HK1056377B - Deodorized yellow colorant of safflower - Google Patents

Description

Deodorized yellow pigment of safflower

Technical Field

The present invention relates to safflower yellow (safflower yellow) and a pigment preparation containing the same, wherein the safflower yellow is odorless or the odor thereof has been significantly reduced to be considerably weak. More particularly, the present invention relates to odorless or slightly odorous safflower yellow pigment and a pigment preparation containing the same, in which odor caused and released by light and heat during storage over time is significantly reduced. The invention also relates to a method for preparing the odorless or slightly odorous safflower yellow pigment.

Background

Safflower yellow is a flavonoid pigment that is widely used primarily for coloring beverages and other food products. However, safflower yellow has a peculiar odor derived from safflower (carthamustatinctorius L.) which is a raw material thereof, and therefore when it is used in foods and other products, the odor may sometimes disguisedly contaminate the flavor and taste, etc., of these foods to humans.

Therefore, there has been a long-felt need for a safflower yellow preparation which can be added to foods and the like, whose fragrance has been reduced to such an extent that the peculiar odor of safflower is not detected, and various purification methods have been studied so far. Methods for refining safflower yellow which have been proposed include a method of treating an aqueous solution of safflower yellow with an ion exchange resin (Japanese patent laid-open publication No. Hei 4-214767), a method of extracting a water-soluble food pigment with an organic solvent or supercritical carbon dioxide (Japanese patent laid-open publication No. Hei 4-48420), and a method of bringing a water-soluble natural pigment into contact with an adsorbent resin and subcritical or supercritical carbon dioxide (Japanese patent laid-open publication No. Hei 10-36701).

However, few methods have revealed the peculiar odor of safflower yellow. The safflower yellow preparation produced by one of the above-mentioned refining treatments still has a strong and peculiar odor from safflower petals, and such a preparation cannot be regarded as having solved the above-mentioned problems.

Furthermore, conventional safflower yellow preparations have been shown to have a so-called "aftertaste" (i.e., the odor gradually becomes more intense over time during storage due to the action of heat, light, etc., and the various purification treatments discussed above have not solved this "aftertaste".

DISCLOSURE OF THE INVENTION

It is an object of the present invention to provide a safflower yellow preparation which has little side effect on various products such as foods, medicines, semi-medicines and cosmetics for a long period of time and which can be added to these products without worry.

More specifically, it is a first object of the present invention to provide a safflower yellow pigment and a pigment preparation containing the pigment, which is free from an odor derived from aromatic components contained in safflower (Carthamus tinctorius l.), or in which the odor has been significantly reduced. It is a second object of the present invention to provide a stable safflor yellow pigment which hardly changes as so-called "aftertaste" with the passage of time when exposed to heat or light during long-term storage, and a pigment preparation containing the same. It is a third object of the present invention to provide a method for preparing odorless or slightly odorous safflower yellow.

The present inventors spent a long time studying safflower yellow preparations in an effort to solve the problems encountered in the past, and they found that aromatic components contained in safflower are a source of offensive odor or malodor, which can be effectively removed, and can prepare odorless or slightly odorous safflower yellow by the method of the present invention. They also found that the safflower yellow obtained with this method does not have any "aftertaste" (a result of long-term storage or of thermal or light influences). From these findings, it was confirmed that a safflower yellow preparation which is odorless or slightly odorous and has excellent stability with the passage of time can be prepared by using the safflower yellow as an ingredient.

The present invention has been accomplished on the basis of these findings.

Specifically, the present invention is a safflower yellow pigment given by the following (1) to (8).

(1) A safflower yellow pigment with color value E^10％ _1cmAt 160 f, the concentration of the aromatic component contained therein does not exceed 100 ppm.

(2) A safflower yellow pigment with color value E^10％ _1cmAt 160 f, the concentration of the aromatic component contained therein does not exceed 75 ppm.

(3) A yellow pigment of safflowerColor number E^10％ _1cmAt 160 f, the concentration of the aromatic component contained therein does not exceed 50 ppm.

(4) The safflower yellow according to any one of (1) to (3), wherein the aromatic component is at least one selected from the group consisting of acetic acid, isovaleric acid, phenethyl alcohol, phenol and 4-vinylphenol.

(5) A safflower yellow pigment with color value E^10％ _1cmAt 160, the total concentration of acetic acid and/or isovaleric acid contained therein does not exceed 20 ppm.

(6) A safflower yellow pigment with color value E^10％ _1cmAt 160, the total concentration of acetic acid and/or isovaleric acid contained therein is no more than 5 ppm.

(7) The safflower yellow according to (5) or (6), wherein when the color value E is^10％ _1cmAt 160, the concentrations of phenethyl alcohol, phenol and 4-vinylphenol contained therein were each not more than 50 ppm.

(8) The safflower yellow according to (5) or (6), wherein when the color value E is^10％ _1cmAt 160, the concentrations of phenethyl alcohol, phenol and 4-vinylphenol contained therein were each not more than 20 ppm.

The present invention also relates to a colorant preparation containing safflower yellow as described in the following (9) to (11).

(9) A yellow pigment preparation comprising the safflower yellow according to any one of (1) to (8).

(10) The yellow pigment preparation according to (9), which is in the form of a solution.

(11) The yellow pigment preparation according to (9) or (10), wherein the safflower yellow pigment is contained in an amount of 1 to 90% by weight per 100% by weight of the preparation.

The present invention also relates to a method for producing the high-purity safflower yellow as described in the following (12) to (22).

(12) A method for preparing odorless or slightly odorous safflower yellow pigment comprises subjecting an extract of safflower yellow pigment subjected to adsorption treatment to at least one treatment selected from adsorption, ion exchange, pH adjustment, extraction and membrane separation.

(13) The process for producing safflower yellow according to (12), wherein the pH adjustment is an acid treatment with an acid used as a food additive.

(14) The process for producing safflower yellow according to (12) or (13), wherein the pH adjustment is an acid treatment with at least one inorganic acid selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid.

(15) The process for producing safflower yellow according to any one of (12) to (14), wherein the pH adjustment consists of: subjecting the extract of safflower yellow to adsorption treatment or one of various other treatments to a condition of pH 3-6.

(16) The process for producing safflower yellow according to any one of (12) to (15), wherein the membrane separation is at least one membrane treatment selected from the group consisting of membrane filtration, ultrafiltration, reverse osmosis, electrolysis, ion selection and ion exchange.

(17) A method for preparing odorless or slightly odorous safflower yellow pigment comprises subjecting extractive solution of adsorbed safflower yellow pigment to deproteinization treatment and membrane separation.

(18) The process for producing a safflower yellow according to (17), wherein the membrane separation treatment is reverse osmosis or ultrafiltration.

(19) The process for producing a safflower yellow according to (17) or (18), wherein the membrane separation treatment uses a membrane having a molecular weight cut off of 2000-4000.

(20) The process for producing safflower yellow according to any one of (17) to (19), wherein the deproteinization is at least one treatment selected from the group consisting of ion exchange, extraction, membrane separation and gel filtration.

(21) The process for producing safflower yellow according to (20), wherein the deproteinization treatment is carried outMolecular weight cut-off for membrane separation of 10⁴-10⁶The film of (1).

(22) The process for producing safflower yellow according to any one of (17) to (21), wherein pH adjustment is carried out before membrane separation.

Brief Description of Drawings

Fig. 1 is a graph showing the results of measuring the amount of aromatic components contained in the safflower yellow preparation (fig. 1A) prepared in example 1 and the safflower yellow preparation (fig. 1B) prepared in comparative example 1 by a gas chromatography-mass spectrometer (GC-MS). In FIG. 1B, (-) is the peak for acetic acid, (-) is the peak for isovaleric acid, (-) is the peak for phenethyl alcohol, and (R) is the peak for 4-vinylphenol. The peak of IS IS 2, 6-di-tert-butyl-4-methylphenol (BHT), which was used as an internal standard. In this curve, the vertical axis is abundance and the horizontal axis is retention time.

Best Mode for Carrying Out The Invention

The present invention is a red flower yellow pigment which is odorless or slightly smelly, wherein there is no odor derived from red flowers used as a raw material, or the odor has been significantly reduced.

In the present invention, "safflower yellow" refers to a flavonoid pigment containing carthamin (carthamus yellow) as a main component, which is obtained from safflower (carthamus tinctorius) belonging to the family Compositae, specifically from its petals.

"color value" (E) used in the present invention^10％ _1cm) Is a value obtained by measuring the absorbance in the visible region of a solution containing the safflower yellow (buffer pH 5) at a maximum absorption wavelength (around 402 nm) and converting the absorbance into the absorbance of a solution containing 10 w/v% safflower yellow.

The term "aromatic ingredient" used in the present invention means a volatile aromatic ingredient derived from safflower, more specifically from petals thereof, which is a source of offensive odor or malodor, and examples thereof include acetic acid, isovaleric acid, phenethyl alcohol, phenol and 4-vinylphenol, without particular limitation.

The safflower yellow pigment of the present invention is characterized in that when the color value of the pigment is adjusted to E10% and 1cm to 160, the total concentration of the above-mentioned aromatic components contained in the pigment is not more than 100 ppm. Preferably, the concentration is about 75ppm or less, more preferably 50ppm or less, and especially preferably 20ppm or less. The concentration of the aroma component is substantially proportional to the color value. Therefore, as long as the total concentration of the aromatic components in the safflower yellow pigment of the present invention is within the above range when the color value is adjusted as above, the pigment itself does not need to have the above color value.

Preferably, when the color value is adjusted to the above value, the safflower yellow of the present invention is such that: the concentration of the combination of acetic acid and/or isovaleric acid contained in the pigment is about 20ppm or less, preferably 5ppm or less. These ingredients have a very low odor threshold and give off odor even in an extremely small amount, and thus are volatile aromatic ingredients derived from safflower which is a main cause of malodor. At this time, it is preferable that the concentrations of the above-mentioned various other aromatic components (phenethyl alcohol, phenol and 4-vinylphenol) contained in the safflower yellow be each about 50ppm or less, preferably about 20ppm or less.

The safflower yellow of the present invention which is odorless or reduced in odor by drastically reducing the content of aromatic components can be produced by subjecting the adsorption-treated extract solution of safflower yellow to at least one treatment selected from adsorption, ion exchange, pH adjustment, extraction and membrane separation, or a combination of any two or more treatments.

Accordingly, the present invention provides a method for preparing the above odorless or slightly odorized safflower yellow (deodorized safflower yellow). From another point of view, the preparation method of the present invention can also be referred to as a method for purifying safflower yellow which can be used for removing or reducing the amount of aromatic components causing offensive odor or offensive odor, particularly the above-mentioned acetic acid, isovaleric acid, phenethyl alcohol, phenol and 4-vinylphenol, contained in an extract solution of safflower pigment. From another point of view, the preparation method of the present invention can also be referred to as a method of deodorizing safflor yellow.

The solvent extract of the safflower plant discussed above can be used as the "safflower yellow pigment extract" used in the production method of the present invention. The plant part used in the extraction should be a part containing the target pigment, particularly safflower yellow pigment, without particular distinction between the whole plant and its parts (e.g., petals or buds). Preferably a petal section. The purification operation may be carried out on the whole or part of the plant as it is (raw material) or after crushing (coarsely pulverizing, finely chopping, etc.), or may be carried out after drying and, if necessary, crushing (pulverizing, etc.).

The solvent used in the above purification is not particularly limited as long as it can extract carthamin contained in safflower. It may be preferred to use alcohol, water or mixtures thereof. Examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol and others₁-C₄Lower alcohols. Water or water containing alcohol (aqueous alcohol) is preferred.

Any commonly used extraction method may be used without particular limitation thereto, and examples include a method in which whole or part of safflower (as it is, or after coarsely pulverizing, finely chopping), or a dried product thereof (including those produced by dry pulverization (e.g., powder)), is cold-dipped, hot-dipped or otherwise immersed in a solvent, a method in which extraction is carried out under heating and stirring and an extract is obtained by filtration, and a percolation method.

The extract obtained is filtered, coprecipitated or, if necessary, centrifuged to remove solids, after which the product is subjected to an adsorption treatment, either directly or after concentration.

The adsorption treatment can be carried out by a standard method, for example, adsorption using activated carbon, silica gel or porous ceramics; or using synthetic adsorbent resins such as styrene-based Duolite S-861 (trademark Duolitc, Diamond Shamrock U.S. A.; the same below), Duolite S-862, Duolite S-863, and Duolite S-866; aromatic Sepabeads SP70 (trademark of Mitsubishi Chemical; the same applies below), Sepabeads SP700 and Sepabeads SP 825; diaion HP10 (trademark of Mitsubishi Chemical; the same applies below), Diaion HP20, Diaion HP21, Diaion HP40 and Diaion HP 50; or Amberlite XAD-4 (trademark of Organo; the same applies hereinafter), Amberlite XAD-7 and Amberlite XAD-2000.

The adsorption-treated extract used in the production method of the present invention can be obtained by: washing the resin carrier loaded with the safflower yellow pigment extract liquid and having the pigment component adsorbed thereon with an aqueous alcohol or other suitable solvent, and recovering the desired extract liquid. Water containing 10 to 60% by volume of ethanol is generally advantageously used as the aqueous alcohol in the present invention.

The thus obtained adsorption-treated safflower yellow is then subjected to any of various treatments such as another adsorption treatment, ion exchange, pH adjustment, extraction or membrane separation.

Examples of the adsorption treatment of the present invention are the same as those listed above.

The ion exchange treatment is not particularly limited, and the treatment can be carried out by a conventional method using a general ion exchange resin (cation exchange resin or anion exchange resin). For example, examples of the cation exchange resin include Diaion SK1B (trademark of Mitsubishi Chemical; the same applies hereinafter), Diaion SK102, Diaion SK116, Diaion PK208, Diaion WK10 and Diaion WK 20; examples of anion exchange resins include Diaion SA10A (trademark of Mitsubishi Chemical; the same applies hereinafter), Diaion SA12A, Diaion SA20A, Diaion PA306, Diaion WA10 and Diaion WA20, but other products may be used instead.

The "pH adjustment" referred to in the present invention can be accomplished by: the safflower yellow pigment subjected to adsorption treatment or any of various other treatments (adsorption, ion exchange, pH adjustment, extraction or membrane separation) is adjusted to pH 1 to 8, and the extract is subjected to acidic to neutral conditions. Preferably, the pH adjustment is an acid treatment in which the treated extract is adjusted to pH 3 to 6. The acid treatment can be easily performed by adding an acid to the treated extract. The acid is not particularly limited as long as it is an acid generally used as a food additive, and any such acid can be selected as desired. For example, organic acids such as citric acid, acetic acid, malic acid and lactic acid, or inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid may be used. Preferably, mineral acids, which are commonly used as food additives, are used in the acid treatment.

The temperature at the time of pH adjustment is not particularly limited, and any temperature of 5 to 100 ℃ may be generally selected as required. Examples include 20-100 ℃ or 40-100 ℃. The time for the pH adjustment is not particularly limited, or is generally selected from the range of 1 to 300 minutes as required. If the treatment is carried out at elevated temperatures, generally short treatment times are sufficient, so that if the temperature is from 40 to 100 ℃ the treatment time is from 5 to 60 minutes. The treated extract may or may not be agitated during this time.

The present invention is not particularly limited to the extraction treatment, and one example is a method of contacting the safflower yellow extract subjected to adsorption treatment or any of various other treatments (adsorption, ion exchange, pH adjustment, extraction or membrane separation) with carbon dioxide gas or a liquid such as ethylene or propane in a closed vessel at a temperature above the critical point and under a pressure.

The "membrane separation" used in the present invention includes a wide range of filtration by a membrane, and examples thereof include filtration treatment using a Membrane Filter (MF), an Ultrafiltration (UF) membrane, a reverse osmosis membrane (NF), an electrolytic membrane, or other such functional macromolecular membrane. In addition to ultrafiltration, reverse osmosis and other such methods using these membranes, known membrane separation methods include dialysis using a concentration gradient generated by an ion selective membrane, and electrolysis using an ion exchange membrane as a separation membrane and applying a voltage thereto. For industrial purposes, a membrane separation method using a reverse osmosis membrane is preferred. The membrane raw material used in the membrane separation may be natural, synthetic or semisynthetic, and examples include cellulose, cellulose diethyl ester or cellulose triethyl ester, polyamide, polysulfone, polystyrene, polyimide and polyacrylonitrile.

The membrane separation method used in the present invention includes, for example, using a molecular weight cut-off of 10⁴-10⁶And a method of separating a low molecular weight compound using a membrane having a molecular weight cut-off of about 2000-4000, preferably about 3000. Specific examples of the former method include using an NTU-3150 membrane, an NTU-3250 membrane, an NTU-3550 membrane or an NTU-3880 membrane (all manufactured by Nitto Denko); Cefilt-UF (manufactured by NGK instruments); and an Ultrafiltration (UF) membrane treatment of an AHP-2013 membrane, an AHP-3013 membrane or an AHP-1010 membrane, all manufactured by Asahi Chemical. Specific examples of the latter method include using an NTR-7250 membrane, an NTR-7410 membrane, an NTR-7430 membrane or an NTR-7450 membrane (both manufactured by Nitto Denko); or an AIP-3013 film, an ACP-2013 film, an AIP-2013 film or an AIO-1010 film (all manufactured by Asahi Chemical) with a reverse osmosis membrane (molecular weight cut-off of about 3000).

These various treatments may be carried out alone or in any combination of two or more. Also, the same treatment may be performed a plurality of times under the same or different conditions.

The preferred treatment method is not particularly limited, but one example is a method of deproteinizing the adsorption-treated safflower yellow extract and then subjecting the product to membrane separation.

The deproteinization treatment can be efficiently performed by the above-mentioned extraction treatment, ion exchange treatment, or membrane separation treatment using an ultrafiltration membrane or the like. Further, the molecular weight cut-off used in the separation and removal of high molecular weight compounds is about 10⁴-10⁶The treatment of the membrane of (2) can be preferably used for the membrane separation treatment in this case. However, the deproteinization treatment is not limited to these methods and may be performed by gel filtration or any other standard deproteinization treatment.

If desired, another adsorption treatment may be performed after the above-described deproteinization treatment. An example of a preferable treatment method is to subject the deproteinized pigment extract to adsorption treatment as needed, followed by pH adjustment and preferably acid treatment, and finally subjecting the thus obtained treated pigment extract to membrane separation. The membrane separation treatment of the present invention is preferably reverse osmosis or ultrafiltration, and particularly preferably reverse osmosis membrane treatment. The membrane separation is preferably carried out using membranes having a molecular weight cut-off of about 2000-4000, preferably close to 3000.

The aromatic components derived from safflower are a source of offensive odor or malodor, which can be effectively removed from the safflower yellow obtained in the present invention as described above, and therefore the present invention provides a odorless or slightly odorous safflower yellow whose odor has been reduced to such an extent that the addition of the colorant to food has little adverse effect on the flavor thereof. In addition, the safflower yellow of the present invention obtained by the above method hardly changes with the passage of time, i.e., the so-called "aftertaste" (odor due to the influence of heat or light during long-term storage) does not occur. The reason for this is considered to be that the precursor of the fragrant component capable of emitting an offensive odor or malodor is decomposed or removed by the above-mentioned production method of the present invention, but this theory is not confirmed.

The pigment preparation can be prepared by the following method: in the form of a solution obtained by dissolving or dispersing (emulsifying) the safflower yellow of the present invention in water, an alcohol such as ethanol or propylene glycol, or another solvent, or by making into powder, granules, tablets, pills, etc. by using dextrin or the like as an excipient. The form of a solution is preferred.

Therefore, the invention also provides a yellow pigment preparation containing the safflower yellow pigment.

The pigment preparation may consist of only the safflower yellow of the present invention, or may contain a carrier and various additives useful in foods in addition to the safflower yellow described above.

Specific examples of such carriers and additives include dextrin, lactose, and powdered syrup, as well as preservatives (such as sodium acetate and protamine), stabilizers (such as sodium phosphate and sodium metaphosphate), antioxidants (such as rutin and ascorbic acid), and other such food additives commonly used with color and color preparations.

When the pigment preparation of the present invention contains any of various carriers, additives and the like, the proportion of the above-mentioned safflower yellow pigment in the pigment preparation is not particularly limited, but generally the amount is 1 to 90% by weight, and preferably 10 to 80% by weight.

The pigment preparations of the present invention are useful as yellow colorants for foods, pharmaceuticals, semi-pharmaceuticals, cosmetics, animal feeds, etc., particularly as natural color colorants.

There are no particular limitations on the foods to which the pigment preparations of the present invention can be applied, so long as they can be colored or have a hue, and examples include ice cream, milk jelly, sherbet, iced foods, and other such frozen preparations; milk beverages, lactic acid bacteria beverages, fruit juice-containing soft drinks, carbonated beverages, fruit juice beverages, powdered beverages, and other such beverages; milk puddings, puddings containing fruit juice, and other such puddings; jelly, bavaria cheese, yogurt, and other such confections; chewing gum, bubble gum, and other such gums (stick gum and dragee particles); chocolate beans, and other such coated chocolates, as well as strawberry chocolate, blueberry chocolate, melon chocolate, and other flavored chocolates, and other such chocolates; hard candies (including bonbons, butter balls, and sugar balls (marbles)), soft candies (including caramel, nougat, gummy, and marshmallow), sugar balls, toffee, and other such candies; hard cookies, koaki (sliced and dried sticky rice), senbei (sliced and dried non-sticky rice), and other such baked snacks; asazuke (fresh vegetables or malt salted with salt), soy sauce kimchi, salt kimchi, japanese bean paste (miso) kimchi, kasuzuke (rice bran kimchi), malt kimchi, sugar kimchi, vinegar kimchi, mustard kimchi, moromizuke (unrefined sake kimchi), plum kimchi, fukujinzuke (flaky vegetables salted with soy sauce and dye red), shibazuke (various vegetables cut and pickled with salt), ginger kimchi, plum vinegar kimchi, and other such kimchi; vingrel sour sauce seasoning, non-oil seasoning, ketchup sauce, bouillon, worcestershire chili sauce, pork fillet sauce, and other such sauces; strawberry jam, blueberry jam, mandarin orange jam, apple jam, almond jam, preserves, and other such jams; red wine and other such wines; cherry preserves, almonds, apples, strawberries, and other such processed fruits; ham, sausage, roast pork, and other such processed meats; fish ham, fish sausage, benthic fish, cooked fish dough, chikuwa (tubular fish cake), hanpen (fish cake), satsumaage (fried fish cake), datemaki (rolled omelet), whale bacon, and other fine seafood; udon (udon), hiyamugi (cold buckwheat noodles), soumen (vermicelli), soba (hot buckwheat noodles), chinese buckwheat noodles, macaroni, bifun noodles, harusame (winter flour), ravioli, and other such dry pasta; and various types of side dishes and processed foods such as boiled fish dough, wheat gluten bread, and denbu (crushed and seasoned fish).

The coloring of food products includes not only artificial coloring by adding pigments to food, but also extensive coloring by using pigments already contained in food materials such as fruit juice.

In pharmaceutical products, [ the present invention ] can be used, for example, as colorants for various tablets, capsules, drinkable preparations, troches, gargles, and the like; in the semi-drugs, it can be used as colorant for dentifrice, breath freshener, gargle, etc.; in cosmetics, it can be used as pigment for skin lotion, lipstick, sunscreen emulsion, cosmetics, etc.; and it can be used in feeds and the like, such as cat feeds, dog feeds, and other such pet feeds, aquarium fish feeds, aquaculture feeds, and the like.

The present invention includes the following aspects:

(a) a method for purifying safflower yellow is characterized in that an extract of safflower yellow subjected to adsorption treatment is subjected to at least one treatment selected from adsorption, ion exchange, pH adjustment, extraction and membrane separation.

(b) A method for purifying safflower yellow pigment is characterized in that the adsorbed safflower yellow pigment extract is subjected to deproteinization treatment and then membrane separation.

(c) The method for purifying safflower yellow according to the above (b), wherein the deproteinization is at least one treatment selected from the group consisting of ion exchange, extraction, membrane separation and gel filtration.

(d) The method for purifying safflower yellow according to the above (b), wherein the pH adjustment is carried out before the membrane separation.

(e) A method for deodorizing safflower yellow is characterized in that an extract solution of safflower yellow subjected to adsorption treatment is subjected to at least one treatment selected from adsorption, ion exchange, pH adjustment, extraction and membrane separation.

(f) A method for deodorizing safflower yellow pigment is characterized in that the safflower yellow pigment extract after adsorption treatment is subjected to deproteinization treatment and then is subjected to membrane separation.

(g) The method for deodorizing safflower yellow according to the above (f), wherein the deproteinization is at least one treatment selected from the group consisting of ion exchange, extraction, membrane separation and gel filtration.

(h) The method for deodorizing safflower yellow according to the above (f), wherein the pH adjustment is performed before the membrane separation.

(i) Use of safflower yellow as a colorant for foodstuffs, wherein the color value E is^10％ _1cmAt 160 f, the concentration of the aromatic component contained therein does not exceed 100 ppm.

(j) The use of the safflower yellow as a colorant for foods according to the above (i), wherein the aromatic component is at least one selected from the group consisting of acetic acid, isovaleric acid, phenethyl alcohol, phenol and 4-vinylphenol.

(k) Use of safflower yellow as a food colorant, wherein the color value E is^10％ _1cmAt 160, the total concentration of acetic acid and/or isovaleric acid contained therein does not exceed 20 ppm.

(1) Use of safflower yellow as a food colorant, wherein the color value E is^10％ _1cmAt 160, the total concentration of acetic acid and/or isovaleric acid contained therein does not exceed 20ppm, and the respective concentrations of phenethyl alcohol, phenol and 4-vinylphenol contained therein does not exceed 50 ppm.

Examples

The present invention will now be described in detail by way of examples and comparative examples, but the present invention is not limited to these examples in any way.

Comparative example 1

10kg of safflower petals were immersed in 200L of water and left overnight at room temperature to extract pigments. The extract was filtered under reduced pressure using a filter aid and celite to obtain about 195L of a safflower yellow extract as a filtrate. The pigment component was adsorbed from the extract with Amberlite XAD-7 (trademark of Organo) (synthetic adsorbent resin, amount of resin: 30L, SV: 1), and the resin was thoroughly washed with 5L of water, after which the pigment was eluted with 30% aqueous ethanol, and the eluate obtained was used as an adsorption-treated extract of safflower yellow pigment (100L: once purified pigment extract). The extract thus subjected to adsorption treatment was concentrated under reduced pressure to obtain 5kg of a color value E^10％ _1cmIs 320 of pigment extracting solution. 2kg of water and 3kg of ethanol were added to the 5kg of pigment extract to prepare a color value E^10％ _1cm160 kg of safflower yellow preparation (comparative). When smelled, the preparation has malodor peculiar to safflower petal.

Example 1Safflower yellow pigment preparation (solution)

10L of the once-purified pigment extract (adsorption-treated safflower yellow pigment extract) obtained by the same method as in comparative example 1 was further treated with a synthetic adsorbent resin (AmbcriteXAD-2000, trademark of Organo; amount of resin: 5L, SV: 10), and the portion passing through the resin was used as a pigment solution (adsorption treatment). The pigment solution was treated with an ultrafiltration membrane (trademark: AHP-2013 membrane, manufactured by Asahi Chemical, molecular weight cut-off: 50000) at 20 ℃ and 3.5kg/cm (membrane separation treatment). The treated extract thus obtained was then adjusted to pH 2.0 with sulfuric acid, and the product was stirred at a temperature of 40-80 ℃ for 30 minutes (pH adjustment treatment).

Then, 80L of water was added to the acidic solution to carry out reverse osmosis treatment (trademark: NTR-7250 membrane, manufactured by Nitto Denko, molecular weight cut-off: about 3000) to obtain 10L of membrane-treated extract (membrane separation treatment). The invention removes aromatic components and impurities in safflower as filtrate, and concentrates the purified and deodorized pigment components into residual liquid. The residue was concentrated under reduced pressure to obtain 4.5kg of a pigment extract which had been significantly deodorized and purified and had a color value of E^10％ _1cmIs 320. 1.8kg of water and 2.7kg of ethanol were added to the 4.5kg of the pigment extract solution to prepare a color value E^10％ _1cmIs 160 kg of safflower yellow preparation (product of the invention).

Example 2Safflower yellow pigment preparation (solid)

6.0kg of water and 1.5kg of dextrin were added to the already significantly deodorized and purified color number E^10％ _1cm3.2kg of a pigment extract solution (320), which was prepared in the same manner as in example 1. The product was spray-dried to give 2.5kg of color E^10％ _1cmIs 400 of safflower yellow pigment powder preparation. The preparation is odorless.

Example 3GC-MS determination

The preparation of safflower yellow (comparative product) contained in comparative example 1 and the preparation of safflower yellow prepared in example 1 were measured by gas chromatography-mass spectrometryThe amounts of fragrance components in the formulations (products of the invention) were compared. Specifically, 5g each of the pigment preparations (color value E) were extracted with 200ml of diethyl ether containing 3ppm of an internal standard (IS: 2, 6-di-tert-butyl-4-methylphenol (BHT))^10％ _1cm160). The ether solution was then evaporated to dryness, and the thus-obtained concentrate was placed in a gas chromatography-mass spectrometer (GC-MS) to determine the amount of aromatic components.

GC-MS measurement conditions

GC/MS：Hewlett-Packard 5973 Mass Selective Detector

Column: DB-WAX (0.25 mm. times.60 m) manufactured by J & W

Temperature: the inlet is 250 ℃, the interface is 230 ℃,

column temperature 50 deg.c (2 min) -220 deg.c,

the heating rate is 3 ℃/min.

Separation ratio (split ratio): 70: 1

Ionization voltage: 70eV

The results are shown in FIG. 1. As shown in FIG. 1A, the total ion chromatogram of the safflower yellow preparation (product of the present invention) of example 1 shows that the aromatic components other than the internal standard are contained in only a very slight amount (73ppm or less). In contrast, as shown in FIG. 1B, it was found that the safflower yellow preparation (comparative product) of comparative example 1 contained a large amount of volatile aromatic components (215 ppm). These results are consistent with the fact that the pigment preparation of comparative example 1 has a characteristic odor of safflower petals, whereas the pigment preparation of example 1 has no odor.

In fig. 1B, (-) IS a peak of acetic acid, (-) IS a peak of isovaleric acid, (-) IS a peak of phenethyl alcohol, (-) IS a peak of 4-vinylphenol, and IS a peak of BHT, which are used as internal standards.

Example 4Taste evaluation and storage test

Paired by a group of ten trained seasoning expertsThe safflower yellow preparation (comparative product) prepared in comparative example 1 and the safflower yellow preparation (product of the present invention) prepared in example 1 were evaluated for their tastes immediately after the preparation, and their tastes after storage at 5 ℃, 25 ℃, or 38 ℃ for 15 and 30 days. In addition, beverage-type solutions (color value E) were prepared with the respective pigment preparations^10％ _1cmBrix 10 °, 0.2 citric acid solution without added flavor), the flavor of each solution was evaluated immediately after preparation and after storage in the same manner as described above, and the results are given in table 1.

TABLE 1

			Immediately after preparation	After 15 days of storage	After 30 days of storage
						C.E.1	Preparation	5℃	C	C	D
25℃	C	D	E
				38℃	C			E	E
Beverage and its preparing process	5℃	B	B							B
				25℃	B		C	C
	38℃	B	D						D
				Example 1	Preparation		5℃	A		A	A
25℃	A	A	A
						38℃	A	A	A
Beverage and its preparing process	5℃	A	A							A
					25℃	A	A	A
	38℃	A	A						A

(C.E. comparative example)

Evaluation criteria:

a: no odor was perceived at all

B: very slight off-odor

C: has abnormal odor

D: strong off-flavor

E: very strong off-flavor

As can be seen from the results of the evaluation immediately after the preparation in table 1, the odor of the product of the present invention has been significantly reduced compared to the odor of the comparative product, and the former is considered to be a substantially odorless pigment. Furthermore, when the storage time was extended to 15-30 days, the taste of the comparative product became increasingly strong, whereas the product of the present invention hardly changed with the passage of time, maintaining the same odorless state as evaluated immediately after the preparation. This shows that not only the safflower yellow of the present invention prepared by the method of example 1 itself does not contain any odor-emitting aromatic components, or hardly contains, but also does not contain these impurities as precursors of the aromatic components.

Industrial applicability

The yellow pigment of safflower of the present invention is very pure, and therefore it does not have offensive odor or malodor originating from aromatic components contained in safflower used as a raw material, particularly its petals, or has reduced the odor significantly to the extent that the pigment is odorless or slightly odorous. In addition, the change of safflower yellow caused by the influence of heat and light during long-term storage is remarkably reduced with the passage of time. Therefore, when the pigment of the present invention or the pigment preparation containing the pigment is used for coloring beverages or other foods, pharmaceuticals, cosmetics, animal feeds, etc., the product will not be affected by the odor peculiar to the aromatic component of the safflower yellow pigment, and a product having a better taste can be prepared.

Claims (15)

1. A method for preparing odorless or slightly odorous safflower yellow pigment comprises subjecting an extract of safflower yellow pigment subjected to adsorption treatment to acid treatment at 40-100 deg.C, and subjecting to at least one treatment selected from adsorption, ion exchange, extraction and membrane separation.

2. The method for preparing safflower yellow according to claim 1, wherein the acid treatment comprises using an acid used as a food additive.

3. The method for preparing safflower yellow according to claim 1, wherein the acid treatment comprises using at least one inorganic acid selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid.

4. The method for preparing safflower yellow according to claim 1, wherein the acid treatment consists essentially of: subjecting the extract of safflower yellow to adsorption treatment or one of various other treatments to a condition of pH 3-6.

5. The method for preparing safflor yellow according to claim 1, wherein the membrane separation is at least one membrane treatment selected from the group consisting of membrane filtration, ultrafiltration, reverse osmosis, electrolysis, and ion exchange.

6. A method for preparing odorless or slightly odorous safflower yellow pigment comprises subjecting the extractive solution of safflower yellow pigment to deproteinization treatment, optionally adsorbing, acid treatment, and membrane separation.

7. The method for preparing safflor yellow according to claim 6, wherein the membrane separation treatment is reverse osmosis or ultrafiltration.

8. The process for preparing safflower yellow according to claim 6, wherein the membrane separation treatment uses a membrane having a molecular weight cut-off of 2000-4000.

9. The method for preparing safflower yellow according to claim 6, wherein the deproteinization is at least one treatment selected from the group consisting of ion exchange, extraction, membrane separation and gel filtration.

10. The method for preparing safflor yellow according to claim 9, wherein the membrane separation as the deproteinization treatment uses a molecular weight cut-off of 10⁴-10⁶The film of (1).

11. The method for preparing safflower yellow according to claim 6, wherein the acid treatment is carried out at 40 to 100 ℃.

12. The method for preparing safflor yellow according to claim 11, wherein the membrane separation is at least one treatment selected from the group consisting of reverse osmosis and ultrafiltration.

13. The method for preparing safflower yellow according to claim 11, wherein the membrane separation uses a membrane having a molecular weight cut-off of 2000-4000.

14. The method for preparing safflower yellow according to claim 11, wherein the deproteinization is at least one treatment selected from the group consisting of ion exchange, extraction, membrane separation and gel filtration.

15. The method for preparing safflor yellow according to claim 11, wherein the membrane separation as the deproteinization treatment uses a molecular weight cut-off of 10⁴-10⁶The film of (1).