CN105767158A - Fruit freshness-keeping fruit wax and preparation method thereof - Google Patents

Fruit freshness-keeping fruit wax and preparation method thereof Download PDF

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Publication number
CN105767158A
CN105767158A CN201610242780.XA CN201610242780A CN105767158A CN 105767158 A CN105767158 A CN 105767158A CN 201610242780 A CN201610242780 A CN 201610242780A CN 105767158 A CN105767158 A CN 105767158A
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deionized water
fruit
morpholine
wax
light
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CN105767158B (en
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樊惠昌
黄益芸
徐钱海
朱显庆
王天浩
张文兵
凌军
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SHANGHAI HUICHANG CHEMICAL FACTORY
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SHANGHAI HUICHANG CHEMICAL FACTORY
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23BPRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00Preservation or chemical ripening of fruit or vegetables
    • A23B7/16Coating with a protective layer; Compositions or apparatus therefor
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23VINDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00Food compositions, function of food ingredients or processes for food or foodstuffs

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention provides fruit fresh freshness-keeping fruit wax which is composed of, by mass, 6.0-10.0% of light eleostearic acid ester salt, 8.0-12.0% of silicone acrylic resin and the balance deionized water. The invention further provides a preparation method of the fruit freshness-keeping fruit wax. The fruit freshness-keeping fruit wax has the comprehensive and excellent effects of being shinning bright after wax membrane formation, free of whitening, breathable, water controllable, durable, stable and capable of keeping freshness and quality and is environmentally friendly and sanitary.

Description

A kind of fruit freshness preserving fruit wax and preparation method thereof
Technical field:
The invention belongs to chemical field, particularly relate to a kind of preservative fruit wax, specifically a kind of fruit freshness preserving fruit wax and preparation method thereof.
Background technology:
Fruit wax means the liniment for general fruit surface treatment.Due to social development, fruit has not been pluck that to eat on the spot be main on the spot, but wants large-scale popularization national market even to export, so waxing fresh-keeping has been the merchandized handling historical link that must process in time after modern fruit picking.Waxing can strengthen lustrous surface exterior quality and improve commodity value;Fruit surface pores can also be closed simultaneously and reduce fruit moisture loss reduction weightlessness, reduce or avoid making, because of the factor such as gas and water, bacterium, the fruit caused and go bad to protect human consumption healthy, be conducive to extending the fruit fresh-keeping time.This series products is developed in recent decades human development.World's most countries and area have routinized to generalize and have used fruit wax.In the world, the U.S. and Spain are engaged in fruit wax research country earlier.The nearly more than ten years, China has also played an active part in research and development and has delivered multinomial patent, but due to dog-eat-dog, dragons and fishes jumbled together in current China domestic market, also once several times because waxing problem causes citizen's phychology uneasy, and from the applicable cases of domestic market, for capability and performance, it appears that still to approve U.S.'s product 402, and its price is also the highest, really make us sighing with feeling.How to change and to improve this state, among the numerous scientific research personnel of China and unit are just actively made great efforts.
According to market situation, the fruit wax of current great majority use is still based on fatty acid alkylbenzyldimethylasaltsum saltsum.The U.S. in last century the seventies namely develop this type of fruit wax set up corresponding FDA standard, it should be recognized that, its design has history reason, natural acid is in conjunction with morpholine, one is itself namely have the effect sense of natural material health, two be and have can water-soluble one-tenth wax liquid, after film light attractive in appearance, not easily whiting, Keep the quality and freshness, three be and carried out alkylbenzyldimethylasaltsum saltsum cracking health detection.Generally, the basic main points of good fruit wax are exactly 2 points: one is that health has evidence, and two is mutation of not easily whitening.
Domestic good multi-vendor all uses fatty acid morpholine hydrogen bond salt and fatty acid morpholino amide as preservative fruit wax, but although these fruit wax prices cheaply, but personal safety can be produced hidden danger.
Known to current data, the U.S. 402 is morpholine fatty acid salt is main body, and its FDA detects also as standard object, there is not yet other chemistry general introductions.The present invention is U.S. 402 recent decades effects certainly, but the present invention inquires into and Comparison study through chemistry, it is believed that should turn and improve.
Summary of the invention:
For above-mentioned technical problem of the prior art, the invention provides a kind of fruit freshness preserving fruit wax and preparation method thereof, described this fruit freshness preserving fruit wax and preparation method thereof to solve that fruit wax cost of the prior art is high, fresh-keeping function is weak, to the unsafe technical problem of human body.
nullThe invention provides a kind of morpholine fatty acid ester salt,By light eleostearic acid (bleaching shellac)、Abietic acid resin (PL 101、Meet SGS)、Morpholine、Ethanol、Ammonia and deionized water are prepared from,Described light eleostearic acid (bleaching shellac)、Abietic acid resin (PL 101、Meet SGS)、Morpholine、Ethanol、The weight ratio of ammonia and deionized water is 10.0~18.0:5.0~15.0:1.93~3.95:8.0~10.0:0.5~1.2:60.0~70.0,First the deionized water of ethanol and 3~20% is added in a reactor,It is preheated to 65~73 DEG C,Put into light eleostearic acid and abietic acid resin,Promote temperature to 76~83 DEG C,Add the morpholine of 70~80%,Stirring 10~30min,Pressure,It is warming up to 85~93 DEG C,It is incubated 1~5 hour,It is cooled to 73~83 DEG C,Add residue morpholine、Ammonia and remaining deionized water,Continue stirring 20~35 minutes,Drive still and be cooled to 20~50 DEG C,Filter and obtain morpholine fatty acid ester salt.
nullPresent invention also offers a kind of light eleostearate,By light eleostearic acid (bleaching shellac)、Morpholine、Ethanol、Ammonia and deionized water are prepared from,Described light eleostearic acid (bleaching shellac)、Morpholine、Ethanol、The weight ratio of ammonia and deionized water is 10.0~18.0:1.93~3.95:8.0~10.0:0.5~1.2:60.0~70.0,First the deionized water of ethanol and 3~20% is added in a reactor,It is preheated to 65~73 DEG C,Put into light eleostearic acid,Promote temperature to 76~83 DEG C,Add the morpholine of 70~80%,Stirring 10~30min,Pressure,It is warming up to 85~93 DEG C,It is incubated 1~5 hour,It is cooled to 73~83 DEG C,Add residue morpholine、Ammonia and remaining deionized water,Continue stirring 20~35 minutes,Drive still and be cooled to 20~50 DEG C,Filter and obtain light eleostearate.
Present invention also offers a kind of organosilicon acrylic resin, it is prepared from by acrylic acid or acrylate, propylene organosilicon, potassium peroxydisulfate, isopropanol, ammonia and deionized water, the weight ratio of described acrylic acid or acrylate, propylene organosilicon, potassium peroxydisulfate, isopropanol, ammonia and deionized water is 20~25:0.5~1.5:0.3~0.6:10.0~16.0:3.0~5.0:60.0~66.0, first deionized water and isopropanol are added heating in a reactor, it is preheated to 65~75 DEG C, adds the K of 5~15%2S2O8, be again heated to 76~85 DEG C, start to drip acrylic acid or acrylate, propylene organosilicon and 70~83% K2S2O8, 82~85 DEG C are incubated 2~3 hours, and dropwise reaction terminates to add remaining K2S2O8, it is incubated 0.5~1.5 hour at 85`90 DEG C, is subsequently cooled to 60~75 DEG C, add ammonia and regulate PH7~8, continue to be cooled to 20~50 DEG C, filter and obtain organosilicon acrylic resin.
Present invention also offers a kind of fruit freshness preserving fruit wax (SW-68A), it is made up of above-mentioned morpholine fatty acid ester salt and above-mentioned organosilicon acrylic resin, deionized water, described morpholine fatty acid ester salt mass percent in preservative fruit wax is 9.0%~12.0%, described organosilicon acrylic resin mass percent in preservative fruit wax is 8.0%~10.0%, and surplus is deionized water.
The preparation method that present invention also offers above-mentioned a kind of fruit freshness preserving fruit wax, weigh morpholine fatty acid ester salt and organosilicon acrylic resin, deionized water by mass percentage, in a reaction vessel, first add organosilicon acrylic resin and deionized water, it is warming up to 45~50 DEG C, add morpholine fatty acid ester salt, stirring 30~60min, is cooled to 25~40 DEG C, filters and get final product.
Present invention also offers a kind of fruit freshness preserving fruit wax (SW-68B), it is made up of above-mentioned light eleostearate and above-mentioned organosilicon acrylic resin, deionized water, described light eleostearate mass percent in preservative fruit wax is 6.0%~10.0%, described organosilicon acrylic resin mass percent in preservative fruit wax is 8.0%~12.0%, and surplus is deionized water.
The preparation method that present invention also offers above-mentioned a kind of fruit freshness preserving fruit wax, weigh light eleostearate and organosilicon acrylic resin, deionized water by mass percentage, in a reaction vessel, first add organosilicon acrylic resin and deionized water, it is warming up to 45~50 DEG C, add light eleostearate, stirring 30~60min, is cooled to 25~40 DEG C, filters and get final product.
Present invention also offers a kind of fruit freshness preserving fruit wax (SW-68C), be made up of above-mentioned organosilicon acrylic resin and deionized water, described organosilicon acrylic resin mass percent in preservative fruit wax is 16.0~18.0, and surplus is deionized water.
The preparation method that present invention also offers above-mentioned a kind of fruit freshness preserving fruit wax, weighs organosilicon acrylic resin and deionized water by mass percentage, first adds organosilicon acrylic resin in a reaction vessel, it is warming up to 35~45 DEG C, add deionized water, stir 20~60min, cold filtration and get final product.
The invention provides a kind of Novel fruit wax bulk composition morpholine fatty acid ester salt, the another kind of auxiliary ingredients that can do can do again macromolecule resin in the water-soluble organic silicon modified acroleic acid of main component, then pass through and converted, by ester salt and organosilicon acrylic resin, the preservative fruit wax joined, after not only having into cere, light is bright and new, do not whiten, ventilative control water, lasting stability, fresh-keeping comprehensive excellent effect such as guarantee the quality, and environmentally-friendly sanitary.
Detailed description of the invention:
Embodiment 1
nullThe invention provides a kind of morpholine fatty acid ester salt,By light eleostearic acid (bleaching shellac)、Abietic acid resin (PL 101、Meet SGS)、Morpholine、Ethanol、Ammonia and deionized water are prepared from,Described light eleostearic acid (bleaching shellac)、Abietic acid resin (PL 101、Meet SGS)、Morpholine、Ethanol、The weight ratio of ammonia and deionized water is 10.0~18.0:5.0~15.0:1.93~3.95:8.0~10.0:0.5~1.2:60.0~70.0,First the deionized water of ethanol and 3~20% is added in a reactor,It is preheated to 65~73 DEG C,Put into light eleostearic acid and abietic acid resin,Promote temperature to 76~83 DEG C,Add the morpholine of 70~80%,Stirring 10~30min,Pressure,It is warming up to 85~93 DEG C,It is incubated 1~5 hour,It is cooled to 73~83 DEG C,Add residue morpholine、Ammonia and remaining deionized water,Continue stirring 20~35 minutes,Drive still and be cooled to 20~50 DEG C,Filter and obtain morpholine fatty acid ester salt.
Embodiment 2
nullPresent invention also offers a kind of light eleostearate,By light eleostearic acid (bleaching shellac)、Morpholine、Ethanol、Ammonia and deionized water are prepared from,Described light eleostearic acid (bleaching shellac)、Morpholine、Ethanol、The weight ratio of ammonia and deionized water is 10.0~18.0:1.93~3.95:8.0~10.0:0.5~1.2:60.0~70.0,First the deionized water of ethanol and 3~20% is added in a reactor,It is preheated to 65~73 DEG C,Put into light eleostearic acid,Promote temperature to 76~83 DEG C,Add the morpholine of 70~80%,Stirring 10~30min,Pressure,It is warming up to 85~93 DEG C,It is incubated 1~5 hour,It is cooled to 73~83 DEG C,Add residue morpholine、Ammonia and remaining deionized water,Continue stirring 20~35 minutes,Drive still and be cooled to 20~50 DEG C,Filter and obtain light eleostearate.
Embodiment 3
Present invention also offers a kind of organosilicon acrylic resin, it is prepared from by acrylic acid or acrylate, propylene organosilicon, potassium peroxydisulfate, isopropanol, ammonia and deionized water, the weight ratio of described acrylic acid or acrylate, propylene organosilicon, potassium peroxydisulfate, isopropanol, ammonia and deionized water is 20~25:0.5~1.5:0.3~0.6:10.0~16.0:3.0~5.0:60.0~66.0, first deionized water and isopropanol are added heating in a reactor, it is preheated to 65~75 DEG C, adds the K of 5~15%2S2O8, be again heated to 76~85 DEG C, start to drip acrylic acid or acrylate, propylene organosilicon and 70~83% K2S2O8, 82~85 DEG C are incubated 2~3 hours, and dropwise reaction terminates to add remaining K2S2O8, it is incubated 0.5~1.5 hour at 85`90 DEG C, is subsequently cooled to 60~75 DEG C, add ammonia and regulate PH7~8, continue to be cooled to 20~50 DEG C, filter and obtain organosilicon acrylic resin.
Embodiment 4
Present invention also offers a kind of fruit freshness preserving fruit wax (SW-68A), it is made up of above-mentioned morpholine fatty acid ester salt and above-mentioned organosilicon acrylic resin, deionized water, described morpholine fatty acid ester salt mass percent in preservative fruit wax is 9.0%~12.0%, described organosilicon acrylic resin mass percent in preservative fruit wax is 8.0%~10.0%, and surplus is deionized water.
The preparation method that present invention also offers above-mentioned a kind of fruit freshness preserving fruit wax, weigh morpholine fatty acid ester salt and organosilicon acrylic resin, deionized water by mass percentage, in a reaction vessel, first add organosilicon acrylic resin and deionized water, it is warming up to 45~50 DEG C, add morpholine fatty acid ester salt, stirring 30~60min, is cooled to 25~40 DEG C, filters and get final product.
Embodiment 5
Present invention also offers a kind of fruit freshness preserving fruit wax (SW-68B), it is made up of above-mentioned light eleostearate and above-mentioned organosilicon acrylic resin, deionized water, described light eleostearate mass percent in preservative fruit wax is 6.0%~10.0%, described organosilicon acrylic resin mass percent in preservative fruit wax is 8.0%~12.0%, and surplus is deionized water.
The preparation method that present invention also offers above-mentioned a kind of fruit freshness preserving fruit wax, weigh light eleostearate and organosilicon acrylic resin, deionized water by mass percentage, in a reaction vessel, first add organosilicon acrylic resin and deionized water, it is warming up to 45~50 DEG C, add light eleostearate, stirring 30~60min, is cooled to 25~40 DEG C, filters and get final product.
Embodiment 6
Present invention also offers a kind of fruit freshness preserving fruit wax (SW-68C), be made up of above-mentioned organosilicon acrylic resin and deionized water, described organosilicon acrylic resin mass percent in preservative fruit wax is 15.0~18.0, and surplus is deionized water.
The preparation method that present invention also offers above-mentioned a kind of fruit freshness preserving fruit wax, weighs organosilicon acrylic resin and deionized water by mass percentage, first adds organosilicon acrylic resin in a reaction vessel, it is warming up to 35~45 DEG C, add deionized water, stir 20~60min, cold filtration and get final product.
Next the present invention mainly proves from three aspects:
Embodiment 7 sanitary considerations
Fruit wax bulk composition natural fat hydrochlorate demonstration: natural acid such as lac (light eleostearic acid class), Colophonium (abietic acid class), Palmic acid (palmitic acid) etc. and ammonia (NH3-H2O), morpholine (HNO) chemical combination.Chemically principle is inferred, is mainly following four big reaction species.
1, fatty acid ammonium salt: R-COOH+NH3·H2O→R-COO·NH4+H2O
Reaction condition: relatively low >=30 DEG C i.e. solubilized reaction, activity is maximum.
Performance effect: water solublity is good, it is possible to machine spray effect in very effective raising fruit wax storage stability and fruit wax.Other, without very positive interaction, are auxiliary element in fruit wax.
Environmentally-friendly sanitary: be easier to decompose, is reduced into organic acid and volatilization ammonia, poisons very little, discuss slightly.
2, morpholine fatty acid salt (hydrogen bond salt):
Reaction condition: moderate, after fatty acid dissolves, 60~80 DEG C can be reacted, and activity is bigger.
Performance effect: good water solubility, stable.Fruit wax glued membrane levelability, adhesive force, brightness, a series of effects such as vibrancy can be effectively improved, and because glued membrane water suction is moderate, namely a large amount of water suctions are readily soluble not easily whitens, also can recover after a small amount of water suction whiting, therefore can as the main component of fruit wax, there is good fresh-keeping effect, be succeeded in developing, early than the seventies in last century, the main body fruit wax composition being developed so far by the U.S. 402.
Environmentally-friendly sanitary: can decompose.Morpholine and corresponding fatty acid is resolved into after entering human body.U.S. testing result rat oral LD50 is 1600mg/kg, and within 1977, morpholine fatty acid salt is classified as GRAS material by U.S. FDA.
3, morpholine fatty acid ester salt:
(this ester salt is one of subject matter, and ester salt is the fruit wax bulk composition of the present invention)
Reaction condition: slightly higher.Should fatty acid after alcohol water fully dissolves in 80~90 DEG C, a few hours react, activity moderate.
Performance effect: good water solubility, stable.Waxing effect equally can be effectively improved fruit wax levelability, adhesive force, brightness, a series of effects such as vibrancy with hydrogen bond salt, and because ester bond salt not easily cracks because of steady chemical structure, therefore can absorb water and not easily return white, protect light fresh-keeping effect time ester salt and certainly will be better than hydrogen bond salt.
Environmentally-friendly sanitary: not easily crack.Enter human body still substantially can esters state to discharge, though cracking, also than morpholine much less produced by hydrogen bond salt.Clearly, morpholine belongs to a kind of harmful organic amine, though U.S. FDA through rat entrance test after be classified as GRAS material, indicate can not be immediately poisoning boundary.Nevertheless, trace takes in morpholine organic amine when if human body is few or time long, its harmful consequences is uncertain.In brief, human body had better not take in such material, at least more few more non-hazardous.
4, morpholine fatty acid amide:Reaction condition: higher, it is necessary in high temperature dehydration state response.Activity is little.
Performance effect: poorly water-soluble, nontransparent stable.Upper machine sprayability, quick-drying are better than ester salt and hydrogen bond salt, but adhesive force, brightness, freshness etc. in other all not as good as ester salt and hydrogen bond salt, being particularly susceptible water suction whiting difficulty recovers even degumming, cannot function as fruit wax bulk composition at all.There is not yet this type of report both at home and abroad, but the author it is reported, some Guo La manufacturer domestic is because considering that dissolving hard fat acid (lac class etc.) needs, intensification (how at 110~130 DEG C) that water body is pressed is reacted with morpholine with dissolved fat acid again and is converted wax, possible some do not know, at this point in the reaction, the probability generating morpholine fatty acid amide is greatly improved, so that often occurring the sequela such as whiting dewaxing on this market.
Environmentally-friendly sanitary: being difficult to cracking, toxicity is not surveyed, enters human body and certainly easily drains not as good as ester salt and hydrogen bond salt, should not become fruit wax composition.
Morpholine fatty acid salt class (ester salt and hydrogen bond salt) contrast demonstration:
Acid number according to natural acid, may infer that the compound molecular weight being combined with morpholine, thus judging that morpholine accounts for the number of components of its compound, by solid content contrast weightless after solid content original after film forming and baking, and then infer the soap structure component because cracking weightless composition.
Lac resin: acid number mostly is about 70, single moles of carboxylic acids molecular weight is about 800, is 887 in conjunction with molecular weight after morpholine, and wherein morpholine occupancy volume is 9.81%.Rosin resin: acid number mostly is 100~130, single moles of carboxylic acids molecular weight is 560~430, and in conjunction with molecular weight 647~517 after morpholine, wherein morpholine occupancy volume is 13.44~16.82%.Palmic acid: acid number 218.8, single moles of carboxylic acids molecular weight 256, in conjunction with molecular weight 343 after morpholine, wherein morpholine occupancy volume is 25.36%.
The present invention specially utilizes lac and Colophonium respectively to do one group of contrast test, formula identical (especially fatty acid is consistent with morpholine ratio), differs mainly from reaction controlling condition.
S-49: after alcohol hydrolysis, 80~85 DEG C are reacted three hours;S-50: after alcohol hydrolysis, 75~80 DEG C are reacted one hour, Colophonium;(formulation weight percentage ratio: abietic acid: morpholine: ammonia: ethanol: deionized water=18.0~19.0:3.0~3.2:2.8~3.0:8.0~10.0:65.0~68.0)
After C-410:80 DEG C of hydrolysis, >=90 DEG C are reacted three hours;After C-425:65 DEG C of alcohol hydrolysis, >=90 DEG C are reacted three hours, lac;(formulation weight percentage ratio: eleostearic acid: morpholine: ammonia: ethanol: deionized water=18.0~19.0:3.6~3.8:2.0~2.5:8.0~10.0:65.0~68.0)
Test imagination, same reaction formula difference controls condition, and Colophonium group should be many with S-49 ester salt composition, and weightlessness should less than S-50;Lac should be many with C-425 ester salt composition, and weightlessness should less than C-410.
Experimental Comparison result: original solid content (0) [100 DEG C of * 2hr], baking solid content (1) [130 DEG C of * 3hr], after weight-loss ratio is baking, weight loss accounts for the percentage ratio of original solid content.Result of the test is determined for compliance with test imagination, and S-50 and C-410 weight-loss ratio, obviously higher than S-49 and C-425, refers to table 1.
Meanwhile, the present invention is to SW-68 and the U.S. 402 and how the domestic fruit wax sample of group has carried out tens groups test baking weight-loss ratios repeatedly, refers to table 2.
Table 1
Table 2
Deduction, above-mentioned fruit wax main component can be inquired into.
SW-68A: natural acid morpholine ester salt, silicone-acrylic water-soluble resin;
SW-68B: silicone-acrylic water-soluble resin, light eleostearic acid morpholine ester salt;
SW-68C: silicone-acrylic water-soluble resin, (lysate is mainly NH3);
U.S. 402: fatty acid morpholine hydrogen bond salt masterpiece, FDA author;
Beautiful 402D:402 improves thing, it is clear that ester salt composition improves, and hydrogen bond salt composition substantially lowers perhaps added with modified resin, is the maximum imported product of the current consumption of China, and reaction is good;
State sample A: approximate 402D, ester salt hydrogen bond salt equilibrium, concentrated expression is normal, is increasingly becoming a domestic brand;
State sample B: it will be apparent that main body is palmitic acid morpholine hydrogen bond salt, with low cost, Market reaction still can, but because of very easily water-soluble delustring, therefore the effect such as fresh-keeping is not as good as domestic sample A;
State sample C: fatty acid morpholino amide is many, therefore muddiness is not durable, and the whiting that easily absorbs water, future trouble is not surveyed, and is prepared by High Temperature High Pressure, in currently improving;
State sample D: similar domestic sample C, there is a morpholino amide composition, but fewer than C (translucent and store this point of susceptible of proof of a specified duration), it is coated with fruit also hygroscopic whiting.
Integration test result is seen, SW-68 high temperature weight-loss ratio is all significantly lower than 402D (being more far more than 402), then last it is inferred that SW-68 mono-aspect had both met current FDA standard, it is not surveyed hazardness and is less than 402D yet on the other hand.From this point, whether relevant hygiene department should revised sanitary standard: improves ester salt composition, minimizing hydrogen bond salt composition, stops amide composition.Saying namely permanently effective science health angle point from another point, the direction of fruit wax development should be SW-68C series products, without morpholine organic amine, even if stable not easily cracking fission and the polymer waterborne thing without other bad sequela are eaten by mistake and also easily normally mediated.
It is presently believed that development fruit wax based food contact series products even other direct foodstuff products, chemical based reason discussion must be made full use of and speculate and then resolution, so just meet the scientific development of human survival.
Machine effect in embodiment 8
Any industrial products, if supreme machine operability, even if environmentally-friendly sanitary, performance are good more again, all are futile effort.Fruit wax is operated the computer to be become China and waxes now the actual state of industry, therefore upper machine controllability must be paid attention to, the present invention result according to on-the-spot experimental observation, is summarized as follows.
1, upper machine spraying (is mainly fruit wax sprayability): SW-68A, SW-68B are bordering on 402D, and current machine performance is operable;SW-68C atomization shortcoming (Polymer Systems, though water-soluble good, viscosity is slightly higher);
2, aridity (being mainly quick-drying and non-viscosity): SW-68A, SW-68B, SW-68C are significantly better than that 402D;
3, brightness (being mainly performance aesthetic property): due to the factor containing natural acid, so SW-68A, SW-68B are coated with the vibrancy all same 402D of fruit, though SW-68C bright property is good, but vivid degree is not as good as SW-68A, SW-68B, 402D;
4, smoothness (performance handling property): SW-68 is superior to 402D, the viscous packaging of tack-free viscous bag;
5, storing property of a specified duration: current Tu Guo enterprise mostly is open place, and go out the fruit phase and mostly be early autumn to the early spring, different places or areas, affecting the heaviest phase is the severe winter, and namely fruit wax have thick change or weak to freezing in case of cold, necessarily affects painting fruit efficiency and performance, so item requires to give attention.Resistance to for a long time freezing all is store in SW-68 and 402, even if when subzero 10 degree~20 degree of fully charges, defrosting can recover rapidly ortho states.
In sprayability, ester salt is micro-is inferior to hydrogen bond salt (hydrogen bond water-soluble is slightly higher than ester salt);In light freshness and storage property of a specified duration, the two is consistent;In aridity with smoothness, ester salt is substantially better than hydrogen bond salt.Here it is the comparison of both upper machine effects.
Embodiment 9 fresh keeping property
Fruit film function: one is appearance looks elegant;Two is persistently fresh-keeping.From primary efficacy, should be the latter, but the two is consistent in fact.Inventor arrives through experimental observation over the years, if being often coated with wax fruit outward appearance have mutation water suction, delustring or coloured different, finally just easily goes mouldy rotten.
Namely fruit is anhydrous has no result, and water, for fruit growth and storage, has basic biotic factor, but water is also maximum the easiest to the destructive degree of fruit exactly.For Fructus Citri tangerinae orange Citrus chachiensis Hort., once not process in time after soaking water, then namely can go rotten soon.Naturally observation is preserved from fruit, also can every day weightless (in fact namely dehydration), weightlessness to a certain extent that is is gone rotten, so, the at all fresh-keeping key element of fruit waxing safeguards water balance in sporocarp exactly, extending equilibration time, reduce weight-loss ratio, its key element controls chemical equilibrium in fact exactly.In this way: fruit wax fruit wax, should can water-soluble be first to become water-based system, even if next to that eat by mistake and can excrete after being fully hydrolyzed, these are environmentally-friendly sanitary requirements;Also want can control Wax with water contained film after not hygroscopic, meet cold and hot change and not easily crack change, these are fresh-keeping requirements.How to study well the performance chemical balance of water, here it is that develops fruit wax at all will be.
For fatty acid, potassium, sodium salt should be not only stable water soluble but also preferably, but due to potassium, sodium salt water suction i.e. easily whiting, and dying upper selects with this without producer, and amide is water-soluble well not easily to whiten again, so numerous manufacturer also all selects its adapted.Morpholine is not only water-soluble not only has corresponding adhesive force simultaneously but also not easily to whiten relatively stable, therefore the U.S. has started this type of fruit wax and continued into the present.But the present from that discussed above in known chemically structure, ester salt is more stable than hydrogen bond salt and water solublity is also good, and after becoming cere, ester salt is all better than hydrogen bond salt in water-fast anti-whiting, brightness, fresh-keeping persistent period.
The author in recent years from China fruit the field observation of wax market and repeatedly contrast sampling test learn, water-fast fresh-keeping effect on current market, really with U.S. 402D for best.
Table 3 (fruit wax is coated with Fructus Citri tangerinae submerging test):
Chemical analysis structural agent is discussed: 68A combines natural acid morpholine ester salt and organosilicon acrylic resin;68B combines light eleostearic acid morpholine ester salt and organosilicon acrylic resin;The pure organosilicon acrylic resin of 68C.The little activity of abietate's molecules of salt amount relatively easily splits mutability greatly, and light eleostearate is relatively stable, and silicon third is the most stable without mutation.Immersion failure test exactly adds clear this point.
Table 4 (fruit wax immersion go mouldy weightless contrast) A (SW-68A) D (402D)
Table 5 (after fruit wax is coated with fruit, natural storage weightlessness contrasts)
Illustrate: it is similar with 402D that the present invention has SW-68A structural constituent only, therefore the contrast taken.It is shown that in immersion destructive testing, both contrasts are relatively big, and SW-68A is substantially better than 402D, and in natural storage, both are very nearly the same, but still SW-68A to be better than 402D slightly.
Immersion 4 minutes SW-68A, 402D homogeneous weeks of failure test are out of control, but contrast test SW-68B of the present invention soaks 5 minutes one or two weeks also normally, and SW-68C soaks and was more as good as more than 15 minutes January.Much more no longer known have chemical analysis master control to be become, to state.
Embodiment 10 comprehensively illustrates
The ultimate constituent (include other by-products or leave over composition) of novel fruits preservative fruit wax SW-68A, SW-68B, SW-68C of the present invention refers to lower list 6 (percentage ratio).
Table 6
Novel fruits preservative fruit wax SW-68A, SW-68B and SW-68C of the present invention are full water-soluble system;SW-68A, SW-68B outward appearance is purplish red as clear as crystal, and SW-68C outward appearance pure water color is colourless as clear as crystal;Its master control water-soluble components is fatty acid salt and middle polyphosphazene polymer ester ammonium salt.
Complete water-soluble system wax liquid is all better than oil-in-water type or floating type wax liquid in stability, the carefully property tied, film property each side, also just owing to combining the water soluble natural sex of salt, also the environmentally-friendly sanitary that is highly advantageous to controls particularly to become cere also to be able to normally excrete after eating by mistake, so namely these main points are the primary starting points of the present invention.
Design synthesis, with fatty acid morpholine ester salt for main body fruit wax composition, is possible not only to substantially reduce morpholine lysate and improves hygiene and health effect to reduce harm human factor, and its water solublity is imitated with morpholine fatty acid hydrogen bond salt face.Its comprehensive preservation effect is also better than hydrogen bond salt, and this is one of the main points of the present invention.
Design synthesis be polymerized with the aqueous solution of organosilicon-modified acrylic in macromolecule resin for fruit wax auxiliary ingredients or main component, reduce or completely Chu fatty acid morpholine salt composition.Such technical products should become the controlled environmentally-friendly sanitary of the mankind and cheap and good-quality Novel fruit wax (or other similar hygienic article) developing direction.This is the two of main points of the present invention.
Although pure acrylic acid is water-soluble good stable again, but is extremely short of in adhesive force, water-resistance, cold-and-heat resistent etc., introduce active organosilicon copolymerized therewith, it is possible to overcome this respect to be short of completely, it is possible to the advantage extremely efficient reaching not only molten water but also controlling water.
By-product (unreacting propylene acid esters, potassium sulfate): one of future trouble factor of high molecular polymerization, it is necessary to control.The present invention utilizes special process (particularly adding initiator, such as potassium peroxydisulfate) to reduce or to eliminate, current unreacted monomer trace, adds that toxicity own is very little, more go up film and almost volatilizees nothing left, so nothing very hidden danger.More for potassium peroxydisulfate consumption in this this formula, its effect one is to cause macromolecule, and two is close macromolecule, and namely residue person becomes K in body series2SO4Potassium sulfate, for mankind's edible salts class, harmless.
Auxiliary ingredients: fatty acid ammonium salt, auxiliary body, improves water-soluble;Ammonium hydroxide regulates finished product PH;Ethanol, isopropanol are controllability food grade solvent.This kind solvent contributes to fat acid dissolution reaction and high molecular weight reactive in a word, is also highly advantageous to and plays table bactericidal action at the beginning painting fruit, namely volatilizees after achievement wax;Deionized water is the pure water specially processed, and is the bulk solvent of water-borne wax liquid.

Claims (2)

  1. null1. a fruit freshness preserving fruit wax,It is characterized in that: by light eleostearate and organosilicon acrylic resin、Deionized water forms,Described light eleostearate,By light eleostearic acid、Morpholine、Ethanol、Ammonia and deionized water are prepared from,Described light eleostearic acid、Morpholine、Ethanol、The weight ratio of ammonia and deionized water is 10.0~18.0:1.93~3.95:8.0~10.0:0.5~1.2:60.0~70.0,First the deionized water of ethanol and 3 ~ 20% is added in a reactor,It is preheated to 65 ~ 73 DEG C,Put into light eleostearic acid,Promote temperature to 76 ~ 83 DEG C,Add the morpholine of 70~80%,Stirring 10 ~ 30min,Pressure,It is warming up to 85 ~ 93 DEG C,It is incubated 1 ~ 5 hour,It is cooled to 73 ~ 83 DEG C,Add residue morpholine、Ammonia and remaining deionized water,Continue stirring 20 ~ 35 minutes,It is cooled to 20 ~ 50 DEG C,Filter and obtain light eleostearate;Described organosilicon acrylic resin is prepared from by acrylic acid or acrylate, propylene organosilicon, potassium peroxydisulfate, isopropanol, ammonia and deionized water, the weight ratio of described acrylic acid or acrylate, propylene organosilicon, potassium peroxydisulfate, isopropanol, ammonia and deionized water is 20~25:0.5~1.5:0.3~0.6:10.0~16.0:3.0~5.0:60.0~66.0, first deionized water and isopropanol are added heating in a reactor, it is preheated to 65 ~ 75 DEG C, adds the K of 5 ~ 15%2S2O8, be again heated to 76 ~ 85 DEG C, start to drip acrylic acid or acrylate, propylene organosilicon and 70 ~ 83% K2S2O8, 82~85 DEG C are incubated 2~3 hours, and dropwise reaction terminates to add remaining K2S2O8, it is incubated 0.5 ~ 1.5 hour at 85`90 DEG C, is subsequently cooled to 60 ~ 75 DEG C, add ammonia and regulate PH7 ~ 8, continue to be cooled to 20 ~ 50 DEG C, filter and obtain organosilicon acrylic resin;Described light eleostearate mass percent in preservative fruit wax is 6.0%~10.0%, and described organosilicon acrylic resin mass percent in preservative fruit wax is 8.0%~12.0%, and surplus is deionized water.
  2. 2. the preparation method of a kind of fruit freshness preserving fruit wax described in claim 1, it is characterized in that: weigh light eleostearate and organosilicon acrylic resin, deionized water by mass percentage, in a reaction vessel, first add organosilicon acrylic resin and deionized water, it is warming up to 45~50 DEG C, add light eleostearate, stirring 30~60min, is cooled to 25 ~ 40 DEG C, filters and get final product.
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CN101040630A (en) * 2007-04-27 2007-09-26 中国林业科学研究院资源昆虫研究所 Bleached lac nanometer fresh-keeping agent of mango
CN101053343A (en) * 2007-05-10 2007-10-17 上海交通大学 Shellac fresh keeping fruit wax and its preparation method
CN101828150A (en) * 2007-10-15 2010-09-08 佳能株式会社 Toner
CN101177650A (en) * 2007-12-11 2008-05-14 中国林业科学研究院资源昆虫研究所 Method for extracting shellac wax and shellac wax prepared by this method
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