relatively washed when 65 ℃ of process temperatures extract mixture.Have positive slope to show not have a kind of be consoluet to all 3 kinds of samples in the time of 65 ℃.The spinosum that crosses of spinosum that relatively washed and washing of extruding shows that both slopes have a little different, but the spinosum that extrudes and washed is significantly increased in Cuba's grade, illustrate that raising is from extruding.Spinosum that relatively extrudes and washed and toothpaste extract mixture and show similar 1 day, 25 ℃ toothpaste Cuba grades, although processing viscosity has a great difference.These two kinds of sample slope differences are very big, are interpreted as the difference of thermal oscillation.The slope of extract is 28.8BU/ minute, and showing increases by 4 Cuba units, from 5 to 9; Yet slope is 2.0BU/ minute the spinosum that extrudes and washed, and showing increases by 2 Cuba units, from 6 to 8.Think acceptablely although increase by 2 Cuba units, increase by 4 Cuba units and then can not accept.
Table 14 is at 71 ℃ of same down relatively 3 kinds of samples of process temperature.The negative slope of spinosum that extrudes and washed and toothpaste extract shows their dissolvings fully under this higher process temperature.Higher Cuba's grade also reflects this point, and these three kinds of samples do not have thermal oscillation.
Brabender elixir test result also provides about the different information of processing viscosity, and Cuba's grade does not have.Although relatively near the toothpaste extract, the processing viscosity of the spinosum that extrudes and washed is much lower, shown in Brabender elixir test result on Cuba unit and high final cooling viscosity for the spinosum that extrudes and washed.In this example, low processing viscosity is advantage in general toothpaste preparation.
Table 13
Toothpaste elixir solvability distributes and toothpaste Cuba grade compares, 65 ℃ of processing down
Begin finish to finish 65 ℃ 1 day 2 days
65 ℃ of 65 ℃ of 25 ℃ of rate of curve Cuba, Cuba,
(BU) (BU) 25 ℃ 50 ℃ of (BU) (BU/ minutes)
Washed 29 44 538 1.0 33
spinosum
Extrude, washed 92 122 837 2.0 68
spinosum
Toothpaste extracts mixture 293 725 1,216 28.8 59
Table 14
Toothpaste elixir solvability distributes and toothpaste Cuba grade compares, 71 ℃ of processing down
Begin finish to finish 71 ℃ 1 day 2 days
71 ℃ of 71 ℃ of 25 ℃ of rate of curve Cuba, Cuba,
(BU) (BU) 25 ℃ 50 ℃ of (BU) (BU/ minutes)
47 71 850* 1.6 12 12
Washed
spinosum
Extrude, washed
101 89 850* -0.8 11 12
spinosum
Toothpaste extracts mixture 850 740 1416-7.3 66
* from curve extrapolation
Embodiment 11
Glycerine/Sorbitol Powder chalk toothpaste
Two kinds of spinosum samples that extrude, that washed (EWS-1 and EWS-2) are tested in cheap glycerine/Sorbitol Powder chalk toothpaste 65 ℃ of processing temperatures.Dry straight and demonstration does not have thermal oscillation.Table 15 is Cuba's grade of two kinds of toothpaste relatively.
Table 15
Toothpaste is to show in the basic toothpaste at chalk
1 day Cuba, 25 ℃ of 2 days Cuba, 50 ℃
EWS-1 6 5
EWS-2 7 6
Result (from embodiment 10 and 11):
(1) using the toothpaste elixir of imitation toothpaste is to obtain the not only information of the finished product stablizer performance, and the method for the important information that shows in about toothpaste processing.
(2) the toothpaste thermal oscillation occurs in and keeps in the comparatively high temps course of processing, and is directly proportional with increase of solubility curve obliquity or positive slope.
(3) observe easily, explain in the variant production performance of two differing temps processed samples and with the solubility data that elixir Brabender line chart provides.
(4) processing viscosity is directly not proportional with final toothpaste intensity.
(5) carrageenan performance in actual toothpaste is predicted in the test of Brabender toothpaste elixir admirably.It can make does function character and determines that required time is from several weeks or several days reducing to several hours.
(6) toothpaste processing elixir Brabenders test helps to determine any toothpaste system's processing temperature restriction and scope.
Analyze(based on embodiment 10 and 11):
The Brabender solubleness line chart in two zones helps to predict the performance of special stroke of cream sample:
(1)
Kept comparatively high temps 15 minutes: it is the strong indication of potential toothpaste thermal oscillation that viscosity when keeping comparatively high temps in the solubility curve and viscosity changed the time (slope).Steeper slopes, thermal oscillation may be big more.Slope is flat more, and the chance of thermal oscillation is few more.
(2) finally be cooled to 25 ℃: the processing elixir finally cools off viscosity and shows the contribution of the potential viscosity of carrageenan sample to toothpaste.Final cooling viscosity is different from processing viscosity.
Claims (36)
1. produce the method for the product that contains half refining carrageenan, may further comprise the steps:
Provide the marine alga material that contains carrageenan that the marine alga solids content is less than 25% weight and
The marine alga material that contains carrageenan that described marine alga solids content is less than 25% weight carries out shear-stress to be handled to provide and contains half refining carrageenan product;
Described shear-stress is enough to destroy the plain structure of seaweed fiber, and described shearing treatment is undertaken by extruding.
2. the method for claim 1 wherein contains carrageenan marine alga material and half refining carrageenan and is characterized as color distinction that the dry powder measurement of at least 99% powder by 100 mesh sieves record less than 4.0L* unit with Macbeth ColorEye 3000 colourimeters and granular size.
3. method as claimed in claim 2, the described carrageenan product that contains is measured with 2% weight solid aqueous solution with the Brabender viscometer, shows the beginning hydration when being lower than 50 ℃.
4. the method for claim 1, the described carrageenan product that contains is measured with 2% weight solid aqueous solution with the Brabender viscometer, shows the beginning hydration when being lower than 50 ℃.
5. as each described method among the claim 1-4, wherein the marine alga material is the aqueous mixture of solids component 5%-20% weight.
6. as each described method among the claim 1-4, wherein the marine alga material is the aqueous mixture of solids component 10%-20% weight.
7. as each described method among the claim 1-4, wherein the marine alga material is the aqueous mixture of solids component 13%-17% weight.
8. as each described method among the claim 1-4, the described carrageenan product that contains is measured with 2% weight solid aqueous solution with the Brabender viscometer, shows the beginning hydration when being lower than 30 ℃.
9. as each described method among the claim 1-4, wherein extrude with twin screw extruder and carry out, speed is 500rpm at least, at least 90 ℃ of temperature.
10. method as claimed in claim 9 is wherein extruded by carrying out for the twin screw extruder charging with single screw extrusion machine.
11. method as claimed in claim 10 is wherein extruded and is contained carrageenan marine alga material and comprise material by rapid released vapour of extruding dies and pressurization.
12. method as claimed in claim 11 wherein contains carrageenan marine alga material and granulates after extruding dies discharges.
13. method as claimed in claim 12, wherein granule surface area is bigger than the granule surface area that contains carrageenan marine alga material that does not discharge rapidly by extruding dies.
14. as each described method among the claim 1-4, the marine alga material that wherein contains carrageenan is used alkaline purification before shear-stress is handled.
15., wherein contain the process preparation of marine alga material by may further comprise the steps of carrageenan as each described method among the claim 1-4:
Wash the marine alga that marine alga was washed with formation with water;
The marine alga of washing with alkaline purification is to form the marine alga of alkaline purification;
With the marine alga of water rinse alkaline purification to form the marine alga of rinsing;
Wash the marine alga of rinsing with the aqueous solution, the described aqueous solution comprises water and salt, and described salt is selected from Repone K, sodium-chlor or their mixture.
16. method as claimed in claim 15, the marine alga of wherein washing is handled at 25-95 ℃ with alkali.
17. method as claimed in claim 16, the marine alga material that wherein contains carrageenan comprises the marine alga and the aqueous solution of alkaline purification, and the described aqueous solution comprises water and sodium-chlor.
18. method as claimed in claim 16, the marine alga material that wherein contains carrageenan comprises the marine alga and the aqueous solution of alkaline purification, and the described aqueous solution comprises water and salt, and described salt is selected from Repone K, sodium-chlor or their mixture.
19., wherein contain carrageenan marine alga material and additive co-processing as each described method among the claim 1-4.
20. method as claimed in claim 19, described additive are selected from fibrinous material, Seaweed Extract, natural gum, biosynthesizing natural gum, protein, synthetic hydrocolloid, starch, dextrin, sugar, tensio-active agent, emulsifying agent and salt.
21. method as claimed in claim 20, described additive is selected from chemically-modified cellulose, treated starch and glucose.
22. method as claimed in claim 19, wherein additive adds before shear-stress is handled.
23. method as claimed in claim 19, wherein additive adds in shear-stress is handled.
24. method as claimed in claim 19, wherein additive is handled the back adding at shear-stress.
25. as each described method among the claim 1-4, wherein marine alga is Eucheuma spinosum, Eucheuma cottonii or their mixture.
26. method as claimed in claim 25, wherein the marine alga material is from Eucheuma cottonii.
27. method as claimed in claim 25, wherein the marine alga material is from Eucheuma spinosum.
28. as each described method among the claim 1-4, wherein half refining carrageenan comprises at least 65% weight carrageenan and the insoluble material of at least 2% weight acid.
29., comprise that further drying contains the carrageenan product as each described method among the claim 1-4.
30. as each described method among the claim 1-4, what further comprise mill-drying contains the carrageenan product.
31., also comprise as each described method among the claim 1-4:
Provide and comprise the solution that contains the carrageenan product;
Make this solution accept condition for validity and handle and be converted into barrier substance.
32. method as claimed in claim 31, described barrier substance are film, pearl or capsule.
33. method as claimed in claim 31 also is included in formation barrier substance and near small part solution deposition and heated the solution that contains the carrageenan product before on the substrate.
34. method as claimed in claim 33, described barrier substance is a capsule, and described carrageenan material comprises κ-carrageenan, and described substrate is the refrigerative rotating cylinder.
35. formulation of tooth-paste comprises tackiness agent, wetting agent, abrasive and water, wherein tackiness agent comprises the half refining carrageenan product that contains that the described method of claim 1 makes.
36. formulation of tooth-paste as claimed in claim 35, wherein formulation of tooth-paste contains the tackiness agent less than 1.5% weight.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US25527900P | 2000-12-13 | 2000-12-13 | |
| US60/255,279 | 2000-12-13 | ||
| US09/798,012 | 2001-03-02 |
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| CN100513427C true CN100513427C (en) | 2009-07-15 |
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| US8663728B2 (en) * | 2009-07-21 | 2014-03-04 | Cp Kelco U.S., Inc. | Protein stabilizer systems comprising carrageenan for weakly acidic flavored milk drinks |
| IN2012DN01100A (en) * | 2009-08-07 | 2015-04-10 | Fmc Corp | |
| CN103788225B (en) * | 2014-01-22 | 2016-04-06 | 石狮市新明食品科技开发有限公司 | The production method of modified form carrageenin |
| CN105995948B (en) * | 2016-05-13 | 2019-12-24 | 东北农业大学 | Agar compound colloid with high low-temperature dissoluble gel strength and preparation method thereof |
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