Background technology
Konjaku is used as suspension agent, emulsifying agent, stablizer, thickening material, weighting agent, quality improver etc. in foodstuffs industry, with the konjaku powder is that main raw material can be produced various konjakus (bionical) low-heat heath food, and this is the foods with high dietary fiber of a class international popular.Konjaku also is applied to pharmaceutical industry except that being mainly used in food.High-purity konjac polysaccharide has characteristics such as not producing heat, strong suction, desirable food fiber, in the interpolation and the release of medicine, helps the control body weight, food fibre, get rid of heavy metal ion, enzyme fixed bed, control blood fat, improve immunizing power, diabetes, aspects such as crystalline material have unique function.
The chitosan chemical name is β-1, and 4-2-amino-2-deoxidation-D-dextran claims chitosan, chitin, chitosan, soluble chitin etc. again, is the derivative that chitin obtains behind the concentrated base deacetylation, and is water insoluble, but be dissolved in the diluted acid.Chitosan is widely used in pharmaceutics (drug release at present, hemodialysis), medical science (medical textile, operating sutures, artificial blood vessel, the health auxiliary material, medical parting material), the daily use chemicals makeup, food (healthcare products, foodstuff additive, fodder additives etc.), metal-chelating and sewage disposal (flocculation agent etc.).Chitin and chitosan (Chinese marine industry standard SC/T3403-2004) are divided into low degree of deacetylation (<75.0%) according to the degree of deacetylation size; middle degree of deacetylation (75.0-89.0%); high degree of deacetylation (90.0-95.0%), superelevation degree of deacetylation (>95.0%).
The method one of the edible konjaku of people is that konjaku is made all kinds of finished products at present, as konjak food (preparation methods of number of patent application 93112615.0 shrimp meat-like konjak products), konjak noodle (number of patent application 02111265.7 konjak noodle and working method thereof), taro vermicelli (number of patent application 98113677.X instant vermicelli made from bean starch containing konjak) etc., another kind method is exactly directly to use Rhizoma amorphophalli powder, make capsule or use the Rhizoma amorphophalli powder bath, fruit juice etc. are drunk (ZL99117437.2 konjak solid beverage, number of patent application 200510010731.5 soak type konjak edible fiber food with primary taste, number of patent application 200810236691.X konjak dietary fiber effervescent tablet and preparation method thereof), but at the above konjaku that is used to make solid beverage, no matter be directly to use konjaku also to be to use konjaku and some edible gum bonded konjakus, dissolving fast can make the beverage quick-gelatinizing of these konjak solid beverage pulvis punching out in hot water, and drinking way not too meets the people's conventional requirement.
Summary of the invention
Problem to be solved by this invention provide a kind of in hot water insoluble or dissolved konjac compositions at a slow speed, said composition has most of good characteristics of konjaku itself, and use range advantage widely.
Technical scheme provided by the invention is: a kind of chitosan packing konjak composition, and be encapsulated in the Rhizoma amorphophalli powder particle surface by chitosan and constitute, wherein the mass ratio of chitosan and konjaku is 0.5: 99.5~5: 95.
Above-mentioned Rhizoma amorphophalli powder is konjaku powder, Rhizoma amorphophalli micropowder, konjaku purifying powder or konjak gum, and the chitosan degree of deacetylation is not less than 75%.
The particle diameter of above-mentioned Rhizoma amorphophalli powder is 75~550 μ m or is lower than 120 μ m.Flotation property when being used for beverage for the guarantee konjaku, the konjaku grain diameter that is proposed to be used in beverage is less than 120 μ m.Need to select in addition the different konjaku of particle diameter (as the time particle diameter can at 75~550 μ m) when being used for other purposes as abrasive particle.
The present invention also provides the method for making of above-mentioned chitosan packing konjak composition: chitosan imbedded liquid is made in chitosan and acid and alcohol; At 15 ℃ to 60 ℃, Rhizoma amorphophalli powder added in the chitosan imbedded liquid stir, after mixture mixes, in reaction system, add the alkali neutralization, the centrifugation solid substance is chitosan packing konjak composition behind the cleaning-drying.
The acid that the chitosan imbedded liquid of above-mentioned preparation uses is formic acid, acetate, lactic acid, phenylformic acid, vinylformic acid, Mono Chloro Acetic Acid, hydrochloric acid, citric acid or tartrate, wherein adding the amount of acid and the amount ratio of chitosan is 1~9: 1, and described ratio be the ratio of glucosamine residue weight in sour chemical magnitude and the chitosan.
More than 30%, described alcohol is ethanol, methyl alcohol or Virahol to pure content in volume percent in the above-mentioned chitosan imbedded liquid.
Above-mentioned konjaku adds time of stirring in the chitosan imbedded solution more than 30 minutes.
Among the present invention and used alkali be sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, yellow soda ash or salt of wormwood, the add-on of alkali is counted 0.6~5 times that the used acid of dissolving chitosan is measured by the ratio of amount of substance, and the temperature in the N-process is at 15 ℃ to 60 ℃.
The present invention not only composition has most of good characteristics of konjaku itself, and insoluble or dissolving at a slow speed in hot water, and use range is extensive.Chitosan packing konjak composition of the present invention is used to prepare the konjak solid beverage raw material or as the additive of makeup etc.
Embodiment
In the accompanying drawings, Fig. 1 is the synoptic diagram of chitosan packing konjac compositions, and the konjaku particle surface is wrapped up by chitosan.
Fig. 2 is the infrared colour spectrogram of Rhizoma amorphophalli glucomannan, and Fig. 3 is the infrared colour spectrogram of chitosan, and both marked differences are at 1600cm
-1Place's chitosan has-NH
2The absorption peak that in-plane bending vibration causes.The infrared colour spectrogram of chitosan packing konjac compositions can be seen 1600cm in Fig. 3
-1Near (1574.02cm
-1) the chitosan characteristic peak, the existence of chitosan packing effect is described.Fig. 4 for the present invention solidify after after filtration, washing, the infrared colour spectrogram of dry konjaku chitosan composite, 1600cm
-1The characteristic peak at place is close to disappearance, can think that this mainly is the konjaku composition of chitosan after dissolved.
The peakology of table 1 Rhizoma amorphophalli glucomannan infrared spectrogram
Chitosan is except that specifying in the embodiment of the invention, and degree of deacetylation is about 90% chitosan.
Embodiment 1
1.5 gram chitosan (degree of deacetylation 90%, infared spectrum are seen accompanying drawing 3) and 2.25cm
-3Glacial acetic acid is dissolved in 150cm
-330% (percent by volume) ethanolic soln, be configured to chitosan solution.Adding 20 gram Rhizoma amorphophalli powders (particle diameter 120-550 μ m, infared spectrum is seen accompanying drawing 2, peakology sees attached list 1), stirred 30 minutes.Add 4.5 gram yellow soda ash and enter in the embedding liquid, 60 ℃ solidified 2 hours.After filtration, washing, the dry konjaku chitosan composite (infared spectrum is seen accompanying drawing 4) that gets.Get in 100 ℃ of hot water of said composition and not dissolve in 10 minutes, minimal amounts of dissolved was arranged in 30 minutes, the aqueous solution becomes sticky.After filtration, washing, the dry konjaku chitosan composite (structural representation is seen accompanying drawing 1) that gets.Get dried konjaku chitosan composite, be dissolved in the even liquid solution of formation in the diluted acid, add and diluted acid equal-volume 95% ethanol, collect and separate out component, can obtain konjaku chitosan composite lysate (infared spectrum is seen accompanying drawing 5) after the drying.
Embodiment 2
1 gram chitosan and 2cm
-3Vinylformic acid is dissolved in 250cm
-330% (percent by volume) methanol solution, be configured to chitosan solution.Add 20 gram Rhizoma amorphophalli powders (75-120 μ m), 60 ℃ were stirred 30 minutes, and adding calcium hydroxide 2.27 grams enter in the embedding liquid, solidify 2 hours.Sampling is checked insoluble in boiling water.After filtration, washing, the dry konjaku chitosan composite that gets.
Embodiment 3
0.5 gram chitosan (degree of deacetylation 75%) and 1 gram tartrate are dissolved in 150cm
-330% (percent by volume) ethanolic soln, be configured to chitosan solution.Add 20 gram Rhizoma amorphophalli powders (120-550 μ m), stirred 30 minutes.Add 3.5 gram yellow soda ash and enter in the embedding liquid, 60 ℃ solidified 2 hours.After filtration, washing, the dry konjaku chitosan composite that gets.Get in 100 ℃ of hot water of said composition and not dissolve in 15 minutes.
Embodiment 4
0.5 gram chitosan and 1 gram phenylformic acid are dissolved in 150cm
-330% (percent by volume) methanol solution, be configured to chitosan solution.Add 20 gram Rhizoma amorphophalli powders (120-550 μ m), stirred 30 minutes.Add 2.0 gram sodium hydroxide and enter in the embedding liquid, 60 ℃ solidified 0.5 hour.After filtration, washing, the dry konjaku chitosan composite that gets.Get in 100 ℃ of hot water of this said composition and not dissolve in 15 minutes.
Embodiment 5
Chitosan 1 gram and Mono Chloro Acetic Acid 1 gram are dissolved in 150cm
-3In 30% (percent by volume) isopropanol water solution, be configured to chitosan solution.Add 20 gram Rhizoma amorphophalli micropowders (75-120 μ m), stirred 30 minutes.Add 0.9 gram lithium hydroxide and enter in the embedding liquid, solidified 1 hour.About sampling 0.5 gram, add 200cm
-3In the boiling water, do not dissolve.Mixed solution washs through centrifugation, 60 ℃ of dry konjaku chitosan composites that get.
Embodiment 6
1.5 gram chitosan and 3.0 gram lactic acid are dissolved in 150cm
-330% (percent by volume) ethanolic soln, be configured to chitosan solution.Add 20 gram Rhizoma amorphophalli powders (75-120 μ m), stirred 30 minutes.Add 3.25 gram potassium hydroxide and enter in the embedding liquid, 60 ℃ solidified 0.2 hour.After filtration, washing, the dry konjaku chitosan composite that gets.Get in 100 ℃ of hot water of said composition and not dissolve in 15 minutes.
Embodiment 7
1.0 gram chitosan (degree of deacetylation 89%) and 2.0cm
-3Glacial acetic acid is dissolved in 150cm
-330% (percent by volume) ethanolic soln, be configured to chitosan solution.Add 10 gram Rhizoma amorphophalli powders (75-120 μ m), stirred 5 minutes.Add 80cm
-35% (weight ratio) wet chemical enters in the embedding liquid, solidifies 3 minutes.Get in 100 ℃ of hot water of said composition sample and not dissolve in 15 minutes.After filtration, washing, the dry konjaku chitosan composite that gets.
Embodiment 8
1.0 gram chitosan and 2.0cm
-3Formic acid (purity 88%, volume percent) is dissolved in 150cm
-330% (percent by volume) ethanolic soln, be configured to chitosan solution.Add 10 gram Rhizoma amorphophalli powders (75-120 μ m), stirred 30 minutes.Add 80cm
-35% (weight ratio) aqueous sodium carbonate enters in the embedding liquid, solidifies 65 minutes.Get in 100 ℃ of hot water of said composition sample and not dissolve in 15 minutes.After filtration, washing, the dry konjaku chitosan composite that gets.
Embodiment 9
0.1 gram chitosan (degree of deacetylation 95%) and 0.1 gram Mono Chloro Acetic Acid are dissolved in 10cm
-3In the water, stirring and dissolving.In this system, add 20cm
-35% (weight ratio) aqueous sodium carbonate, stirring at room 1 hour adds 50cm again
-35% (weight ratio) aqueous sodium carbonate stirred under 60 ℃ of temperature 70 minutes, did not dissolve in 10 minutes in the 100 ℃ of hot water of taking a sample, and liquid was sticking slightly in 15 minutes, and particle is clearly demarcated, and still comparatively I am clear for solid and liquid surface.
Embodiment 10
0.5 the gram chitosan dissolves in 100cm
-3In 1% (mass percent) hydrochloric acid soln, add 50cm
-395% (volume percent) aqueous ethanolic solution, the back that stirs add 5 gram Rhizoma amorphophalli micropowders (75-120 μ m), add 80cm again
-35% (weight ratio) aqueous sodium carbonate stirred 50 minutes under 60 ℃ of temperature.Get in 100 ℃ of hot water of said composition sample and not dissolve in 15 minutes, place the back particle and can float.After filtration, washing, the dry konjaku chitosan composite that gets.
Embodiment 11
0.5 gram chitosan and 1 gram citric acid are dissolved in 150cm
-330% (percent by volume) ethanolic soln, be configured to chitosan solution.Add 10 gram Rhizoma amorphophalli powders (75-120 μ m), stirred 15 minutes.Add 2.4 gram calcium hydroxides and enter in the embedding liquid, 60 ℃ solidified 2 hours.After filtration, washing, the dry konjaku chitosan composite that gets.Get in 100 ℃ of hot water of said composition and not dissolve in 15 minutes.
Embodiment 12
Under room temperature (20-30 ℃) condition, with 100 gram chitosans (degree of deacetylation 75%), 200cm
-3Glacial acetic acid, 4000cm
-360% (volume percent) aqueous ethanolic solution mixed dissolution is even, leaves standstill to filter standby in 12 hours.In this chitosan solution, add 6670cm
-360% (volume percent) aqueous ethanolic solution and 2000 gram konjaku powders (particle diameter 120~-550 μ m) stirred 1 hour.Add the aqueous solution of 224 gram yellow soda ash preparations, stirred 1 hour.Product is through centrifugation, and washing is dried, and obtains finished product konjaku chitosan composite.Finished product konjaku chitosan composite brews down at 100 ℃ of boiling water, and internal volume did not change in 30 minutes.24 hours internal volumes do not change in the cold water.
Embodiment 13
3 gram konjaku chitosan composite finished products (75-120 μ m) and the spray-dired bean milk powder of 30 grams mix, and add proper amount of sugar or sweeting agent, are mixed with new bean milk powder.This bean milk powder 250cm
-3Boiling water brews, and has good suspension property, and no foreign body sensation in drinking has certain satiety after the drink.
Embodiment 14
3 gram konjaku chitosan composite (75-120 μ m) finished products and 30 gram whole milk powders mix, and add proper amount of sugar or sweeting agent, are mixed with the new milk powder that brews.This milk powder 250cm
-3Boiling water brews, and has the good suspension property energy, can produce certain satiety after the drink.
Embodiment 15
Prescription: konjaku chitosan composite (75-120 μ m) 30 grams, citric acid 16 grams, sodium bicarbonate 15 grams, lactose 2 grams, aspartame 1.5 grams, orange flavor 1 gram, polyvinylpyrrolidone (PVP-K30) 4 grams, polyoxyethylene glycol (PEG6000) 1 gram, Magnesium Stearate 0.5 gram.The effervescent tablet that above component compatibility is pressed into can accomplish that quick disintegration disperses better can drink fast, also can gelatinization and place for some time.
Embodiment 16
The konjaku chitosan composite is applied to clean facial scrub, prescription (weight percent): glyceryl monostearate 12.00, mineral oil 25.00, spermaceti 5.00, stearic acid 2.00, propylben 1.10, water 48.75, glycerine 5.00, trolamine 1.00, konjaku chitosan composite (particle diameter 120~-550 μ m) 1.00, Tegosept M 0.15.This cleaning facial scrub has outside certain skin care, the skin moisten effect, also has the function of cleaning skin.The konjaku chitosan composite does not have corner angle as abrasive particle, and good toughness is not hindered skin but had good frosted effect.