CN105614653B - Comprising carotenoid crystals and for assigning red water-dispersible composition - Google Patents

Abstract

The present invention relates to comprising carotenoid crystals and for assigning red water-dispersible composition.Project is to provide containing the hydrocarbon carotenoid crystals through miniaturizeing and for assigning cherry water-dispersible composition.When solution is to provide to be included hydrocarbon carotenoid crystals, especially beta carotene or lycopene crystal and measured the absorbance of 0.004% aqueous solution (W/V) with the state being dispersed in particular emulsifier, the ratio of the specific absorbance for showing yellow and the absorbance being specifically displayed in red is steady state value water-dispersible composition below and its manufacturing method.The composition can assign cerise to by coloured material or product.

Description

Comprising carotenoid crystals and for assigning red water-dispersible composition

Technical field

The present invention relates to the micro mists that the state to be dispersed in the decentralized medium containing emulsifier includes hydrocarbon carotenoid crystals It minces cerise to be presented and for water-dispersible composition and its manufacturer for being assigned red by coloured material or product Method and purposes.And then specifically, among the above, as hydrocarbon carotenoid, it is selected from beta carotene and lycopene, is coloured Material or product are selected from the beverage/foods such as beverage, aquatic products processed goods, jelly, product of other people intake etc..

Background technique

As food red colour system natural coloring mattes, it is known to carrot prime system pigment (carotenoid pigment), cochineal Haematochrome, anthocyanin system pigment, gardenin, monascorubin etc..For these natural pigments, it is desirable that by these pigment coloreds Heat resistance, the light resistance that tone of the beverage/food in preservation/circulation will not change.Especially status are as follows: in drink applications, The natural pigment preparation of storage stability difference, which is easy to produce because of light, heat, to be occurred fading and generates precipitating, ring due to destruction because emulsifying The adverse effects such as shape object, can gratifying quality it is few.

In the case where using natural coloring mattes in food, due to the difference of pigment, tone depends on sometimes to be made The pH of food, natural coloring mattes is mixed it is a variety of in use, since the matching between colouring matter is different, it some times happens that Condensation, precipitating, tone variations etc. sometimes interfere with free coloring due to reason as above.It is therefore desirable to be able to show to disappear The extension of delicious sense, the toning for the natural coloring mattes naturally felt that expense person welcomes.

Carrot prime system pigment is usually widely used as red colour system pigment, but in the past in beverage/food on the way, mainly uses By the pigments crystal such as beta carotene, lycopene dissolve by heating in edible oil and fat etc. and into dissolved matter add emulsifier and into Row emulsification treatment, so that water-soluble or water dispersible pigment preparation be made.In this preparation method, due to carotenoid pigment point The a part for the double bond for including in son is isomerizated into cis- body from trans- body, dilutes additionally, due to by grease, therefore presents and crystalline substance Different orange ~ the yellow of the red tone that body has originally.Therefore, carrot prime system pigment is used as red colour system pigment phase with previous Than being gradually used as orange ~ yellow class pigment, the utility value as red colour system pigment is not so high.

On the other hand, in order to open up the purposes as red colour system pigment of carrot prime system pigment, exploitation is sent as an envoy to through miniaturizeing Crystal be scattered in the method for solution.For example, by carrot prime system pigmentolysis in the case where grease, as described above, having The tone of orange ~ yellow, but send out and present now with when crystal dispersion method close to red tone, to propose using the skill Art is (identical as lycopene by lycopene.) method for obtaining red colour system colouring matter is crushed in the solvent for not dissolving it (patent document 1).It should be noted that it is disclosed that the obvious red of lycopene is different, brilliant because of crystal habit in the document Body can lose the tinting strength, tinting power of its red area when dissolving.In turn, the preparation method as this crystal dispersibility pigment preparation, it is also proposed that Following method: being dissolved in carotenoid in the organic solvent of water Combination, thereafter mixed with water and make carotenoid with Dispersity is precipitated, and removes solvent from dispersion liquid and obtains the method (patent document of 0.5 μm of carotenoid crystals below 2)；To be mixed dissolved with the solution of pigment with specific dextrin in aqueous solution, thus obtain fine pigment crystal without Method (patent document 3) being mechanically pulverized etc..

In turn, it is also proposed that following method: the carrot prime system pigment in the dispersed solution of crystal is miniaturize Afterwards, so that it is dispersed in aqueous materials, or make carrot prime system pigment dispersion after aqueous materials, miniaturize and obtained Method (patent document 4) of colorant etc..However, important parameter when not disclosing for food substantially in patent document 4 is i.e. micro- Refine partial size of the pigment crystal in emulsifier, size distribution or itself and the relationship of the tone of pigment preparation etc..

In turn, molten as the oil for obtaining fast light/excellent heat resistance, storage stability is miniaturize in patent document 5 Property pigment crystal method, propose following method: it is (high to disperse particular emulsifier for the oil-soluble pigment crystal through miniaturizeing The combination of the sorbitan fatty acid ester and/or diglycerine fatty acid ester of the polyglyceryl fatty acid ester of HLB and low HLB), water and The method of the mixed liquor of polyalcohols.It is described in patent document 5: when the partial size of oil-soluble pigment crystal is more than 10 μm, pigment Poor ductility, therefore usually require for crystal to be crushed to 10 μm hereinafter, in addition, be dispersed with the tone of the pigment preparation of crystal because The granularity and size distribution of crystal and it is substantially different.That is, for example crystal particle diameter gradually less than 10 μm when, beta carotene or tomato The tone of the aqueous dispersions of red pigment crystal is gradually varied to peony ~ red ~ orange red ~ orange ~ yellow with miniaturization.Cause And propose: in order to prepare the preparation stablized and without irregular colour, by the way that the average grain diameter of oil-soluble pigment crystal to be set as The range of 100nm ~ 400nm can obtain pigment stable dispersion and the crystal formulations with bright-coloured tone.

However, being still unaware of among the previous preparation or composition comprising hydrocarbon carotenoid crystals and making us meeting , natural cerise is presented and the water dispersible combination of the red colour system oil-soluble pigment crystal with abundant storage stability Object.

Existing technical literature

Patent document

Patent document 1: No. 3592333 bulletins of Japanese Patent No.

Patent document 2: Japanese Patent Publication 03-35347 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2010-132767 bulletin

Patent document 4: Japanese Unexamined Patent Publication 07-90188 bulletin

Patent document 5: No. 4673273 bulletins of Japanese Patent No..

Summary of the invention

Problems to be solved by the invention

The previous pigment preparation for being dispersed with beta carotene or lycopene crystal through miniaturizeing is used as colouring matter When, it is red more apparent when compared with the pigment preparation that beta carotene or lycopene crystal are dissolved in grease and emulsified, but It is still the tone mixed by yellow, orange or red, can not say it is the color for enabling demander sufficiently meet.In addition, by Pigment crystal be scattered with the usage mode of colorant and require light resistance, heat resistance can not be said is sufficient.Thus, the present invention wants The project of solution is that the red tone presentation provided in the water-dispersible composition of beta carotene or lycopene crystal allows People associates the natural cerise naturally felt and light resistance, excellent heat resistance, in addition eats to the beverage added with invention formulation Product also assign the water dispersion of natural cerise and the good miniaturization beta carotene of storage stability or lycopene crystal Property composition.

The means used to solve the problem

According to the present invention people etc. result of study discovery: prepare hydrocarbon carotenoid crystals, especially beta carotene or When the water-dispersible composition of lycopene crystal, the selection of emulsifier is the main of the stability of influence tone and dispersity Factor, such as when exclusive use polyglyceryl fatty acid ester, sucrose fatty ester or sorbitan fatty acid ester, it is difficult to prepare grain Diameter is small, apparent red and even particle size distribution pigment crystal dispersive composition is presented in tone.In addition it finds: in this feelings Under condition, the water dispersion state of beta carotene or lycopene crystal through miniaturizeing becomes unstable, for generating face when food The tendency for phenomena such as tendency of color unevenness is stronger, and chromogenesis is at fractional precipitation, separation when being scattered in beverage is stronger.

Thus, the inventors of the present invention further investigate further directed to the type of emulsifier, combination.The result found that It is lipophilic that low HLB(is further added in the mixed liquor of polyoxyethylene sorbitan fatty acid ester and water and polyalcohol) emulsification After agent and mixing, disperse beta carotene or lycopene crystal, and utilize wet crushing mill by beta carotene or tomato red Beta carotene obtained from cellulose crystal crushes or lycopene crystal dispersive composition have natural cerise tone, thus The stabilized composition of dispersity as miniaturization pigment crystal.In addition it finds: the polyglycereol fat for being 10 ~ 15 to HLB It is lipophilic that low HLB(is further added in acid esters and ethyl alcohol and the mixed liquor of polyalcohols) emulsifier and after mixing, make β-Hu Radish element or lycopene crystal dispersion, the color obtained from wet crushing mill crushes beta carotene or lycopene crystal Cellulose crystal water-dispersible composition has natural cerise tone, so that the water dispersion state for becoming miniaturization pigment crystal is steady Surely the composition changed.About these compositions, as described above, beta carotene or lycopene crystal exist when manufacturing composition In situ (in situ) is pulverized, when adjusting their partial size, especially comprising at least two different emulsifiers and it is not aqueous or Person at most in terms of total composition quality criteria comprising 8 mass parts, to preferably comprise the decentralized media of 5 mass parts water substantially insoluble Or insoluble carotenoid crystals, it is desired for purposes of the present invention.

The water diluent of these water-dispersible compositions comprising beta carotene or lycopene crystal observes by the naked eye It can confirm that the cerise being not present in the past is presented in it.Those skilled in the art have been generally acknowledged that hydrocarbon carotenoid is water-insoluble, When measuring the absorbance in UV, visible light region, it is dissolved in hexane.On the other hand, of the invention includes hydrocarbon carotenoid The water-dispersible composition of crystal contains foregoing emulsifier etc., but finds: being directed to the composition high dilution to water In made of solution or solubilized liquid, using ultraviolet-uisible spectrophotometer measure absorbance when, be capable of providing specific suction Receive spectrum.And then find: the ratio of the absorbance under two different specific wavelengths in this absorption spectrum, which becomes, can determine The parameter of cerise tone that is that the composition is presented and particular product being assigned.It is possible thereby to confirm: if before utilizing Parameter is stated, then can certainly provide and aforementioned cerise tone is presented and assigns the red of the tone to other materials or product Water-dispersible composition.

Therefore, the present invention provides the following technical solutions.

(1) composition, the state to be dispersed in the decentralized medium comprising emulsifier with hydrocarbon carotenoid crystals are deposited And for assigning cherry water-dispersible composition,

The carotenoid crystals be beta carotene or lycopene crystal,

The decentralized medium includes at least two different emulsifiers and not aqueous, or at most with total composition quality criteria Meter includes the water of 8 mass parts, substantially insoluble or insoluble carotenoid crystals, and

In the case where the composition containing beta carotene crystal, 0.004% aqueous solution (W/V) of the composition is measured When absorbance, the ratio (A430nm/A550nm) of the absorbance of 430nm and 550nm be 0.95 hereinafter,

In the case where the composition containing lycopene crystal, 0.004% aqueous solution (W/V) of the composition is measured When absorbance, the ratio (A430nm/A575nm) of the absorbance of 430nm and 575nm is 1.0 or less.

(2) according to the composition of above-mentioned (1), contain:

(A) beta carotene or lycopene crystal；And the sorbitan that (B) HLB as decentralized medium is 2 ~ 6 Diglycerine fatty acid ester that aliphatic ester and/or HLB are 2 ~ 6, (C) polyoxyethylene sorbitan fatty acid ester, (D) water and (E) polyalcohols,

The composition is dispersed in the presence of the state in the mixed liquor of (B), (C), (D) and (E) with (A).

(3) according to the composition of above-mentioned (1), contain:

(A) beta carotene or lycopene crystal；And the sorbitan that (B) HLB as decentralized medium is 2 ~ 6 Diglycerine fatty acid ester that aliphatic ester and/or HLB are 2 ~ 6, the polyglyceryl fatty acid ester that (F) HLB is 10 ~ 15, (G) ethyl alcohol and (E) polyalcohols,

The composition is dispersed in the presence of the state in the mixed liquor of (B), (F), (G) and (E) with (A).

(4) composition according to any one of above-mentioned (1) ~ (3), wherein beta carotene or lycopene crystal Average grain diameter is 100 ~ 400nm.

(5) method is the manufacturing method of the water-dispersible composition of (1) comprising following process:

Beta carotene or lycopene crystal is set to be scattered in the process of decentralized medium, the decentralized medium includes at least two Kind different emulsifier and not aqueous, or include the water of 8 mass parts at most in terms of total composition quality criteria, it is substantially insoluble Solution or insoluble hydrocarbon carotenoid crystals；And

To be dispersed with water dispersible existing for the state of beta carotene or lycopene crystal obtained from operating in this way Composition is diluted in water and measures absorbance, the process for being confirmed as follows gained absorbance:

In the case where the composition containing beta carotene crystal, 0.004% aqueous solution (W/V) of the composition is measured When absorbance, the ratio (A430nm/A550nm) of the absorbance of 430nm and 550nm be 0.95 hereinafter,

In the case where the composition containing lycopene crystal, 0.004% aqueous solution (W/V) of the composition is measured When absorbance, the ratio (A430nm/A575nm) of the absorbance of 430nm and 575nm is 1.0 or less.

(6) method contains the water of beta carotene or lycopene crystal as hydrocarbon carotenoid crystals for manufacture The method of dispersible compositions, which is characterized in that comprise the following steps:

(B) is added into the mixed liquor of (C) polyoxyethylene sorbitan fatty acid ester, (D) water and (E) polyalcohols After diglycerine fatty acid ester that the sorbitan fatty acid ester and/or HLB that HLB is 2 ~ 6 are 2 ~ 6 and mixing, make (A) β-Hu Luo Bu Su or lycopene crystal dispersion in the resulting mixture, with wet crushing mill by the flat of beta carotene or lycopene crystal Equal partial size is crushed, is adjusted to the process of 100 ~ 400nm, and

In the case where measuring the absorbance of 0.004% aqueous solution (W/V) of the dispersible compositions, contain beta carotene When crystal, the ratio (A430nm/A550nm) of the absorbance of 430nm and 550nm is 0.95 hereinafter, containing lycopene crystal When, the ratio (A430nm/A575nm) of the absorbance of 430nm and 575nm is 1.0 or less.

(7) method contains the water of beta carotene or lycopene crystal as hydrocarbon carotenoid crystals for manufacture The method of dispersible compositions, which is characterized in that comprise the following steps:

It is 2 ~ 6 to addition (B) HLB in the mixed liquor of (C) polyoxyethylene sorbitan fatty acid ester and (E) polyalcohols Sorbitan fatty acid ester and/or HLB be 2 ~ 6 diglycerine fatty acid ester and mixing after, make (A) beta carotene or kind Lycopene crystal is dispersed in gained decentralized medium, with wet crushing mill by beta carotene or the average grain of lycopene crystal Diameter is crushed, is adjusted to 100 ~ 400nm, the adjustment liquid that obtains in this way backward in add the process of (D) water, and

In the case where measuring the absorbance of 0.004% aqueous solution (W/V) of the dispersible compositions, contain beta carotene When crystal, the ratio (A430nm/A550nm) of the absorbance of 430nm and 550nm is 0.95 hereinafter, containing lycopene crystal When, the ratio (A430nm/A575nm) of the absorbance of 430nm and 575nm is 1.0 or less.

(8) method contains the water of beta carotene or lycopene crystal as hydrocarbon carotenoid crystals for manufacture The method of dispersible compositions, which is characterized in that comprise the following steps:

(B) is added into the mixed liquor of polyglyceryl fatty acid ester, (G) ethyl alcohol and (E) polyalcohols that (F) HLB is 10 ~ 15 After diglycerine fatty acid ester that the sorbitan fatty acid ester and/or HLB that HLB is 2 ~ 6 are 2 ~ 6 and mixing, make (A) β-Hu Luo Bu Su or lycopene crystal are dispersed in gained decentralized medium, with wet crushing mill by beta carotene or lycopene crystal Average grain diameter is crushed, is adjusted to the process of 100 ~ 400nm, and

In the case where measuring the absorbance of 0.004% aqueous solution (W/V) of the dispersible compositions, contain beta carotene When crystal, the ratio (A430nm/A550nm) of the absorbance of 430nm and 550nm is 0.95 hereinafter, containing lycopene crystal When, the ratio (A430nm/A575nm) of the absorbance of 430nm and 575nm is 1.0 or less.

The effect of invention

Water dispersible containing hydrocarbon carotenoid crystals, especially beta carotene or lycopene crystal of the invention Composition is presented natural cerise, rather than the previous tone mixed by the yellow such as pigment preparation, orange or red, Have following excellent effect when being added to the food such as breaded fish stick, jelly, beverage: can show is more natural and makes one to feel delicious Color, and heat resistance and excellent in light-resistance, the tone variations as caused by pH are few, and then being dispersed to after the aqueous solutions such as beverage will not Precipitating, ring etc. after there is long-time.

Detailed description of the invention

Fig. 1 is invention product 1,2 when having used based on beta carotene crystal of the invention and the water dispersible for comparing product 1 The spectrum (400 ~ 700nm) of 0.004% aqueous solution (W/V) of composition.

Fig. 2 is invention product 3,4 when having used based on lycopene crystal of the invention and the water dispersible group for comparing product 2 Close the spectrum (400 ~ 700nm) of 0.004% aqueous solution (W/V) of object.

Specific embodiment

Hereinafter, being described in detail for further progress of the present invention.

Technical term used in this specification etc. is can be regarded as in case of no particular description with this technology neck Usually used meaning, content in domain.

Water-dispersible composition refers to: the combination of the two or more ingredients comprising the property for being shown to disperse in water Object.With crystal dispersion, state presence refers in a dispersion medium: the crystal is deposited in which will not precipitate or assemble in a dispersion medium State.One of (A) ingredient being able to use in such a composition i.e. beta carotene can be slaves to the palm fibre of natural goods The ingredient extracted in the fruits such as yellow greens vegetables, the mango such as palmitic acid oil, carrot, pumpkin, be also possible to be obtained by synthetic method at Point.Lycopene as another (A) ingredient can be slaves to the ingredient extracted in the fruits such as the tomato of natural goods, It can be the ingredient obtained by synthetic method.Aforementioned beta carotene or lycopene use the substance of crystal state, can also make crystalline substance Body is suspended in grease etc. and adjusts to the state with appropriate partial size.

This beta carotene or lycopene crystal can be broken by a certain size Crystal Powders in advance and by average grain diameters It is mixed after adjusting to 100 ~ 400nm into aforementioned decentralized medium.

Cerise refers to: not being the state of the beta carotene present in water-dispersible composition or lycopene crystal And the tone of observable yellow, orange or red through mixing, and make by reducing or reducing the tone other than red And the tone shown.Objectively, the case where measuring the absorbance of 0.004% aqueous solution (W/V) of water-dispersible composition Under, when containing beta carotene crystal, the ratio (A430nm/A550nm) of the absorbance of 430nm and 550nm has 0.95 or less Value, when containing lycopene crystal, the ratio (A430nm/A575nm) of the absorbance of 430nm and 575nm has 1.0 or less Value, thus, it is possible to identify such tone.

As usual opinion, the wavelength of yellow is that the wavelength of 430nm nearby, red is near 550nm.Therefore, 430nm Absorbance indicate that the intensity of yellow, the absorbance of 550nm indicate red intensity.That is, the absorbance of 430nm and 550nm When ratio (A430nm/A550nm) is big, present yellow be mixed into it is more it is red, i.e. close to orange tone, the value hour, presentation Yellow is mixed into less red, i.e. cerise.It could be said that composition of the invention by make aforementioned ratio 0.95 hereinafter, from But cerise is presented and the water-dispersible composition of cherry red colour system oil-soluble pigment crystal can be assigned.

In the present invention, the average grain diameter of beta carotene or lycopene crystal is preferably 100 ~ 400nm.Such as patent document 5 Shown in recording like that, in the miniaturization of beta carotene or lycopene crystal, in general, when crystal particle diameter is more than 10 μm, The extension of pigment is poor, and crystal is usually crushed to 10 μm hereinafter, but being dispersed with the beta carotene or lycopene pigment of crystal The tone of preparation is significantly different because of crystal size and size distribution.For example, the crystal particle diameter of beta carotene or lycopene is big When 10 μm (10000nm), coloring is insufficient, when making crystal particle diameter gradually less than 10 μm in order to improve coloration efficiency, with It miniaturize and gradually becomes peony ~ red ~ orange red ~ orange ~ yellow.In the present invention, by by beta carotene or tomato red The average grain diameter of cellulose crystal is set as that the range of 100nm ~ 400nm, the former is preferably set to 180 ~ 230nm, is more preferably set as 190 ~ 210nm, the latter are preferably set to 210 ~ 280nm, are more preferably set as 230 ~ 270nm, so as to obtain stable dispersion With the crystalliferous water-dispersible composition with bright-coloured tone.

In the present invention, it is set as the models such as 100nm ~ 400nm for by the average grain diameter of beta carotene or lycopene crystal The method enclosed, is not particularly limited, and the substance that average grain diameter micro mist is broken to 100 ~ 400nm in advance can be used, can also lead to It crosses dry grinding and average grain diameter is set as 100 ~ 400nm, it is usually mixed with other raw material used in the present composition After conjunction, carries out case of wet attrition and the subparticle that average grain diameter is 100 ~ 400nm is made.That is, the method as dry grinding, it can It exemplifies beta carotene or lycopene crystal can be crushed to and powder is carried out with the device that average grain diameter is calculated as 100 ~ 400nm Broken method.As this device, as long as the average grain diameter of crushed material can be crushed to the device of 100 ~ 400nm, then may be used To use any device.As their various commercially available pulverizers, such as fluidized bed-type jet pulverizer JEDI can be enumerated (registered trademark: ア ー ス テ Network ニ カ corporation), continous way dry type ball mill DRYSTAR SDA(registered trademark: ア シ ザ ワ Off ァ イ Application テ ッ Network corporation), miniature ACM pelletizer AC-30H(registered trademark: ホ ソ カ ワ ミ Network ロ Application corporation), MicronJet MJ-3 shape (registered trademark: ホ ソ カ ワ ミ Network ロ Application corporation), マ イ Network ロ ス (MIC) (registered trademark: how Good opportunity tool corporation), New Cosmo miser(N-COS) (registered trademark: nara machinery corporation), SINGLE TRACK JET MILL, JET O MILL(the above are match new spectra Co. Ltd. system), Super Spray formula pulverizer/SJ series (Nisshin Engineering Inc. system), jet pulverizer (ア イ シ Application industry companies system) etc..It can be by a kind or 2 kinds in them Combination of the above, or repeat miniaturization using same machines and handle.However, in the case where dry grinding, due to micro mist Disperse, generate heat and lead to resolidification etc., therefore efficiency is not so good, to usually carry out case of wet attrition.

In addition, the method as case of wet attrition, can exemplify following method: with constitute the aftermentioned present composition other After raw material mixing, using beta carotene or lycopene crystal capable of being crushed in terms of average grain diameter by wet crushing mill It is crushed for the device of 100 ~ 400nm, in other words, when manufacturing water-dispersible composition, beta carotene or lycopene is existed (in situ) in situ is ground into appropriately sized crystal, their partial size is adjusted to the method for aforementioned average grain diameter.As that Any device then can be used as long as the average grain diameter of crushed material can be crushed to the device of 100 ~ 400nm in kind device. As their various commercially available pulverizers, such as pearl type case of wet attrition device (OB MILL, Ultra Apex Mill can be enumerated Deng), the roller of roller mill rotation mill (ロ ッ シ ェ ミ Le etc.), centrifugal roller mill (thunder covers pulverizer etc.), high-speed rotation mill turbine Grind the circulation tube mill (Sand of type (turbo-mill etc.), fixed impact template (wet mill etc.), medium stirring mill Grinder), jet-stream wind impingement (the マ ジ ャ ッ Network パ Le ペ ラ of stirring slot type mill (grater etc.), jet pulverizer イ ザ ー etc.), impact template compound (SUPER SINGLE TRACK JET MILL etc.), other colloid mills etc..It can be by it In one kind or two or more combination, or using same machines repeat miniaturization handle.

The use level of beta carotene or lycopene crystal in water-dispersible composition is relative to water-dispersible composition 100 mass parts are 1 ~ 10 mass parts.When the use level of beta carotene or lycopene crystal is less than 1 mass parts, as pigment system The efficiency of agent is weaker, cooperate more than 10 mass parts when, beta carotene or lycopene crystal are difficult to miniaturize, beta carotene or Lycopene crystal will not be fully dispersed, it is possible to phenomena such as aggregation/precipitating occurs.

In the present invention, as in the case where measuring the absorbance of 0.004% aqueous solution (W/V) of water-dispersible composition The ratio (A430nm/A550nm) of the absorbance of 430nm and 550nm when for by containing beta carotene crystal is set as 0.95 or less and the ratio (A430nm/A575nm) of the absorbance of 430nm when by containing lycopene crystal and 575nm set It is set to 1.0 emulsification systems below, as long as there can be the emulsification system of this feature absorbance, so that it may not limit ground It uses.But it is based on aftermentioned theoretically intelligible content, it can exemplify comprising at least two different emulsifiers and be free of Water or at most in terms of total composition quality criteria include 8 mass parts water, and substantially insoluble or insoluble β-carrot The emulsification system of element or lycopene crystal.In addition, being not limited to this, as typical example, two individual below can be exemplified System.

Firstly, being containing ingredient (A) ~ (E) as the 1st system: (A) beta carotene or lycopene crystal, (B) HLB Diglycerine fatty acid ester that sorbitan fatty acid ester and/or HLB for 2 ~ 6 are 2 ~ 6, (C) polyoxyethylene sorbitol acid anhydride Aliphatic ester, (D) water and (E) polyalcohols and (A) are dispersed in composition made of in the mixed liquor of (B), (C), (D) and (E).

In addition, being containing ingredient (A), (B), (F), (G) and (E): (A) beta carotene or tomato red as the 2nd system Diglycerine fatty acid ester that cellulose crystal, the sorbitan fatty acid ester that (B) HLB is 2 ~ 6 and/or HLB are 2 ~ 6, (F) HLB are 10 ~ 15 polyglyceryl fatty acid ester, (G) ethyl alcohol and (E) polyalcohols and (A) are dispersed in the mixed liquor of (B), (F), (G) and (E) In made of composition.It is explained for (A) ingredient, therefore first against the common ingredient of the 1st system and the 2nd system It is illustrated.

In the present invention, cooperation is 2 ~ 6 sorbitans sugar as the lipophilic emulsifier of (B) ingredient, i.e. HLB in composition The diglycerine fatty acid ester that aliphatic ester and/or HLB are 2 ~ 6.β-Hu by cooperation (B) ingredient, in water-dispersible composition The dispersion stabilization of radish element or lycopene crystal improves, and dispersion can be also stably kept when being in addition engaged to beverage/food. In addition, beta carotene when preparing the present composition or in the Crushing of Ultrafine of lycopene crystal, in the feelings for carrying out case of wet attrition Under condition, play the role of being easy to be micronized as grinding aid.

It is 2 ~ 6 sorbitan sugar fatty acid esters as the i.e. HLB of (B) ingredient being able to use in the present invention, can enumerates Sorbitan monooleate, sorbitan monostearate, sorbitan distearate, sorbitan three are stearic Acid esters, sorbitan tribehenin acid esters etc. among these, can particularly preferably exemplify sorbitan monooleate, mountain Pears sugar alcohol acid anhydride monostearate.

In addition, the diglycerine fatty acid ester for being 2 ~ 6 as another HLB for belonging to (B) ingredient, can enumerate diglycerol list Stearate, Sunsoft Q 16D, Diglycerin monomyristate, diglyceryl monooleate etc. can be special among these Preferably exemplify diglyceryl monooleate.

Can exemplify: use level of (B) ingredient in water-dispersible composition is relative to 100 mass of water-dispersible composition Part is 1 ~ 5 parts by weight or so.(B) when the use level of ingredient is less than 1 mass parts, beta carotene or lycopene crystal are difficult to micro- Refinement, furthermore, it is possible to can not be evenly dispersed.

In the present invention, polyalcohol of the cooperation as (E) ingredient in composition.Pass through cooperation (E) ingredient, water dispersible combination The dispersion stabilization of beta carotene or lycopene crystal in object improves, in addition, can also stablize when being engaged to beverage/food Ground keeps dispersion.In addition, the mobility of water-dispersible composition entirety improves, in addition, diffusivity when being engaged to water improves, deposit This excellent effect is easily processed when being engaged to beverage/food.

As ingredient (E) the i.e. polyalcohols being able to use in the present invention, such as glycerol, propylene glycol, sorb can be exemplified The carbohydrates such as sugar alcohol, maltitol, starch decomposition-reduction object, glucose, sucrose, maltose and their two or more mixing Object among these, can particularly preferably exemplify glycerol, D-sorbite, propylene glycol.As the use level of ingredient (E), relative to 100 mass parts of water-dispersible composition, can exemplify 60 ~ 87 mass parts.

For realizing in the 1st system of the object of the invention, as distinctive constituent, (C) polyoxyethylene is used Sugar alcohol acid anhydride aliphatic ester and (D) water.By cooperating both ingredients in water-dispersible composition, can make beta carotene or The less cerise of yellow is presented in lycopene crystal.The less cherry the principles of science of yellow is presented still by the combination Indefinite, in addition, without being bound by theory, the inventors of the present invention are presumed as follows.That is, in the present invention, the sorbose that (B) HLB is 2 ~ 6 The diglycerine fatty acid ester that alcohol acid anhydride aliphatic ester and/or HLB are 2 ~ 6 is the crushing of beta carotene or lycopene crystal and divides Stabilized important component is dissipated, but it is oil-soluble, therefore a part of meeting of the red colour system oil-soluble pigment crystal through miniaturizeing Dissolution (it is believed that: when being miniaturize, the surface area of every phase homogenous quantities be will increase, therefore be easy dissolution), become the portion of solution Divide and orange ~ yellow is presented, which can assign yellow to the tone of composition entirety.On the other hand, polyoxyethylene sorbitol Acid anhydride aliphatic ester is the stronger emulsifier of hydrophily, therefore the dissolution part of the beta carotene crystal through miniaturizeing is few, therefore, Color (orange ~ yellow) when pigmentolysis is in the mixed solution of the ingredient of constitution system will not influence the color of composition entirety It adjusts.

Polyoxyethylene sorbitan fatty acid ester as (C) ingredient is condensed about into sorbitan fatty acid ester Made of 20 molecule ethylene oxide, also referred to as polysorbate.As the preferred of polyoxyethylene sorbitan fatty acid ester Example, it is hard can to enumerate polyoxyethylene sorbitan monolaurate (polysorbate 20), polyoxyethylene sorbitol acid anhydride list Resin acid ester (polysorbate 60), polyoxyethylene sorbitan tristearate anhydride (polysorbate 65), polyoxyethylene Sugar alcohol acid anhydride monoleate (polysorbate 80).The use level of polyoxyethylene sorbitan fatty acid ester is relative to water dispersible 100 mass parts of composition can exemplify 10 ~ 20 mass parts.The use level of polyoxyethylene sorbitan fatty acid ester is the range When outer, in the process of the case of wet attrition then carried out, it is difficult to beta carotene or lycopene crystal are fully miniaturize, It is possible that the uniform and beta carotene of long-time stable or the water-dispersible composition of lycopene crystal can not be become.

As described above, the containing for water as (D) ingredient is purposefully: make the colour generation of the present composition that cerise be presented, And the mobility of composition entirety is improved, the crystal crush efficiency in case of wet attrition is improved and then improves composition in water Combination.The mixing ratio of water can exemplify 2 ~ 6 mass parts relative to 100 mass parts of water-dispersible composition.

For realizing in the 2nd system of the object of the invention, as distinctive constituent, using (F) HLB is 10 ~ 15 Polyglyceryl fatty acid ester and (G) ethyl alcohol.By cooperating both ingredients in water-dispersible composition, beta carotene can be made Or the less cerise of yellow is presented in lycopene crystal.The less cherry mechanism of yellow is presented still not by the combination It is clear, theoretically speculate roughly the same with the mechanism for the narration of aforementioned 1st system.

As (F) ingredient, that is, polyglyceryl fatty acid ester, HLB needs to be 10 ~ 15, in addition, the average degree of polymerization of glycerol is preferred It is 6 ~ 15, more preferably 8 ~ 10.Using HLB be 10 polyglyceryl fatty acid ester below when, it is difficult to preparation uniformly and partial size it is small Pigment granule, in addition, when being added to beverage under the dispersity unstable state of beta carotene or lycopene crystal, The tendency for generating the segregation phenomenons such as precipitating, oil separation is stronger.As the preference of polyglyceryl fatty acid ester, six glycerol can be enumerated Monostearate, SY-Glyster MSW 750, SY-Glyster MO 750, ten monomyristins, ten glycerol list palmitinic acids Ester etc. among these, can particularly preferably exemplify SY-Glyster MSW 750, SY-Glyster MO 750, ten glycerol list palms Acid esters.The use level of polyglyceryl fatty acid ester can exemplify 9 ~ 15 mass parts relative to 100 mass parts of water-dispersible composition.It is poly- When the use level of fatty acid glyceride is outside the range, in the process of the case of wet attrition then carried out, it is difficult to by beta carotene Or lycopene crystal is fully miniaturize, it is possible to can not become uniform and long-time stable beta carotene or tomato red Cellulose crystal dispersive composition.

As described above, the containing for ethyl alcohol as (G) ingredient is purposefully: the colour generation of the present composition is presented scarlet Color, and improve the mobility of composition entirety, improve the crystal crush efficiency in case of wet attrition and then improve composition in water In Combination.The mixing ratio of ethyl alcohol can exemplify 2 ~ 6 mass parts relative to 100 mass parts of water-dispersible composition.

In addition to that mentioned above, it in water-dispersible composition of the invention, for the purpose for improving keeping quality, can also add The organic acids such as lactic acid, citric acid, malic acid, tartaric acid.Alternatively, it is also possible to functional former by addition vitamins, fragrance etc. Material further assigns functionality.

As vitamins to be added, such as liver oil, vitamin A, oleovitamin A, vitamine D3, dimension life can be enumerated Plain B2 butyrate, natural VE mixture etc..As the concrete example of fragrance, orange oil, lemon oil, oil of grapefruit, acid can be enumerated The tangerine oils classes such as orange oil, tangerine oil, mandarin orange oil and bergamot oil；The essential oils class such as peppermint oil, spearmint oil, cinnamon oil；It is mostly fragrant Fruit, anise seed, sweet basil, bay tree, cardamom, celery, cloves, cumin, fennel seeds, garlic, ginger, nutmeg (mace), The aromatic condiment essential oils such as mustard, onion, pimiento, parsley, black pepper, cardamom, safron, rosemary or oil-containing rosin class；And Limonene, linalool, nerol, citronellol, geraniol, citral, l-menthol, eugenol, cinnamic acid, anethole, purple Soviet Union aldehyde, vanillic aldehyde, gamma-undecalactone, l- carvol, maltol, furfuryl mercaptan, ethyl propionate, allyl hexanoate, methyl positive penta Flavor compounds well known to base ketone, biacetyl, acetic acid, butyric acid etc.；Sesame oil (reaction flavor)；And by these natural essential oils, Any combination such as oil-containing rosin and flavor compounds and mixed compound perfume, are not limited to them.

It can be exemplified as the use level of these functional raw materials relative to 100 mass parts of water-dispersible composition In the range of 0.001 ~ 5 mass parts.

If exemplifying a preferred implementation of the water-dispersible composition of beta carotene or lycopene crystal of the invention Mode, then as follows.

For example, first in the 1st system, it is previously prepared first by (C) polyoxyethylene sorbitan fatty acid ester, (D) The solution that water and (E) polyalcohols mix, after being heated to about 80 ~ 90 DEG C, is cooled to 40 ~ 50 DEG C.Then, (B) HLB is added After diglycerine fatty acid ester that sorbitan fatty acid ester and/or HLB for 2 ~ 6 are 2 ~ 6 and mixing, (A) β-carrot is put into Element or lycopene crystal, are stirred liquid with mixer for well-distribution etc., to prepare crushing stoste.Herein, in order to improve powder The crush efficiency of crushing device, can also further hydrous water or ethyl alcohol.Then carry out case of wet attrition, be crushed to beta carotene or The average grain diameter of lycopene crystal reaches 100 ~ 400nm.In the range of above-mentioned match ratio to terminate crush liquid in into One step water or ethyl alcohol dilution, and then be stirred, so as to adjust the physical property of water-dispersible composition.In addition, in the 1st system, (D) water of ingredient is not necessarily required to be pre-mixed, and can also add again after being pulverized.

In addition, in the 2nd system, it is previously prepared first by (F) HLB be 10 ~ 15 polyglyceryl fatty acid ester, (G) ethyl alcohol and (E) solution that polyalcohols mix after being heated to about 80 ~ 90 DEG C, is cooled to 40 ~ 50 DEG C.Then, addition (B) HLB be 2 ~ 6 sorbitan fatty acid ester and/or HLB be 2 ~ 6 diglycerine fatty acid ester and mixing after, put into (A) beta carotene or Lycopene crystal is stirred liquid with mixer for well-distribution etc., to prepare crushing stoste.Herein, dress is crushed in order to improve The crush efficiency set, can also further hydrous water or ethyl alcohol.Then case of wet attrition is carried out, beta carotene or tomato are crushed to The average grain diameter of red pigment crystal reaches 100 ~ 400nm.In the range of above-mentioned match ratio further into the liquid for terminating to crush It is diluted, and then is stirred with water or ethyl alcohol, so as to adjust the physical property of water-dispersible composition.

It should be noted that the method being miniaturize to beta carotene or lycopene crystal is as described above.

In the quilt that can be coloured by product of the present invention containing the water-dispersible composition of beta carotene or lycopene crystal It among coloured material or product, as food, is not particularly limited, such as cold drink (drink comprising fruit juice can be enumerated Material), soda, fruit drink, vegetable beverage, vegetables/fruit nectar, sports drink, powder drink, milk beverage, lactic acid bacteria The beverages class such as beverage；The desserts such as the cloth class D such as jelly, pudding-like cold spot, yogurt and cow's milk pudding, milk pudding, fruit juice pudding Class；Breaded fish stick, the flesh of fish shred object, alec, fish sweet potato cake, fried fish cutlet, flesh of fish omelet, fish ham, fish meat sausage, spermaceti The aquatic products prepared food such as meat；The poultry meat processed goods such as ham, sausage, skewer-roasted pork；Ice cream, blancmange, lactic acid ice cream, fruit syrup ice river in Henan Province The frozen desserts class such as leaching, freezing point；The alcohol drinks such as julapium；Coffee beverage；The tea beverage class such as black tea drinks；Clear soup, thick soup etc. Soup class；The chewing gums such as chewing gum, bubble gum class (chip chewing gum, sugar-coat shape grain formula chewing gum)；The sheets such as lemonade dessert point The heart；The coating chocolate and Strawberry Covered with Chocolate, blueberry chocolate and muskmelon chocolate etc. such as sugared beans chocolate impart flavor The chocolate-likes such as chocolate or its sugar-coat；The hard candy classes such as whisky heart chocolate, butter ball, sugared beans, fruit drops, taffy；Toffee, ox Roll the soft sweets class such as sugar, chewing gum, cotton candy；The barbecue snack categories such as hardlack, cookies, snow cake, thin pancake；It salts down vegetables cruelly, soy sauce salts down Salted vegetables, salt salt down vegetables, pickles, vinasse pickle, rice song pickles, rice bran pickles, vinegar pickles, mustard seed pickles, do not filter wine pickles, use The plums of the marinades such as salt or liquor, assorted sweet eight-treasure pickles, bavin pickles (salted chopped pickled vegetables), The pickles class such as ginger pickles, Korea's pickles, plum juice pickles；It separates baste, emulsification baste, oil-free baste, catsup, bake The bastes class such as meat flavorings juice, baste；The jams such as strawberry jam, blueberry jam, organe peel jam, apple jam, apricot sauce, preserved fruit；It is red The fruits wine such as wine；The fruits such as cherry, apricot, apple, strawberry, peach, the plum meat of sugar bowl head process category；The cheese animal husbandry system such as cheese Category；The faces such as Wu Dong, flow surface item, vermicelli, buckwheat flour, Chinese noodle, pasta, macaroni, rice flour, bean vermicelli and won ton Class；And the various processed foods such as various home cookings and gluten, dried meat floss.In addition, such as various can be enumerated as pharmaceuticals Agent, capsule, drink agent, buccal tablet, mouthwash, sugar coated tablet etc. can enumerate in such as toothpaste, mouth as medical exterior-applied article Freshener, anti-halitosis dose etc. can enumerate the various pet foods such as cat food, dog food, ornamental fish is used or cultivation as feed The bait etc. of fish.Furthermore it is also possible to which the coloring for cosmetics such as soap, shampoos, preferably beverage/food, particularly preferably drink Material, jelly and cooked product (crab breaded fish stick etc.).

In addition, can be engaged to the ratio of the colouring matter of the invention of these products according to product type, purpose different, nothing Method is lumped together, and relative to 100 mass parts of product, usually can suitably be selected and be adjusted to 0.01 ~ 20 mass parts, preferably 0.05 ~ 5 mass parts.

Then, enumerating embodiment, present invention be described in more detail.

Embodiment

Product of the present invention and the physical property (tone etc.) for comparing product are measured using following device, method.

Use device:

Ultraviolet-uisible spectrophotometer: ア ジ レ Application ト corporation Agilent(registered trademark) 8453

Colour difference meter: Nippon Denshoku Industries Co., Ltd. spectrial photometer SD5000

Average grain diameter: great Zhong Electronics Co., Ltd laser Z potentiometer ELS-8000.

Measuring method

Zero spectrum, tone, turbidity

0.004% aqueous solution (W/V) for preparing water-dispersible composition measures wavelength using ultraviolet-uisible spectrophotometer Spectrum under 400 ~ 700nm.In addition, using the dulling luminosity ratio of A430nm/A550 or A575nm as hue evaluation (red and yellow Balance) index, by the absorbance (A680nm) of wavelength 680nm be used as turbidity.

Zero color difference (Lab)

0.004% aqueous solution (W/V) for preparing water-dispersible composition determines the transmission of measurement sample using colour difference meter L value, a value, the b value of light.Reference of these values by the balance of brightness, red and yellow as hue evaluation.

(embodiment 1) has used the water-dispersible composition of the beta carotene crystal of polysorbate 80 and water

By polysorbate 80 (C ingredient: 36g), glycerol (E ingredient: 183g) and purified water (D ingredient: 33g) with 90 ~ 95 DEG C after heating for dissolving/sterilization 15 minutes, it is cooled to 50 ~ 55 DEG C.Tocopherol (0.6g) and D-sorbite are added into the mixture Acid anhydride monoleate (B component: 6g), is made water phase portion.Into the water phase portion, addition crystallization beta carotene (A ingredient: 15g), makes With high-speed emulsifying machine (TK- mixer for well-distribution: PRIMIX corporation), is stirred 15 minutes, tied with 6000 ~ 7000 revs/min The broken stoste of crystalline flour.By stoste 250g with case of wet attrition device (0.5 type of OB MILL: FREUND TURBO. corporation) with 2000 revs/min of stirrings crush 3 hours, to obtain pulverization process product.To addition purified water in pulverization process product (234.5g) (20.3g) is stirred 5 minutes with high-speed emulsifying machine with 3000 revs/min, so that the average grain diameter for obtaining beta carotene is about The water-dispersible composition (240g, product 1 of the present invention) of the crystal of 200nm.

(embodiment 2) has used the water-dispersible composition of the beta carotene crystal of polyglyceryl fatty acid ester and ethyl alcohol

By SY-Glyster MO 750 (F ingredient: 36g), glycerol (E ingredient: 183g) and ethyl alcohol (G component: 33g) with 90 ~ 95 DEG C after heating for dissolving/sterilization 15 minutes, it is cooled to 50 ~ 55 DEG C.Tocopherol (0.6g) and D-sorbite are added into the mixture Acid anhydride monoleate (B component: 6g), is made water phase portion.Addition crystallization beta carotene (15g) into the water phase portion, uses high speed Mulser (TK- mixer for well-distribution: PRIMIX corporation) is stirred 15 minutes with 6000 ~ 7000 revs/min, is obtained crystallization and is crushed Stoste.By stoste 250g with case of wet attrition device (0.5 type of OB MILL: FREUND TURBO. corporation) with 2000 revs/min Clock stirring crushes 3 hours, to obtain pulverization process product.Purified water (22.5g) is added in the item for disposal (228g), with high speed Mulser is stirred 5 minutes with 3000 revs/min, thus the moisture for the crystal that the average grain diameter for obtaining beta carotene is about 200nm It dissipates property composition (240g, product 2 of the present invention).

(comparative example 1): the polysorbate of embodiment 1 is replaced (to replace reality using water using polyglyceryl fatty acid ester Apply the ethyl alcohol of example 2)

By SY-Glyster MO 750 (36g), glycerol (183g) and purified water (33g) with 90 ~ 95 DEG C of heating for dissolving/sterilizations 15 After minute, it is cooled to 50 ~ 55 DEG C.Tocopherol (0.6g) and sorbitan monooleate (6g), system are added into the mixture At water phase portion.Into the water phase portion add beta carotene crystal (15g), using high-speed emulsifying machine (TK- mixer for well-distribution: PRIMIX corporation), it is stirred 15 minutes with 6000 ~ 7000 revs/min, obtains crystallization and crush stoste.By stoste 250g with wet Formula grinding device (0.5 type of OB MILL: FREUND TURBO. corporation) is crushed 3 hours with 2000 revs/min of stirrings, thus Obtain pulverization process product.Purified water (22.5g) is added in the item for disposal (228g), with high-speed emulsifying machine with 3000 revs/min Stirring 5 minutes, thus the water-dispersible composition (240g, comparing product 1) that the average grain diameter for obtaining beta carotene is about 200nm.

(physical property (turbidity, tone ratio, tone, average grain diameter) of the product 1 compared with of product 1,2 of the present invention)

By the spectrum of product 1,2 of the present invention and 0.004% aqueous solution (W/V) for the water-dispersible composition for comparing product 1 (400 ~ 700nm) it is shown in Fig. 1.In addition, by the ratio (A430nm/ of the absorbance of product 1,2 of the present invention and the 430nm and 550nm that compare product 1 A550nm) shown in table 1.

[table 1]

。

As shown in figure 1 and table 1, the 0.004%(W/V of product 1 and 2 of the present invention) aqueous solution visually (visually observing) be Red, but the combination for comparing the emulsifier in No. 4673273 inventions of product 1(Japanese Patent No. etc.) it is slightly aobvious orange red Color.

In spectroscopic assay, product 1,2 of the present invention and compare product 1 near 550nm, 500nm and 470nm there are peak, this The peak 550nm in invention product 1 and 2 is top, and comparing the peak 470nm in product 1 is top, along with this, also expanding Acromion until low wavelength side (430nm).Thus, for display yellow 430nm absorbance value be displayed in red When the ratio (A430nm/A550nm) of the absorbance value of 550nm is evaluated, product 1 of the present invention, product of the present invention 2 and compare product 1 Value is respectively 0.679,0.711,1.08, and notable difference can be observed between product 1 compared in product 1 and product of the present invention 2 of the present invention.It examines When considering that compare product 1 be the water-dispersible composition of the beta carotene crystal based on the prior art, if A430nm/A550nm Value for 0.95 or less, preferably 0.90 or less, more preferably 0.85 or less, further preferably 0.80 hereinafter, it can be said that its Obvious red relatively strong, presentation cerise compared with prior art.

In addition, being directed to Lab, the positive side of a value is red index, the index that negative side is green, and the positive side of b value is yellow Index, the index that negative side is blue.Known to when evaluating Lab measurement result: product 1,2 of the present invention and comparing product 1 from the point of view of a value red Without king-sized difference in terms of color, but from the point of view of b value when compare product 1 yellow it is stronger.As a result, it is considered that comparing product 1 It is slightly aobvious orange red.

Among these numerical value, stable measurement knot when carrying out numerical value judgement, can be obtained as red ~ orange index Fruit, one of the index as reflection tone, it is believed that A430nm/A550nm is very effective.

(food preservation test of the water-dispersible composition of beta carotene crystal)

By product 1,2 of the present invention and compare the bottleneck of the vial that product 1 are filled respectively to 15ml capacity, refrigerated (5 DEG C), Room temperature, 40 DEG C, the food preservation test between 2 months carry out turbidity, tone, the average grain diameter measurement of the water-dispersible composition of crystal. It the results are shown in table 2.

[table 2]

。

As clearly shown in the result of table 2, turbidity, tone ratio, color difference and the average grain diameter of product 1 of the present invention refrigeration, room temperature, 40 DEG C, there is no after 2 months food preservation tests and variation immediately after preparation, tone stability and dispersity are good. In addition, product 2 of the present invention also show good tone stability in the same manner as product 1 of the present invention in the food preservation test between 2 months.

It should be noted that the color about product 1 are compared, in the same manner as product 1,2 of the present invention, in 2 months food preservation tests Adjust stability and dispersity good.

(stability test in beverage substrate)

By product 1,2 of the present invention and compares product 1 and be added to beverage substrate group shown in table 3 to assign fragrant rate for 0.004%(W/W) Cheng Zhong is cooled to room temperature after progress heat wraps up in filling (central temperature is 90 ± 2 DEG C) into 300mL plastic bottle and stability is made Sample is used in test.

[table 3]

。

By they refrigeration (4 DEG C), room temperature (about 20 DEG C), 40 DEG C these three under the conditions of save 2 months, evaluation save during After the spectroscopic assay of sample, appearance/tone ongoing change.In evaluation, using freshly prepd beverage as control, visually Appearance (whether dispersity, precipitating and the crystal of pigment are precipitated), tone evaluated.Appearance judges according to following benchmark.◎: with Control is compared to unchanged；△: abnormal state is felt compared with the control；×: ring/aggregation etc. is obviously observed compared with the control It is abnormal.Show the result in table 4.

[table 4]

。

As shown in table 4 when can be confirmed that like that by 2 months, product 1,2 of the present invention and compares product 1 and do not observe in pol Precipitating and crystal are precipitated caused by occurring in two kinds of different beverage substrates because of addition beta carotene crystal dispersive composition Occur, tone is also unchanged compared with the control, maintains kilter, is engaged to also stable in beverage substrate.

(embodiment 3) has used the water-dispersible composition of the beta carotene crystal of polysorbate 20 and water

Other than the polysorbate 80 for using polysorbate 20 to replace embodiment 1, carry out complete with embodiment 1 Identical operation, to obtain product 3(240g of the present invention).

(embodiment 4) has used the water-dispersible composition of the beta carotene crystal of polysorbate 60 and water

It other than replacing the polysorbate 80 in embodiment 1, is carried out complete with embodiment 1 in addition to using polysorbate 60 Exactly the same operation, to obtain product 4(240g of the present invention).

(embodiment 5) has used the water-dispersible composition of the beta carotene crystal of polysorbate 60 and propylene glycol

Replace that the polysorbate 80 in embodiment 1, to use propylene glycol sweet to replace in addition to using polysorbate 60 Except oil, progress and the identical operation of embodiment 1, to obtain product 5(240g of the present invention).

(embodiment 6) has used the water dispersible of the beta carotene crystal of polysorbate 80 and diglyceryl monooleate Composition

In addition to use diglyceryl monooleate come other than replacing the sorbitan monooleate in embodiment 1, carry out with The identical operation of embodiment 1, to obtain product 6(240g of the present invention).

(comparative example 2) replaces the polysorbate 60 of embodiment 5 using SY-Glyster MO 750

Other than the polysorbate 60 for using SY-Glyster MO 750 to replace embodiment 5, carry out complete with embodiment 5 Exactly the same operation, to obtain comparing product 2(240g).

(product 3 ~ 6 of the present invention and the physical property (turbidity, tone ratio, tone, average grain diameter) for comparing product 2)

Product 3 ~ 6 of the present invention and the physical property (turbidity, tone ratio, tone, average grain diameter) for comparing product 2 are shown in table 5.

[table 5]

。

As shown in table 5 like that, the combination of emulsifier of the present invention etc. is that red is presented in product 3 ~ 6 of the present invention, but compares The combination of emulsifier compared with product 2(No. 4673273 inventions of Japanese Patent No. etc.) present slightly show orange red.The present invention The A430nm/A550nm of product is 0.95 hereinafter, but comparing the value in product 2 is more than 0.95.In the moisture of beta carotene crystal It dissipates in property composition, does not know still that this cherry composition is presented, it may be said that realize through the invention and for the first time.

(embodiment 7) has used the water-dispersible composition of the lycopene crystal of polysorbate 80 and water

By polysorbate 80 (C ingredient: 36g), glycerol (E ingredient: 183g) and purified water (D ingredient: 33g) with 90 ~ 95 DEG C after heating for dissolving/sterilization 15 minutes, it is cooled to 50 ~ 55 DEG C.Tocopherol (0.6g) and D-sorbite are added into the mixture Acid anhydride monoleate (B component: 6g), is made water phase portion.Lycopene crystal (A ingredient: 15g) is added into the water phase portion, is used High-speed emulsifying machine (TK- mixer for well-distribution: PRIMIX corporation) is stirred 15 minutes with 6000 ~ 7000 revs/min, is crystallized Crush stoste.By stoste 250g with case of wet attrition device (0.5 type of OB MILL: FREUND TURBO. corporation) with 2000 Rev/min stirring crush 3 hours, to obtain pulverization process product.It is pure to addition in the pulverization process product (228.0g) recycled Change water (22.5g), stirred 5 minutes with high-speed emulsifying machine (TK- mixer for well-distribution: PRIMIX corporation) with 3000 revs/min, To obtain the water-dispersible composition (240g, product 7 of the present invention) for the crystal that the average grain diameter of lycopene is about 200nm.

(embodiment 8) has used the water-dispersible composition of the lycopene crystal of polyglyceryl fatty acid ester and ethyl alcohol

By SY-Glyster MO 750 (F ingredient: 36g), glycerol (E ingredient: 183g) and ethyl alcohol (G component: 33g) with 90 ~ 95 DEG C after heating for dissolving/sterilization 15 minutes, it is cooled to 50 ~ 55 DEG C.Tocopherol (0.6g) and D-sorbite are added into the mixture Acid anhydride monoleate (B component: 6g), is made water phase portion.Lycopene crystal (15g) is added into the water phase portion, uses high speed cream Change machine (TK- mixer for well-distribution: PRIMIX corporation) is stirred 15 minutes with 6000 ~ 7000 revs/min, is obtained crystallization and is crushed original Liquid.By stoste 250g with case of wet attrition device (0.5 type of OB MILL: FREUND TURBO. corporation) with 2000 revs/min Stirring crushes 3 hours, to obtain pulverization process product.Purified water (22.5g) is added in the item for disposal (228g), with high speed cream Change machine (TK- mixer for well-distribution: PRIMIX corporation) is stirred 5 minutes with 3000 revs/min, to obtain the flat of lycopene The water-dispersible composition (240g, product 8 of the present invention) for the crystal that equal partial size is about 200nm.

(comparative example 3): the polysorbate of embodiment 7 is replaced (to replace reality using water using polyglyceryl fatty acid ester Apply the ethyl alcohol of example 8)

By SY-Glyster MO 750 (36g), glycerol (183g) and purified water (33g) with 90 ~ 95 DEG C of heating for dissolving/sterilizations 15 After minute, it is cooled to 50 ~ 55 DEG C.Tocopherol (0.6g) and sorbitan monooleate (6g), system are added into the mixture At water phase portion.Into the water phase portion add lycopene crystal (15g), using high-speed emulsifying machine (TK- mixer for well-distribution: PRIMIX corporation), it is stirred 15 minutes with 6000 ~ 7000 revs/min, obtains crystallization and crush stoste.By stoste 250g with wet Formula grinding device (0.5 type of OB MILL: FREUND TURBO. corporation) is crushed 3 hours with 2000 revs/min of stirrings, thus Obtain pulverization process product.Purified water (22.5g) is added in the item for disposal (228g), (TK- homogeneous mixes with high-speed emulsifying machine Device: PRIMIX corporation) it is stirred 5 minutes with 3000 revs/min, so that the average grain diameter for obtaining lycopene is about 200nm's Water-dispersible composition (240g, compares product 3).

(physical property (turbidity, tone ratio, tone, average grain diameter) of the product 3 compared with of product 7,8 of the present invention)

By the spectrum of product 7,8 of the present invention and 0.004% aqueous solution (W/V) for the water-dispersible composition for comparing product 3 (400 ~ 700nm) it is shown in Fig. 2.In addition, by the ratio (A430nm/ of the absorbance of product 7,8 of the present invention and the 430nm and 575nm that compare product 3 A575nm) it is shown in table 6.

[table 6]

。

As shown in Fig. 2 and table 6, the 0.004%(W/V of product 7 and 8 of the present invention) aqueous solution visually (visually observing) is Red, but the combination for comparing the emulsifier in No. 4673273 inventions of product 3(Japanese Patent No. etc.) it is show slightly yellow red Color.

In spectroscopic assay, product 7,8 of the present invention and compares product 3 and exist near 575nm, 530nm, 490nm and 450nm Peak, the peak 575nm in product 7 and 8 of the present invention is top, and comparing the peak 450nm in product 3 is top, along with this, also expanding Put on display the acromion until low wavelength side (430nm).Thus, for display yellow 430nm absorbance value be displayed in red The ratio (A430nm/A575nm) of absorbance value of 575nm when being evaluated, product 7 of the present invention, product of the present invention 8 and compare product 3 Value be respectively 0.727,0.840,1.098, product 7 and product of the present invention 8 of the present invention can be observed obvious poor compared between product 3 It is different.When in view of comparing product 3 being the water-dispersible composition of the lycopene crystal based on the prior art, if A430nm/ The value of A575nm is 1.0 or less, preferably 0.95 or less, more preferably 0.9 or less, further preferably 0.85 hereinafter, then may be used To say its obvious red relatively strong, presentation cerise compared with prior art.

In addition, being directed to Lab, the positive side of a value is red index, the index that negative side is green, and the positive side of b value is yellow Index, the index that negative side is blue.Known to when evaluating Lab measurement result: product 7,8 of the present invention and comparing product 3 from the point of view of a value red Without king-sized difference in terms of color, but from the point of view of b value when compare product 3 yellow it is stronger.As a result, it is considered that comparing product 3 It is the red for showing slightly yellow taste.

Among these numerical value, stable measurement knot when carrying out numerical value judgement, can be obtained as red ~ orange index Fruit, one of the index as reflection tone, it is believed that A430nm/A575nm is very effective.

(food preservation test of the water-dispersible composition of lycopene crystal)

By product 7,8 of the present invention and compare the bottleneck of the vial that product 3 are filled respectively to 15ml capacity, refrigerated (5 DEG C), Room temperature, 40 DEG C, 2 months food preservation tests carry out turbidity, tone, the average grain diameter measurement of the dispersible compositions of crystal.By its As a result it is shown in table 7.

[table 7]

。

As clearly shown in the result of table 7, turbidity, tone ratio, color difference and the average grain diameter of product 7 of the present invention refrigeration, room temperature, 40 DEG C, there is no after 2 months food preservation tests and variation immediately after preparation, tone stability and dispersity are good. In addition, product 8 of the present invention also show good tone stability in the same manner as product 7 of the present invention in the food preservation test between 2 months.

It should be noted that the color about product 3 are compared, in the same manner as product 7,8 of the present invention, in 2 months food preservation tests Adjust stability and dispersity good.

(stability test in beverage substrate)

By product 7,8 of the present invention and compares product 3 and be added to beverage substrate group shown in table 8 to assign fragrant rate for 0.004%(W/W) Cheng Zhong is cooled to room temperature after carrying out hot filling filling (central temperature is 90 ± 2 DEG C) into 300mL plastic bottle and stabilization is made Property test use sample.

[table 8]

。

By they refrigeration (4 DEG C), room temperature (about 20 DEG C), 40 DEG C these three under the conditions of save 2 months, evaluation save during After the spectroscopic assay of sample, appearance/tone ongoing change.In evaluation, using freshly prepd beverage as control, visually Appearance (whether dispersity, precipitating and the crystal of pigment are precipitated), tone evaluated.Appearance judges according to following benchmark.◎: with Control is compared to unchanged；△: abnormal state is felt compared with the control；×: ring/aggregation etc. is obviously observed compared with the control It is abnormal.Show the result in table 9.

[table 9]

。

As shown in table 9 when can be confirmed that like that by 2 months, product 7,8 of the present invention and compares product 3 and do not observe in pol Precipitating and crystal are precipitated caused by occurring in two kinds of different beverage substrates because of addition lycopene crystal dispersive composition Occur, tone is also unchanged compared with the control, maintains good state, is engaged to also stable in beverage substrate.

(embodiment 9) has used the water-dispersible composition of the lycopene crystal of polysorbate 20 and water

It other than replacing the polysorbate 80 in embodiment 7, is carried out complete with embodiment 7 in addition to using polysorbate 20 Exactly the same operation, to obtain product 9(240g of the present invention).

(embodiment 10) has used the water-dispersible composition of the lycopene crystal of polysorbate 60 and water

It other than replacing the polysorbate 80 in embodiment 7, is carried out complete with embodiment 7 in addition to using polysorbate 60 Exactly the same operation, to obtain product 10(240g of the present invention).

(embodiment 11) has used the water-dispersible composition of the lycopene crystal of polysorbate 60 and propylene glycol

Replace that the polysorbate 80 in embodiment 7, to use propylene glycol sweet to replace in addition to using polysorbate 60 Except oil, progress and the identical operation of embodiment 7, to obtain product 11(240g of the present invention).

(embodiment 12) has used the water dispersible of the lycopene crystal of polysorbate 80 and diglyceryl monooleate Composition

In addition to use diglyceryl monooleate come other than replacing the sorbitan monooleate in embodiment 7, carry out with The identical operation of embodiment 7, to obtain product 12(240g of the present invention).

(comparative example 4) replaces the polysorbate 60 of embodiment 11 using SY-Glyster MO 750

Other than using SY-Glyster MO 750 the polysorbate 60 that replaces in embodiment 11, carry out and embodiment 11 identical operations, to obtain comparing product 4(240g).

(product 9 ~ 12 of the present invention and the physical property (turbidity, tone ratio, tone, average grain diameter) for comparing product 4)

By product of the present invention 9 ~ 12 and compare the physical property (turbidity, tone ratio, tone, average grain diameter) shown in table 10 of product 4.

[table 10]

。

As shown in table 10 like that, red is presented in the i.e. product 9 ~ 12 of the present invention of the combination of emulsifier of the present invention etc., but Compare the combination of emulsifier of product 4(No. 4673273 inventions of Japanese Patent No. etc.) red for showing slightly yellow taste is presented.The present invention The A430nm/A575nm of product is 1.0 hereinafter, but comparing the value in product 4 is more than 1.0.In the water dispersion of lycopene crystal In property composition, do not know still to present in this cherry composition, it may be said that realize through the invention and for the first time.

Claims (4)

1. composition, the state to be dispersed in hydrocarbon carotenoid crystals in the decentralized medium comprising emulsifier exist and For assigning cherry water-dispersible composition,

The carotenoid crystals be beta carotene or lycopene crystal,

The decentralized medium is included at least two different emulsifiers and not aqueous, or is wrapped at most in terms of total composition quality criteria Water containing 8 mass parts, substantially insoluble or insoluble carotenoid crystals, and

In the case where the composition containing beta carotene crystal, the absorbance of the 0.004%W/V aqueous solution of the composition is measured When, ratio, that is, A430nm/A550nm of the absorbance of 430nm and 550nm be 0.95 hereinafter,

In the case where the composition containing lycopene crystal, the absorbance of the 0.004%W/V aqueous solution of the composition is measured When, ratio, that is, A430nm/A575nm of the absorbance of 430nm and 575nm be 1.0 hereinafter,

The composition contains:

(A) beta carotene or lycopene crystal；And the sorbitan esters of fatty that (B) HLB as decentralized medium is 2 ~ 6 The diglycerine fatty acid ester, (C) polyoxyethylene sorbitan fatty acid ester, (D) water and (E) that acid esters and/or HLB are 2 ~ 6 are more First alcohols,

The composition is dispersed in the presence of the state in the mixed liquor of (B), (C), (D) and (E) with (A), or

The composition contains:

(A) beta carotene or lycopene crystal；And the sorbitan esters of fatty that (B) HLB as decentralized medium is 2 ~ 6 Diglycerine fatty acid ester that acid esters and/or HLB are 2 ~ 6, the polyglyceryl fatty acid ester that (F) HLB is 10 ~ 15, (G) ethyl alcohol and (E) Polyalcohols,

The composition is dispersed in the presence of the state in the mixed liquor of (B), (F), (G) and (E) with (A).

2. composition according to claim 1, wherein the average grain diameter of beta carotene or lycopene crystal be 100 ~ 400nm。

3. method is the manufacturing method of water-dispersible composition described in claim 1 comprising following process:

Beta carotene or lycopene crystal is set to be scattered in the process of decentralized medium, the decentralized medium does not include at least two not With emulsifier and not aqueous, or include the water of 8 mass parts at most in terms of total composition quality criteria, it is substantially insoluble or Insoluble carotenoid crystals；And

It will be combined obtained from such operation with being dispersed with water dispersible existing for the state of beta carotene or lycopene crystal Object is diluted in water and measures absorbance, the process for being confirmed as follows gained absorbance:

In the case where the composition containing beta carotene crystal, the absorbance of the 0.004%W/V aqueous solution of the composition is measured When, ratio, that is, A430nm/A550nm of the absorbance of 430nm and 550nm be 0.95 hereinafter,

In the case where the composition containing lycopene crystal, the absorbance of the 0.004%W/V aqueous solution of the composition is measured When, ratio, that is, A430nm/A575nm of the absorbance of 430nm and 575nm be 1.0 hereinafter,

The method includes following process:

It is 2 that (B) HLB is added into the mixed liquor of (C) polyoxyethylene sorbitan fatty acid ester, (D) water and (E) polyalcohols ~ 6 sorbitan fatty acid ester and/or HLB be 2 ~ 6 diglycerine fatty acid ester and mixing after, make (A) beta carotene or Lycopene crystal is dispersed in gained decentralized medium, with wet crushing mill being averaged beta carotene or lycopene crystal Partial size is crushed, is adjusted to the process of 100 ~ 400nm, or

The method includes following process:

To the mountain that addition (B) HLB is 2 ~ 6 in the mixed liquor of (C) polyoxyethylene sorbitan fatty acid ester and (E) polyalcohols After diglycerine fatty acid ester that pears sugar alcohol acid anhydride aliphatic ester and/or HLB are 2 ~ 6 and mixing, in gained decentralized medium, make (A) Beta carotene or lycopene crystal are dispersed in the decentralized medium, with wet crushing mill that beta carotene or lycopene is brilliant The average grain diameter of body is crushed, is adjusted to 100 ~ 400nm, the adjustment liquid obtained so backward in add the process of (D) water.

4. method contains the water dispersible of beta carotene or lycopene crystal as hydrocarbon carotenoid crystals for manufacture The method of composition, which is characterized in that comprise the following steps:

(B) HLB is added into the mixed liquor of polyglyceryl fatty acid ester, (G) ethyl alcohol and (E) polyalcohols that (F) HLB is 10 ~ 15 After diglycerine fatty acid ester that sorbitan fatty acid ester and/or HLB for 2 ~ 6 are 2 ~ 6 and mixing, make (A) beta carotene Or lycopene crystal is dispersed in gained decentralized medium, with wet crushing mill by the flat of beta carotene or lycopene crystal Equal partial size is crushed, is adjusted to the process of 100 ~ 400nm, and

In the case where measuring the absorbance of 0.004%W/V aqueous solution of the dispersible compositions, contain beta carotene crystal When, ratio, that is, A430nm/A550nm of the absorbance of 430nm and 550nm is 0.95 hereinafter, when containing lycopene crystal, Ratio, that is, A430nm/A575nm of the absorbance of 430nm and 575nm is 1.0 or less.