阅读说明：本技术 一种淀粉基高稳定Pickering乳液及其制备方法 (A kind of starch base high stable Pickering lotion and preparation method thereof ) 是由 黄强 李松南 朱子熙 张斌 扶雄 于 2019-07-17 设计创作，主要内容包括：本发明公开了一种淀粉基高稳定Pickering乳液及其制备方法。该制备方法先将淀粉原料配制干基质量分数为5～20％的淀粉浆液,沸水浴糊化后冷却,滴加过量乙醇后离心分级,沉淀烘干后得到V型结晶淀粉；将熔融的脂肪酸与V型结晶淀粉充分混合后持续搅拌,鼓风干燥后得到淀粉脂质复合粒子；将淀粉脂质复合粒子配制成悬浮水溶液,将悬浮水溶液与液态油脂混合,高速剪切,得到淀粉基高稳定Pickering乳液,其乳液的乳化指数均能达到100％,乳滴分布均匀,其平均粒径为10.13～25.20μm,贮藏三个月不分层。本发明具有工艺简单、原料来源丰富、绿色环保等特点,可广泛应用于食品、化妆品、化工和医药等领域。(The invention discloses a kind of starch base high stable Pickering lotions and preparation method thereof.Starch raw material is first prepared the farinaceous size that butt quality score is 5~20% by the preparation method, cooling after boiling water bath gelatinization, and centrifugal classification after excess ethyl alcohol is added dropwise, obtains V-type crystal starch after precipitating drying；It is persistently stirred after the fatty acid of melting is sufficiently mixed with V-type crystal starch, starch lipids compound particle is obtained after forced air drying；Starch lipids compound particle is configured to aqueous suspension, aqueous suspension is mixed with liquid fat, high speed shear, obtain starch base high stable Pickering lotion, the emulsification index of its lotion can reach 100%, emulsion droplet is evenly distributed, and average grain diameter is 10.13~25.20 μm, and storage three months not stratified.The present invention has the characteristics that simple process, raw material sources are abundant, environmentally protective, can be widely applied to food, cosmetics, chemical industry and medicine and other fields.)

1. a kind of preparation method of starch base high stable Pickering lotion, it is characterised in that include the following steps and technique item Part:

(1) starch raw material is prepared into the farinaceous size that butt quality score is 5~20%, under agitation boiling water bath gelatinization 1 ~2h, after being cooled to 30~50 DEG C, the excessive dehydrated alcohol of the lower drop of lasting stirring, centrifugal classification is precipitated, and precipitating air blast is dry V-type crystal starch is obtained after dry；

(2) fatty acid is melted down, persistently stirs 1~2h, form fluid fatty acid；

(3) 1 is persistently stirred after being sufficiently mixed the resulting fluid fatty acid of step (2) and step (1) resulting V-type crystal starch Starch lipids compound particle is obtained after~2h, after forced air drying；

(4) the resulting starch lipids compound particle of step (3) is configured to the aqueous suspension that butt quality score is 2~6%, Aqueous suspension is mixed, high speed shear with liquid fat, obtains starch base high stable Pickering lotion.

2. preparation method according to claim 1, which is characterized in that in step (1), the starch raw material is corn shallow lake Powder, potato starch or tapioca；The butt quality score of the farinaceous size is 5~15%；When the boiling water bath is gelatinized Between be 1~2h；The cooling temperature is 30~50 DEG C.

3. preparation method according to claim 1, which is characterized in that in step (1), with volume fraction, the starch Slurries additive amount is 1 part, 2~5 parts of the dehydrated alcohol additive amount；The temperature of the forced air drying is 40~60 DEG C, dry Time be 12~for 24 hours.

4. preparation method according to claim 1, which is characterized in that in step (2), the fatty acid is lauric acid, palm fibre Palmitic acid acid and stearic acid；The temperature of the melting is 55~75 DEG C；The agitating mode is magnetic agitation or mechanical stirring.

5. preparation method according to claim 1, which is characterized in that in step (3), with volume fraction, the step (2) resulting fluid fatty acid is 1~3 part, and the resulting V-type crystal starch of step (1) is 5~10 parts；The mixing Mode be directly mix or be atomized mix.

6. preparation method according to claim 1, which is characterized in that in step (3), the temperature of the forced air drying is 40~60 DEG C, the dry time be 12~for 24 hours.

7. preparation method according to claim 1, which is characterized in that described in terms of butt quality score in step (4) Aqueous suspension in starch lipids compound particle be 2~6 parts, distilled water be 100 parts.

8. preparation method according to claim 1, which is characterized in that in step (4), with volume fraction, suspend water-soluble During liquid is mixed with liquid fat, the aqueous suspension is 30~60 parts, and liquid fat is 70~40 parts；The liquid fat For soybean oil, corn oil or palm oil.

9. preparation method according to claim 1, which is characterized in that in step (4), the revolving speed of the high speed shear is 5000~25000rpm, the time of high speed shear are 1~5min.

10. a kind of starch base high stable Pickering lotion, which is characterized in that it is as described in claim 1~9 any one Preparation method is made, and the emulsification index of the starch base high stable Pickering lotion can reach 100%, emulsion droplet distribution Uniformly, average grain diameter is 10.13~25.20 μm, and storage three months not stratified.

Technical field

The present invention relates to the compound V-type crystal starches of lipid, and it is newborn as Pickering to be related to a kind of novel hydrophobically modified starch The environment-friendly preparation method thereof of agent, this method is related to " lipid is compound " green hydrophobic modified starch, to obtain a kind of novel foodstuff The amphipathic Pickering emulsifier of grade, belongs to field of food industry.

Background technique

Pickering lotion, which refers to, uses the solid particle being adsorbed at oil-water interfaces to replace surfactant as stabilizer A kind of New Emulsion, preparation process is simple, and stability of emulsion is splendid.With the growing consumption demand of people, market Demand to the product with labels such as " environmental-friendly, green " is continuously increased, the stable Pickering of biology base solid particle Lotion gradually attracts attention, and has huge market latent in industries such as food, cosmetics, chemical industry, material and medicine Power.Pickering emulsion intercalation method depends on the properties such as particle size and the moistened surface degree of solid particle, has compared with granule Diameter and amphiphilic solid particle, which can be equably covered on, forms fine and close film on two-phase interface, generate steric hindrance, thus The coalescence of Ostwald maturation and dispersed phase is fought, often stability is fine for the lotion of formation, can the stored for months even several years.

Starch is a kind of resourceful and green natural large biological molecule, can be used as biology base Pickering emulsifier Raw material.The particle size of native starch is larger and hydrophily is strong, it is difficult to be firmly adsorbed on two-phase interface, limit its Application in Pickering lotion, therefore often change the property of native starch particles by either physically or chemically, make it Grain size and surface nature change, to achieve the purpose that stabilized emulsion system.

Current main method of modifying more concentrates on octenyl succinic acid anhydride (OSA) Hydrophobic Modified Starch.Such as middle promulgated by the State Council Bright patent application 2018105557772 discloses a kind of preparation method of starch base Pickering emulsion gel.This method is first used The small particle starch granules that octenyl succinic acid anhydride is 1~5 μm to average grain diameter carries out esterification modification, and obtaining degree of substitution is 0.028~0.100 modification small particle starch granules；Then modified small particle starch granules is pressed into solid-liquid mass fraction 1~5% It is dispersed in distilled water, persistently stirring 6~12h makes its abundant aquation, forms suspension of starch particles；By resulting starch Starch base Pickering emulsion gel can be obtained after particle suspension liquid is mixed with liquid fat, after high speed shear.Side of the present invention The starch base Pickering emulsion gel of method preparation is a kind of physical gel, does not change the chemical property of oily phase, no trans fats The generation of acid, can be used for constructing function grease, and the carrier for being alternatively arranged as fat-soluble pigment and flavor substance is applied to cosmetics With the fields such as daily necessities.Pickering lotion is prepared using native starch, OSA modified starch and heat treatment starch as emulsifier, The result shows that OSA modified starch shows best storage-stable, storage period was up to 2 years or more (Timgren et al.,2013,Food Science&Nutrition,1(2),157-171).OSA modification rice is compared with quinoa starch granules, The Pickering lotion prepared through the modified quinoa starch of OSA as emulsifier has smaller emulsion droplet size and storage-stable Property (Marefati et al., 2017, Food Hydrocolloids, 63,309-320).It is steady for OSA modification rice starch For fixed Pickering lotion, when starch concentration be 4%, oil phase volume score be 50%, ph value of emulsion at 6~7, With optimal lotion effect (Song et al., 2015, Food Hydrocolloids, 45,256-263).However, due to Excessive chemistry addition may there are potentially hazardous, food and drug administration (FDA) and country's marks to human health The OSA maximum additive amount for the OSA modified starch for being used for food production is limited to 3% by standard (GB) 28303-2012, and degree of substitution is not Greater than 0.02, therefore the product is limited in the application in food and medicine field.

Summary of the invention

It is an object of that present invention to provide a kind of simple process, raw material sources to enrich, environmentally protective novel hydrophobically modified shallow lake Powder is as Pickering emulsifier and preparation method thereof, the cream of the stable Pickering lotion of gained starch lipids compound particle 100% can be reached by changing index, and emulsion droplet is evenly distributed, and average grain diameter is 10.13~25.20 μm, and storage three months are not stratified, It can be widely applied to food, cosmetics, chemical industry and medicine and other fields.

After starch raw material is first sufficiently gelatinized by the present invention in boiling water bath, starch molecule is fully extended, excessive by being added Dehydrated alcohol, formed V-type crystal starch-ethyl alcohol single coil configuration, by forced air drying remove ethyl alcohol, V-type knot can be obtained Brilliant starch.V-type crystal starch and the fatty acid of melting are carried out to compound, formation V-type crystal starch-fatty acid compound particle again, To reach modified to the green hydrophobic of V-type crystal starch, and further by V-type crystal starch-fatty acid compound particle application In Pickering lotion, the Pickering lotion of high stable can be obtained.

The object of the invention is achieved through the following technical solutions:

A kind of preparation method of starch base high stable Pickering lotion, includes the following steps and process conditions:

(1) starch raw material is prepared into the farinaceous size that butt quality score is 5~20%, boiling water bath is pasted under agitation Change 1~2h, after being cooled to 30~50 DEG C, the excessive dehydrated alcohol of the lower drop of lasting stirring, centrifugal classification is precipitated, and precipitates air blast V-type crystal starch is obtained after drying；

(2) fatty acid is melted down, persistently stirs 1~2h, form fluid fatty acid；

(3) continue after being sufficiently mixed the resulting fluid fatty acid of step (2) and step (1) resulting V-type crystal starch After stirring 1~2h, starch lipids compound particle is obtained after forced air drying；

(4) the resulting starch lipids compound particle of step (3) is configured to the water in suspension that butt quality score is 2~6% Solution mixes aqueous suspension with liquid fat, high speed shear, obtains starch base high stable Pickering lotion.

To further realize the object of the invention, it is preferable that in step (1), the starch raw material is cornstarch, potato Starch or tapioca；The butt quality score of the farinaceous size is 5~15%；The boiling water bath gelatinization time is 1~2h； The cooling temperature is 30~50 DEG C.

Preferably, in step (1), with volume fraction, the farinaceous size additive amount is 1 part, and the dehydrated alcohol adds 2~5 parts of dosage；The temperature of the forced air drying be 40~60 DEG C, the dry time be 12~for 24 hours.

Preferably, in step (2), the fatty acid is lauric acid, palmitinic acid and stearic acid；The temperature of the melting is 55 ~75 DEG C；The agitating mode is magnetic agitation or mechanical stirring.

Preferably, in step (3), with volume fraction, the resulting fluid fatty acid of step (2) is 1~3 part, institute Stating the resulting V-type crystal starch of step (1) is 5~10 parts；The mixed mode is directly to mix or be atomized mixing.

Preferably, in step (3), the temperature of the forced air drying is 40~60 DEG C, the dry time is 12~for 24 hours.

Preferably, in step (4), in terms of butt quality score, starch lipids compound particle in the aqueous suspension It is 2~6 parts, distilled water is 100 parts.

Preferably, in step (4), with volume fraction, during aqueous suspension is mixed with liquid fat, the water in suspension Solution is 30~60 parts, and liquid fat is 70~40 parts；The liquid fat is soybean oil, corn oil or palm oil.

Preferably, in step (4), the revolving speed of the high speed shear is 5000~25000rpm, the time of high speed shear For 1~5min.

A kind of starch base high stable Pickering lotion, is made by above-mentioned preparation method, the starch base high stable The emulsification index of Pickering lotion can reach 100%, and emulsion droplet is evenly distributed, and average grain diameter is 10.13~25.20 μm, storage Hiding three months it is not stratified.

The present invention introduces fatty acid molecule shape using the starch of separate sources and fatty acid as raw material in V-type crystal starch At starch lipids compound particle, the hydrophobicity of amylum grain can be improved, to obtain a kind of novel food-grade amphiphilic starch Base Pickering emulsifier, and the unrestricted use in food and medicine field.

The emulsification index of the stable Pickering lotion of gained starch lipids compound particle of the invention can reach 100%, Emulsion droplet is evenly distributed, and average grain diameter is 10.13~25.20 μm, and storage three months not stratified, can be widely applied to food, changes Cosmetic, chemical industry and medicine and other fields.

Compared with prior art, the present invention the invention has the advantages that:

1) fatty acid used in the present invention is a kind of food grade materials, the limit without maximum additive amount in field of food System, and the hydrophilic and hydrophobic of starch lipids compound can be adjusted according to the type, chain length and recombination rate etc. of fatty acid, than 3% OSA maximum additive amount OSA starch in field of food using wider.

2) present invention is different from the preparation of traditional OSA modified starch, is a kind of physically modified starch method, by fatty acid point Son with V-type crystal starch carry out physical mixed, fatty acid molecule can enter V-type crystal starch single-screw cavity in form V-type Starch lipids compound, to change the hydrophilic and hydrophobic of starch.Compared with the converted starches such as OSA modified starch, this hair Bright modifying process is not related to excessive organic and alkaline reagent and uses, and technique is more simple and green；Starch raw material source is more Horn of plenty is not limited to small particle starch granules, and the splendid starch base Pickering emulsifier of emulsifiability can be obtained.

3) the method for the present invention is by the modified V-type crystal starch of " lipid is compound " green hydrophobic, by the way that anhydrous second is added dropwise dropwise Alcohol obtains V-type crystal starch-ethyl alcohol single coil configuration to gelatinized starch system, and V-type crystallization shallow lake can be obtained after drying away ethyl alcohol Powder；It is afterwards that the fatty acid of melting and the progress of V-type crystal starch is compound, starch lipids compound particle is formed, amylum grain is improved Hydrophobicity, to obtain a kind of novel food-grade amphiphilic starch base Pickering emulsifier.

4) the emulsification index of the stable Pickering lotion of present invention gained starch lipids compound particle can reach 100%, emulsion droplet is evenly distributed, and average grain diameter is 10.13~25.20 μm, and storage three months not stratified, can be widely applied to eat Product, cosmetics, chemical industry and medicine and other fields.

Detailed description of the invention

Fig. 1 is the stable apparent photo of Pickering lotion of the V-type crystal starch of comparative example preparation.

Fig. 2 is the microphoto of the stable Pickering lotion of the V-type crystal starch of comparative example preparation.

Fig. 3 is the stable Pickering emulsion particle diameter distribution map of the V-type crystal starch of comparative example preparation.

Fig. 4 is the stable apparent photo of Pickering lotion of the starch lipids compound particle of the preparation of embodiment 1.

Fig. 5 is the microphoto of the stable Pickering lotion of the starch lipids compound particle of the preparation of embodiment 1.

Fig. 6 is the stable Pickering emulsion particle diameter distribution map of the starch lipids compound particle of the preparation of embodiment 1.

Fig. 7 is the stable apparent photo of Pickering lotion of the starch lipids compound particle of the preparation of embodiment 2.

Fig. 8 is the microphoto of the stable Pickering lotion of the starch lipids compound particle of the preparation of embodiment 2.

Fig. 9 is the stable Pickering emulsion particle diameter distribution map of the starch lipids compound particle of the preparation of embodiment 2.

Figure 10 is the stable apparent photo of Pickering lotion of the starch lipids compound particle of the preparation of embodiment 3.

Figure 11 is the microphoto of the stable Pickering lotion of the starch lipids compound particle of the preparation of embodiment 3.

Figure 12 is the stable Pickering emulsion particle diameter distribution map of the starch lipids compound particle of the preparation of embodiment 3.

Specific embodiment

In order to better understand the present invention, the present invention will be further described with reference to the accompanying drawings and examples, but this hair Bright claimed range is not limited only to the range of embodiment statement.