JPS611348A - Color-developing method and color-developing agent for cake - Google Patents

Abstract

PURPOSE:To enable the coloring of a cake such as cookie in yellow or yellowish brown color, using an inexpensive color-developing agent, by adding a specific amount of a specific 2-keto-hexose carboxylic acid in combination with a food additive base to a pastry prepared from cereal flour, and heating with a roaster, etc. CONSTITUTION:A pastry prepared from wheat flour, baking powder, salt, margarine, sucrose, milk, whole egg, etc. is added with an aqueous solution of a color- developing agent composed of the 2-keto-hexose carboxylic acid of formula (M is H, Na, K, NH4, 1/2Ca, 1/2Mg, hydrogen ion adduct of edible amino acid, etc.) or its salt optionally in combination with a base permissible as a food additive, and is heated e.g. by roasting, frying in oil, etc. to effect the color-development of the cake in yellow or yellowish brown color. The amount of the color-developing agent and base is <=1.5%.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Purpose of the Invention (a) Field of Industrial Application The present invention relates to a method for coloring confectionery and a coloring agent for confectionery. The present invention is to be used in the food industry, particularly in the field of confectionery production.

(b) Conventional technology Conventionally, Western sweets such as kutski, crackers, biscuits, donassos, bread, castella, pies, nofu, or choux used as a crust, rice crackers, arare, etc.
In the production of Japanese sweets such as rice crackers, steamed buns, and baked mochi (rice cakes), it is important to develop colors such as yellow, yellow, and other colors on the surface of the sweets by roasting, frying, and other heating methods. It was frequently used for its flavor-generating effect. In order to promote such color development, D-glucose,
Kneading hexoses and pentoses such as D-quinloin into the dough was also a commonly used technique. In this case, the effects of D-quinlose and D-glucose are markedly different, with the former producing a yellow to yellowish color, and the latter producing a reddish-brown to brown tone.

The flavors are also different, with the former being said to have a sharper, richer flavor.

When Ushita D-Kinloth is used, the resulting saccharide has high antioxidant properties and strongly protects against oxidation of fats and oils. As mentioned above, in the prior art, D-kinlose as a pentose and D-glucose as a hexose have been mainly used.

(c) Problems to be Solved by the Invention The present inventors have been searching for a coloring agent that has D-quinlose-like coloring ability. The reason for this is that (A) this is a fairly expensive additive. Current user fee is 200
Although it is about 0 yen/Kg, it is extremely expensive compared to the 200 yen/Kg of other coloring agent D-glucose. The reason for this is (b) no other alternative compound having a similar effect is known yet.

(C) The production and sale of D-*nose is monopolized by several manufacturers.

In particular, the lack of competitive relationships in (b) and (C) is considered to be the main one.

(B) It is known that when this substance is administered to rats, white lesions occur, and there is room for doubt about its safety as a food additive. (For example, "Carbohydrates" page 94,
Please refer to 1964 3rd edition, Asakura Shoten. )Yo,
When considering the deep-rooted concerns of current consumers about food additives, it is difficult to predict whether this will be pointed out and the use of D-xylose will no longer be possible.

Therefore, the present inventor searched for a coloring agent that has similar coloring ability and can be manufactured at a relatively low cost, and finally completed the present invention.

(2) Structure of the Invention (a) Means for Solving the Problem The present invention uses 2-keto-hexosecarboxylic acid represented by the following chemical formula %, or a salt thereof. In the formula, M represents sodium hydrogen, potassium, 1/2 calcium, 1/2 magnesium, NH4, and a hydrogen ion addition room of an edible amino acid. The isomeric structure of is not a problem. Specifically, 2-ke)-L-gluconic acid, 2''-keto-D-gluconic acid, and their salts can be mentioned.According to the experiments of the present inventors, the color-forming activity and flavor-generating activity of both of them are No significant difference was observed.

The amount added is different from these hexo/acids and the conventionally used D.
- Considering the activity ratio of xylose, it is 1.5 for dough.
% or less is used. In experiments conducted by the present inventors, D-xylose and these hexo/acids showed comparable coloring activity in the donut coloring test, but they showed about 1/3 of the former's activity in the Kutsky coloring test. The usual amount of D-xylose added to dough is still 0.
．． Taking into account that the amount of these components is approximately 5%, it is estimated that the maximum amount of these additives to be added should be approximately 1.5%.

There is no problem when adding hexo/acid as a neutral salt, but when adding it as a free acid, an edible base (e.g. Potassium, soda carbonate, bicarbonate nogu, potassium carbonate, potassium bicarbonate, lucium carbonate, calcium bicarbonate, calcium hydroxide, qgnesium carbonate, ammonium carbonate, etc.), or salts with PH buffering ability (e.g. sodium acetate, fumaric acid disodium salt, tartrate disodium salt, citric acid tri(or 2) sodium salt, malic acid disodium salt, phosphoric acid tri(or 2) sodium salt,
It is preferable to use polymerized polysodium phosphate (polysodium phosphate, etc.) in combination. The hexo/acid of the present invention may be formulated not only as a free acid or a salt, but also as a mixture with the above-mentioned bases and salts. In this case, the formulations include simple powders and liquids, as well as diluents (e.g. starch, dextrin, lactose, etc.) and excipients (e.g. gelatin, gum arabic, xanthan gum, pullulan, etc.).
may also be added to formulate a powder, pellet, granule, etc. Furthermore, in the case of D-xylose, amino acids with flavor-enhancing effects (for example, glycine, alanine, tributophane, cysteine, cystine, methionine, homocystine, lysine, etc.) can be added to the dough to enhance flavor. Although it is sometimes used, this technique can also be used in conjunction with the present invention. In addition, these can also be included in the formulation, but in order to avoid deterioration during storage due to contact between hexo/acids and these auxiliary ingredients, edible lipids (e.g. hydrogenated oil, carnauba wax, Coating with beeswax, palm oil, etc.) can also be applied to the present invention.

Raw materials for dough include wheat flour, rice flour, glutinous flour, corn flour, pigeon flour, millet flour, millet flour, millet flour, buckwheat flour, and starches prepared from these flours. These usually include water, butter, margarine, toning, vegetable fat, animal fat, salt, seasoning, sucrose,
Milk, cream, cheese, egg white, egg yolk, whole egg, vegetable protein, cornstarch, yeast, acidulant, fragrance, spices, coloring and other auxiliary materials are mixed, and if necessary, after ripening, it is shaped appropriately, It is made into a product by subjecting it to heat treatments such as teriyaki and oil frying. Specifically, kutsky, crackers, biscuits,
Examples include Western sweets such as donuts, bread, castella cakes, pies, puffs, and choux used as outer shells, and Japanese sweets such as rice crackers, arare, rice crackers, steamed buns, and baked mochi.

As a method for producing the hexo/acid of the present invention, for example, the following industrial method is known, and there is room for it to be available at a low cost.

(a) 2-Keto D-gluconic acid According to "Food Engineering Experiment Book (Volume 2) J pages 182-185 (Yokendo Co., Ltd., 1971 1st edition), this acid can be used to convert D-glucose into Pseudomonas fluo.
It is described that it can be obtained in good yield by fermentation using S. rescens. According to "Applied Microbiology" page 187 (Koseikan Co., Ltd., 1970 11th edition), this compound is an intermediate for the industrial synthesis of D-araboascorbic acid (also known as inascorbic acid and erythorbic acid). It is thought that it is actually manufactured domestically as an intermediate.

(b) 2-Keto L-gulonic acid This is an intermediate in the industrial synthesis method for vitamin 7c. to produce L-enrubose. If this product is reacted with acetone to protect its hydroxyl group, and then chemically oxidized and then hydrolyzed under acidic conditions, it can be obtained in good yield. (For example, He1
v. Chin, Acta Vol. 17, 311-3.
28 Hesi ((phylum e)) This compound is also synthesized in large quantities as an intermediate in Japan.

(b) Effect If the dough to which the hequinonic acid or its salt of the present invention is added is heated by frying, roasting, etc., these will cause yellow to yellow-brown D-xylose to act on the surface of the product. D-xylose is completely different in terms of the coloring effect of 17-bar, which is similar to that of D-xylose. That is, when D-xylose is added to the extent that it produces the above-mentioned coloring effect, it emits a sharp and strongly aromatic flavor, but the hexonoic acid of the present invention has a mild and aromatic flavor, especially in the case of reminiscence. It was confirmed that it emits a unique fu-bar.

Taking into account the above properties, we find that hexouronic acid and lactones, which have similar functional groups but in different positions (specifically, D-glucuronic acid, D-glucuronic acid lactone, It was determined that uronic acids have a similar effect.(However, uronic acids have higher activity than the hexonic acid of the present invention, and the amount added is about 1/2 that of D-xylose, and about 1φ is sufficient. The same applies to applied technologies such as formulation and flavor enhancement.

For more details, please refer to the special patent application issued in 1982.
\) Examples Examples] Wheat flour xoog, bake/gutsuq udder 2.6g, salt Ig, margarine 15g1 sucrose 33g1 milk x1
Add the desired amount of coloring agent dissolved in 5 ml of water to 20 g of whole rabbit, and mix well to form a dough. Make this 7mm thick
7. Punch out into a disc with a diameter of 2 cm using a commercially available Kutsky die.

It was fried in vegetable oil at the specified temperature. After that, the sample was sealed in a plastic bag and stored in the refrigerator for one night, and then the color tone was examined.

The certification is JIS-Z-72/compliant standard color chart (glossy version)
This method is based on the method of comparing the colors and specifying the color that is considered to be the closest match.

Number Color forming agent Addition amount NaOH addition amount Oil temperature Time (
1) D-xylose 0.3g
140802 minutes (2) 20.5g
Same as above Same as above (3) Same as above 0.7g
Same as above Same as above (4) Same as above 0.9g
Same as above Same as above Mu (5) 2-ketomegro 0.3g 0.062g
Same as above Same as above Phosphoric acid (6) Same as above 0.5g 0-103g Same as above = (7) Same as above 0.7g 0.144
g Same as above Same as above (8) Same as above Q, 9g 0
．． 186g Same as above Same as above (9) Same as above 1.1
g 0.227g Same as above Same as above (10) Same as above
1.3g 0.268g Same as above Same as above (11
) 2-keto-roglu 0.4g
Same as above Potassium fluoride (12) Same as above 0.6g Same as above 2
Same as above (13) Same as above 0.8g Same as above
Same as above (14) Same as above 1.0g Same as above
Same as above (15) Same as above 1.2 g Same as above (16) Same as above 1.4 g Same as above Same as above (17) D-xylose 0.3 g
160° 02 minutes (18) ``2''
0.5g - Same as above (19) Same as above
0.7g - Same as above"2 (20) Same as above
0.9g - Same as above (21) 2-keto y
-Glo 0.3g 0.062g Same as above Ponic acid (22) Same as above 0.5g 09103g
Same 1-same”.

(23) Same as above 0-7g O, 144g
Same as above Same as above (24) Same as above -J-, Q, 9g 0.18
6g Same as above Same as above (25) Same as above 1.1g
0.227g Same as above (26) Same as above
1.3g 0.268g Same as above Same as above (27) 2-
Keto-Roguel 0.4g - Same as above Potassium conic acid (2B) Same as above 0.6g
- Same as above 2 Same as above (29) Same as above 0.8g
- Same as above (30) Same as above 1・Og
- Same as above (31) Same as above J-1,2 g - Same as above (32) Same as above 1.4 g - Same as above (33) D-xylose 0.3 g
-180°01min (34) Same as above 0.5g
- Same as above (35) Same as above 0.7g
- Same person as above (36) Same as above 0.9g
- Same as above (3η2-keto L-Glo 0.3g
0.062g Same as above Same as above Phosphoric acid (38) Same as above 0.5g 0.103g
Same as above (39) Same as above 0.7g 0.144
g Same as above (4o) Same as above 0.9g 0
．． 186g Same as above (41) Same as above 1.1g
0.227g Same as above (42) Same as above
1.3g 0.268g Same as above (43) 2
-Ketan-Guru 0.4g - Same as above Same as above Potassium conic acid (44) Same as above 0.6g - Same as above Same as above (45
) Same as above 0.8g - Same as above (46) Same as above
Above l・Og - Same as above (47) Same as above
1.2g - Same as above (48) Same as above 1.
4g - Same as above Results (1) 2.5Y 8.00/6.50 (2) 2
．． 5Y8. OO/7.50(3) 2.5Y 8.0
0. /9.00(4) 2.5Y 8.00/9.0
0 (5) 5 Y 9.0015.00 (7)
' 5 Y 8.50/6.00 (8) 2.5 Y
8.00 melody, 50 (9) 2.5 Y 8.00/6
．． 50(10) 2.5Y 8.00/6.50(1
1) 5 Y s, 5015.5° (1,2)
5 Y 8.50/6.00 (13) 2.5 Y
8.00/6.50 (14) 2.5 Y 8.00/
6.50 (15) 5 Y 8.50/6.00 (
16) 5 Y 8.50/6.00 (17)
10YR7,75/10.00(18) 10YR
7,75/11.00 (19) 10YR7,50
/11. o.

(20) 10YR7,50/11.00 (21)
10YR7,75/10.50 (22) 10
YR7, 75/11.00 (23) 10YR7,
50/11.00 (24) 10YR7, 50/1
1.00 (25) 10YR7,25/11.00
(26) 7.511R6,75/10.00 (27)
10YR7,75/10.00(28) 10
YR7, 75/11.00 (29) 10YR7,
50/11.00 (30) 10YR7, 50/1
1.00 (31) 10YR7,25/11.00
(32) 10YR7,25/11.00 (33)
'7. ! 1YR7, (I)/lO1■ (34)
7.5YR7,OO/11. ．． 0O(35) 7.5
YR6,75/11.00(36) 7.5YR6,
25/12.00 (37) 7.5YR7,OO/1
0.00(38) 7.5■6.50/11.00(
39) 7.5YR6,25/12.00 (40)
7.5YR6,OO/12.00(41) 7.5
YR6,00/12.00 (42) 7.5YR6,
OO/12.00 (43) 7.5YR6,75/1
1.00 (44) 7.5YR6,25/12.00
(45) 7.5YR6,25/12.00 (46)
? , 5YR6, OO/12.00 (47) 7.
5YR6,00/12.00 (48) 7.5Y11
s, oO15,50 When these samples are arranged in order of apparent color depth (Glo is 2-keto L-gulonic acid, xy is D''''
xylose) (A) Category C1o with oil temperature 140°C 0.3g (Glo 0.5g (Glo 0.7
guri Glo 0.9g 'q Xy 0.3g '7
C;lo 1.1g'.

Glo 1.3g<XY 0.5g4Xy 0.7g<
Xy '0.9g) Category XX 0.3g (+1.Io 0.3g (Xy 0.5
g':=611.100.5g (Xy 0.7g
'-Glo O, 7gguXYo, 9g: GIo,
0.9g '-: Glo 1.1g %: Glo 1
．． 3g (C-) oil temperature 180°C classification XyO,
'3g:' C, 1'OO, '3g ('XY 0.
5g('C;10 o,5g(xy O,'7gGl
o O-'7g (C1o 0.9g': Gl'o 1.
'l'g 'q Glo 1.3g (z) Comparison of D-xylose and potassium 2-keto D-gluconate (+1.
Iu is an abbreviation for potassium 2-D-gluconate) Glu 1.06 (Xy o, 5g (xy 0.7g<
Xyo, 9g (O oil temperature 160・C treatment area xy 013g = Gluo, 4g<xy 0.5
g'= Glu o, 6g<xy 0.7g', G
lu 0.8g, xy 0.9g -Glu
1. og < cru 1.2g (Glu 1.4g (oil oil temperature 180°C treatment section xy 0.3g < XY o, 5g (cru 0.4g
'=: xy o, 7g<xy o, 9g 壬Gl
u0.6g 'Mi Glu o, sg<cru ], o
g Atsushi (, Iu t, 2g ('Glu 1.4g,
Regarding the flavor in this example, no major difference was observed between D-xylomiyonium, 2-keto-L-guarconic acid, and 2-keto-D-guarconic acid potassium.

Example 2 Flour loOg, 30g sucrose, 1 egg yolk (chicken), 50fg margarine, 2g salt, desired amount of coloring agent and 5ml water
Knead the dissolved liquid well to make a dough with a thickness of approximately 3111 mm.
111 plate shape. Hit in a Kutsuki type and use in a household gas oven (Hitachl GOA 20
). Preheat the oven sufficiently and set the temperature in two stages (170-C, 200-C) using the adjustment dial.
). Baking time is 10 minutes at 170"C, 2
00°C for 7 minutes. The color development test was conducted in accordance with Example Y.

No. Color forming agent Addition amount NaOH addition amount Temperature (
1) D-xylose 0.2g -170°C
(2) Same as above 0.4g - Same as above (3) Same as above
Above 0.6g - Same as above (4) %”””
;: 40-2g 0.041g
lj￥Iyo (5) Same as above 0.4g 0.082g
Same as above (6) Same as above 2 0.6g
O, 124g Same as above (7) Same as above
0.8g O, 165g Same as above (8) Same as above -
Hi 1. Og 0.205g Same as above (9)
2-Keto-D-0.2g - Same as above Potassium gluconate (10) Same as above 0.4 g - Same as above (1) Same as above 0.6 g - Same as above (12) Same as above 2 0.8
g - Same as above (13) Same as above 1.0g - Same as above (14) Same as above 1.2g - Same as above (15)
D-xylose Q, 2g -2006C (1
6) Same as above 0.4g - Same as above (17) Same as above
Above 0.6g Same as above (18) 2-keto-1,-0.2g 0.041g Same as above Gulonic acid (19) Same as above 0.4g Oo-0B2.
Same as above (20) Same as above 0.6g 0.124g
Same as above (21) Same as above 0.8g 0.1
65g Same as above (22) Same as above 1.0g
0.205g Same as above (23) 2-keto-D-0
, 2g - Same as above Potassium gluconate (24) Same as above 0.4g - Same as above (25) Same as above 0.6g - Same as above (26) Same as above 0
．． 8g - Same as above (27) Same as above 1.0g
- Same as above (28) Same as above 1.2g - Same as above Result (1) 2.5Y8.00/7.50
(15) 10YR7,75/9.00 (2) 2.
5Y8.00/11.00 (16)
1.0YR7,75/10.00 (3110YR7,5
0/9.00' (17) 10Y
R7,51)/11.00(4) 5y8.75/6
．． 09' (18) 5Y8.50
/6. (Xi(5), 5Y 8,5(!/6.09
(19) 2.5Y 7.75/9.0
0(6) 2.5Y g, oo/8. oo
(20) 2.5Y 7.75/9. CX) (7
) 2.5Y 7.75/9.00 (
21) 2.5Y 7.50/10.00 (8) 2.
5Y 7.50/10.00 (22)
2.5j7.50/IQ, 00(9) 5Y 8.
75/4.50 (23) 2.5Y
8.00/9.00 (10), 5Y8.7515
．． 00 (24)2.5Y7.75/
9.00 (11) 5Y 8.7515.50
(25) 2.5Y 7.75/10.0
0(12) 5y 8.7515.50
(26) 2.5Y 7.50/10.0 (1,
3) 2.5Y 8.00/7.50
(27) 2.5Y 7.50/11.00 (14)
2.5Y 8.00/8.00 (
28) 2.5Y 7.50/, 11.50 or less margin These samples were arranged in order of apparent color density as follows.

(A) Comparison of D-xylose and 2-keto L-gulonic acid XX (a) Treatment area with smoking temperature of 170'C Glo O, 2g <cto O, 4g < xy 0.2
g<cto o, ag(xy 0.4g(Glo o,
sg<cto 1.0g (xy O, 6g (b) Treatment area C with teriyaki temperature 200°C; lo 0.2g (Glo ci, 4g<'cxo
0.6g <Xy 0.2g (Glo O, 8g<Gl
o t, og < Glu 0.4g (ctu o, 6
g(Glu 0.8g ” xy o, 2g (Gl
u1. Og (Glu 1.2g <Xy 0.4g
(xy 0.6g The acidity was mild and elegant.

Example 3 Sodium 2-keto L-guulonate or potassium 2-keto-kugluconate alone or as a mixture in any proportion
Coloring agent for liquid confectionery containing 0% by weight.

Example 4 100 parts of the aqueous solution of Example 3, 12 parts of 60 thidextrin solution
A coloring agent for powdered confectionery obtained by mixing 40 parts of 0 parts and 15 parts of tyracto during heating and spray drying.

Example 5 2-l-gulonic acid (1 part), 10 parts of baking soda, 2 parts of citric acid
A coloring agent for confectionery in the form of a powder consisting of 5 parts of sodium water crystal powder and 15 parts of lactose.

Example 6 Potassium 2-keto D-gluconate is a simple confectionery coloring agent.

Example 7 2-parts of L-gulonic acid and (9) parts of hydrogenated oil are mixed while the fats and oils are melted, and the mixture is cold-pulverized. To this, add one part of soda carbonate, 5 parts of disodium citrate ice-containing crystal powder, 2 parts of L-cystine, 2 parts of DL-methionine, 2 parts of DL-alanine,
A coloring agent for confectionery made by mixing lactose omega.

Example 8 A color former for granular confectionery produced by adding 2 parts and 5 inches of xanthan gum to the color former of Example 7 and wet-granulating the mixture.

Example 9 A coloring agent for confectionery using Example 7 but using potassium 2-D-gluconate and excluding soda carbonate. and a confectionery coloring agent obtained by subjecting this to the granulation process of Example 8.

Reference example 1 Commercially available L-sorbose (reagent grade) xsog, Ace73
2. Add 217g of sulfuric acid (98g) to No. Mix and stir in a pen. The reaction system and the outside air are communicated through a calcium chloride tube, and stirring is performed until L-sorbose is completely dissolved. It became uniform in about Shu minutes. The reaction system gradually becomes dark red. 18 after addition time
0 g of sodium hydroxide dissolved in 11' methanol was added to neutralize. Remove the salt from the mouth and wash with acetone. The washing liquid and oral liquid were combined and concentrated under reduced pressure. The residue was extracted three times with 300 ml of ethyl ether, and the remaining red syrup was thoroughly washed with ether. The extract and washing liquid were combined and concentrated to obtain 188 g of dark brown oil. This material was distilled under reduced pressure to obtain Bp129・C/ 1.571g −
111 g of diacetone-L-sorbose as a pale yellow oil at 148°C/2 mmHg. This product will crystallize easily if left after seed crystallization, mp 77-800c
showed that. (Literature value 77-78°C (He1v, Ch
(in, Acta Vol. 17, p. 319) Diace) ``'T''' 7) Bose 120 g 5 Potassium 54 g was added to the water layer 1.2 K, and permanganese acid was added under stirring with water cooling.
A solution prepared by dissolving 3.2 g of water in 2.6 Y of water was added over 1 hour. The mixture was left at room temperature overnight and heated to ω°C on a water bath. The color of the reaction system became almost colorless. The remaining manganese dioxide was washed three times with 200 ml of hot water, and the oral fluid and washing fluid were combined, adjusted to pH 8.5 with hydrochloric acid, and concentrated under reduced pressure. Total amount 50
When the volume reached 0 ml, extraction was performed twice with 100 ml of ether, and the aqueous layer was completely concentrated under reduced pressure. 188 g of solid are obtained. This product was dissolved in 500 ml of water, and 50 ml of hydrochloric acid was added under water-cooled stirring, and after 1 hour, 75 g of colorless crystals formed were taken. This setone-2-L-
Add gulonic acid to 600 m of water and when it becomes a small amount, add 1
The mixture was extracted three times with 00 ml of ether, and the aqueous layer was further concentrated to a total volume of 10 ml. 400 ml of Ingropanol was added to the aqueous layer to form seed crystals and stored in a refrigerator for three days. The produced colorless crystals were taken and air-dried to obtain 38 g of 2-keto L-gulonic acid. . , 169~170°
C decomposition (Reference I&P 171°C decomposition (He1v, C
Him, Acta Vol. 17, p. 324) The oral fluid was concentrated under reduced pressure to a total volume of 20 ml, ethanol was added until it became slightly cloudy, and the mixture was cooled to obtain an additional 5 g of crystals.

g was reacted in the same manner as in Reference Example 1. After 24 hours, the mixture was cooled with water and neutralized with 30% sodium chloride soda. Bori-sai is 200
Wash the mouth twice with 1 ml of acetone. Combine the mouth liquid and the rinsing liquid and concentrate under reduced pressure. A dark brown solid was obtained. 500ml
The remaining syrup was extracted twice with 200 ml of hot benzene. Benzene I was combined and treated with a small amount of activated carbon. If the total volume is 500 sea ml and cooled on ice, 84 g of first crystals of soacetone-D'''fructose will be obtained.The mother liquor will be further concentrated and the total volume will be 300 cm.
It was set as m1. After cooling with water, 15 g of second crystals were obtained. Further, the total volume was adjusted to 100 ml, and 20 ml of petroleum benzine was added thereto and cooled on ice to obtain 37 g of third crystals.

Water 1.5X force I765.7 g, Ma...
1.7-.

Add 146 g of luctose, and dissolve 26 g of lactose in water of 1.
Added at 5 hours. Stir at room temperature for 3 hours,
It was heated to C. After cooling, the pH was adjusted to 8.5 with hydrochloric acid, the mixture was concentrated under reduced pressure with a strainer to a total of 500 ml, and extracted three times with 150 ml of benzene. The aqueous layer was completely concentrated, the remaining solid was dissolved in 400 ml of water, and the pH was brought to 1 with concentrated hydrochloric acid. The precipitated oil was extracted three times with chloroform + 501 TIl, and the chloroform layers were combined, dehydrated with nitric acid, and concentrated under reduced pressure. 118 g of pale yellow syrup was obtained. (Diacetone-2-keto D-gluconic acid) This was dissolved in 1 volume of water and refluxed for 40 minutes while removing water little by little. After cooling with water, it was concentrated under reduced pressure to obtain crude 2-keto D-gluconic acid as an asg syrup. This was dissolved in 300 ml of methanol, and a solution of 25 g of potassium hydroxide dissolved in 150 ml of methanol was added, and the resulting oil was thoroughly washed and solidified. After dissolving in 120 ml of water, 40 ml of isopropanol and 120 ml of methanol were added, cooled on ice, and the resulting light brown crystals were collected. O up 1 obtained 48.5 g of potassium 2-keto D-gluconate
52 ~ 153 °C decomposition (literature value mp 152 °C decomposition (Chemische Berjcht, e 60B
.

Reference Example 3 A donut coloring test was conducted in exactly the same manner as in Example 1. Color formers include D-xylose (XY), D-glucuronic acid (Glu), and D-glucuronic acid lactone (Glu).
-L), D-galacturonic acid monohydrate (G a
E, ) was used.

No. Color forming agent Addition amount NaOH addition amount Temperature
Time tM(1) XY 0.3g -, 1
40°0 3 minutes (2) Same as above 0.5g - Same as above = (3) Same as above 0.7g - Same as above
Same as above (4) Same as above 0.9g - Same as above (
5) Glu 0.3g 0.061g
Same as above Same as above (6) Same as above 2 0.5g 0.102
g Same as above Same as above (7) Same as above 0.7g 0.
143g Same as above Same as above (8) Same as above 0.9g
0.184g Same as above Same as above (9) Glu-L
O,3g 0.068g Same as above Same as above (1
0) Same as above 0.5g 0.113g Same as above (11) Same as above 0.7g O・158g
Same as above Same as above (12) Same as above; 0.9g, 0.2
03g Same as above Same as above (13) Cal O,3
g 0.056g Same as above Same as above (14) Same as above
0.5g 0.093g Same as above Same as above (15
) Same as above 0.7g 0.131g Same as above (16) Same as above 0.9g O, +68g Same as above Same as above (17) XY O, 3g
'160°C
Same as above 2(18) Same as above 0.5g - Same as above
Same as above (19) Same as above 0.7 g - Same as above Same as above (20) Same as above 0.9 g - Same as above Same as above (2
1) &”z -0,: 3g - 0,061g Same as above L (22) Same as above 0.5g 0.102g
Same as above Same as above (23) Same as above 0.7g 0.143g
Same as above Same as above (24) Same as above 0.9g, 0.184
g Same as above Same as above (25) Glu-L 0-3g
0-068g Same as above Same as above (26) Same as above 0.5g
0.113g Same as above Same as above (27) Same as above 0.7
g O, +58g Same as above Same as above (28) Same as above 0.
9g 0.203g Same as above Same as above (29) Cal
0.3g 0.056g Same as above Same as above (30
) Same as above 0.5g 0.093g Same as above Same as above (3
1) Same as above 0.7g 0.131g Same as above (32) Same as above 0.9g 0.168g Same as above Same as above (33) Xy 0.3g -180°C 2 minutes (34) Same as above 0.5g - Same as above (35) Same as above 0 .7g - Same as above Same as above (36) Same as above 0.9
g - Same as above Same as above (37) Glu 0-3g
0.061g Same as above Same as above (38) Same as above 0.5g
0-102g Same as above Same as above (39) Same as above 0.7
g O・143g Same as above Same as above (40) Same as above 0.
9g 0.184g Same as above Same as above (41) Glu
-L 0-3g 0.068g Same as above Same as above (4
2) Same as above 0.5g O, 113g Same as above Same as above (
43) Same as above 0.7g 0.1 ramie 8g Same as above (44) Same as above 0.9g 0.203g Same as above Same as above (45) Gal 0-3g 0-05
6g Same as above f(46) Same as above 0.5g 0.0
93g Same as above 1k (47) Same as above 0.7g 0
．． 131g Same as above Same as above (48) Same as above 0.9g
Q・168g Same as above Same as above Result (1) 2.5Y8.00/7.00 (
5) 2.5Y8. OO/11.00 (2) 2.
5Y 8.00/9.00 (6) 2.
5Y 7.75/11.00 (3) 2.5Y 8. r)
o/lo, oo (7) 2.5Y 7.
75/11.00 (4) 2.5Y 8.00/10
．． 00 (8) 2.5Y 7.75/1
1.00 (9) 2.5Y8.00/9.00
(13) 2.5Y8. OO/9.00(10) 2
+5Y 8. OO/9.50 (14)
2.5Y 8.00/9.50 (11) 2.5Y
8.00/10.00 (15) 2.5
Y 8.00/10.00 (12) 2.5Y 7.
75/10.00 (16) 2.5Y,
8.00/10.00 (17) 10YR7,50/
12.00 (21) l0YR7,
00/12.00 (18) 10YR7, 25/12
．． 00 (22) 10YR7,OO
/12. ■(19) 10YR7,00/12.00
(23) 10YR6, 50/12.
00(20) 10YR7,OO/12.00
(24) 10YR6,25/12.00(
25) 10YR7,75/'12.00
(29) 10YR6, 25/12.00 (26
) 10YR7,50/12.00 (
30) 10YR6,25/12.00(27)
10YR7,50/12.00 (31)
10YR6,00/12.00(28)' 10Y
R6', '75/'12.00 (32)
10YR6,25/12.00(33) 7.5Y
R6,50/12.00 (3n 7.
5YR6, 25/12.00 (34) 7.5YR6,
25/12.00 (38) 7.5Y
R6,00/11.50 (35) 7.5YR6,25
/12.00 (39) 7.5YR6
,00/11.50(36) 7.5YR6,25/1
2.00 (40) 5. OYR5,0
0/9.50 (41) 7.5YR6,75/12.0
0 (45) 7.5YR6,25/1
2.00 (42) 7.5YR6,50/12.00
(46) 7.5YR6, 25/12.
00(43) 7.5YR6,50/12.00
(47) '7.5YR6,00/12.00
(44) 7.5YR5,75/12.00
'(48) When samples of 7.5YR6,00/12.00 or higher were arranged in order of apparent color depth, they were as follows.

(1) 1400C treatment area (A) Comparison of D-xylose and D-glucuronic acid
7 o, 3g (xy 0.5g (xy O, 7g
= Xy o, 9g(Glu 0.3g(Glu 0.
5g + Akatsuki Giu0.7g”: (,lu 0.9
g(B) Comparison with D-glucuronic acid lactone Xy 0
．． 3g (Xy 0.5g':, 1u-L 0.
3g (Glu-L 0.5g (Xy 0.7g').

Xy 0.9g 'q Glu-L O,7g (G
lu-L 0.9g (C) Comparison with D-galacturonic acid monohydrate Xy 0.3g (Xy 0.5g
壬Cal 0.3g (11; al 0.5g (Xy
0.7g'; Cut 0.7g', Xy 0.
9g' = C, al O, 9g (2) 160°C
(A) Comparison with D-glucuronic acid Xy O, 3g (Xy 0.5g (Xy 0.7g
':; Xy O,9g '= C; Iu 0
．． 3g 'E Glu 0.5g (Glu O, 7g
<C1u, 0.9g (B) Comparison with D-glucuronic acid lactone Glu-L 0.3g<xy 0.3g (G
lu-L 0.5g = Glu(, o, 7g(xy
0.5ggXyo, 7g'q Xy 0.9g (G
lu-L 0.9 g (comparison with QD-galacturonic acid monohydrate Xy O, 3 g (Xy 0.5 g (Xy
0.7g #Xy O, 9g (Gal O, 3g
: Gal 0.5g '=Gal Q, 9g
<cat o, 7g'('3) 180°
Treatment area of C (A) Comparison with D-glucuronic acid
．． 5g = xy 0.7g = xy O, 9g〈C
, Iu 0.5g"= C1u 0.7g (clu
0.9g (B) Comparison with D-glucuronic acid lactone C1u-L 0.3g<Xy 0-3g''=Gl
u-L 0.5g 1,000 Glu-t, 0.7g(Xy
0-58 3xy 0.7gXy 'Q, 9g
<cxu6L O, 9g (C) Comparison with D-galacturonic acid monohydrate Xy O, 3g (Xy 095
g'= Xy O, 7g'= Xy 0.9g'
= Gal 0-3g LE Gal O, 5g (Ga
l 0.7g # Cal 0.9g In this experiment, a Kutsky coloring test was conducted in the same manner as in Example 2 for D-glucuronic acid, its lactone, and D-galacturonic acid monohydrate.
It was carried out for 10 minutes at 0°C and for 7 minutes at 200'C.

No. Color forming agent Addition amount NaOH addition amount Temperature (1
) Xy 0.2g, -150'
C(2) Xy 0. Shun - Same as above (3
) Xyo, 6g - same as above (4) Xy
0.2g -170°C (5)
Xy 0.4g - same as above (6),
xy 0.6g - Same as above (7) X
y 0.2g -200'C (8)
Xy O,4g - same as above (9)
Xy O,6g - same as above (10)
Cal 0.2g0-038g 150
'C(11) Gal 0-4g 0
．． 075g Same as above (1,2) C, at
O,6g 0.113g Same as above (13
) Gal 0.8go, 151g
Same as above (14) Gal 0.2g
0-038g 170'C (15) Gai
0-4g 0.075g Same as above (
1,6) Cat O,6g 0.1
13g Same as above (17) Gal 0
．． 8g 0.151g Same as above (18)
Coal 0.2g 0.038g
2000C (19) Gal 0-4g
0-075g @Top (20) Cat
0-6g 0.113g Same as above (2
1) Gal, 0.8g o, 151g
Same result (1) 5. OY (1,00/6.00(2) 2.
5Y 8.00/9.00 (3) 2.5Y7.75/
8.00 (4) 10YR8,OO/8.50 (5)' 10YR7,7!5/12.00(6) =
10yR6,7s/12.0O(7), 10YI?
s, 75/1o, o.

(8) 10YR6,7! ! /11.0Q(9) 10
YR6,25/10.00 (10), 5Y 9.0
Q15.7ri (11) 5Y 8.00/9.50 (12) 5Y 8.00/10.00 (13) 2.
5Y7.75/8.00 (14) 2.5Y 8.00
/6.75(15) 10YR8,OO/8.50(1
6) 10YR7,25/12.00(17) 10
YR6,50/12.00 (18) 2.5Y 7.
75/8.00 (19) 10YR7, 25/11
．． 00(20) 10YR6,75/11.00(
21) 10YR6,00/10.00 These samples were arranged in order of apparent color depth as follows.

(A) x5o6c treatment area Cal 0.2g<xy o, zg(cal o, 4
ggu(,al 0.6g(xy O,4g <Xy O
,6g':.

Gal O-8g (B) 170°C treatment area Ca10.2g (Xy O, 2g # Cal O,
4g(Xy 0.4g(Ga10.6g(Xy 0-6
g (GaI 0.8g (C) ZOOoC treatment section Cal 0.2g (Xy O, 2g = Gal o
, 4g (xy 0.4g: C, al 0.6g (
Xy o-ag<Cal 0.8g In this experiment, the flavor of D-galacturonic acid monohydrate when phosphorous was found to be milder and mellower than that of D-xylose, and that of D-quinlose was sharper and richer. Ta.

Reference example 5 A Kutsky color test was conducted in exactly the same manner as in Example 2.

However, ・150'C, 170°C for 9 minutes ・200°
C was run for 7 minutes.

No. Color former Addition amount HaoHI! lii addition (1) X7 -0・2g -(2)
Xy 0.4g - (3) X7
．． 0.6g - (4) Xy, o・
8g - (5) Glu, 0. Q
0.041g (6) Glu O, 4g
0.082g (7) Glu O, 6g
0.124g (8) C1u 0-8
g 0.165g (9) Glu-Lo, 2g
0.045g (10) Glu-LO
,4g 0.091g(11) ・Glu-L
0.6g 0.136g (12) Glu
-L 0.8g 0.182g% at 150℃
The I-fired ones showed almost no color development, and the ones heated at 170°C and 200°C were clearly colored. When these samples are arranged in order of apparent color depth, they are as follows, but there was no difference in color tone depending on the color former, and all were yellow to yellow-brown.

(1) Comparison of D-xylose and D-glucuronic acid (A
) l'i'o℃ treatment area Glu O, 2g (Xy 002g (Glu O,
4g(X, y O, 4gjG1u O, 6g<Xy O
, 6g Moth Xy O, 8g (B) 2'OO℃ treatment section
(Glu O, 6g (Xy O, 4g<Xy 0
06g (Glu O,8g:Xy 008g(2
) Comparison of D-xylose and D-glucuronic acid lactone (A) l'70°C treatment area (B) 200°C treatment area Glu-L 0.2g (Glu-L O, 4g
<Glu-L 0.65 (Xy 002g<x
yO04g'=HGlu-L O,8g (xy o
, 6g <xy 008g The flavor when making Daichi ware is D“
- Both glucuronic acid and the same lactone were milder and less harsh than D-xylose.

(3) Effects of the Invention The effects of the coloring agent of the present invention are (a) A novel coloring agent, which has been completely unknown heretofore, is brought to the field of confectionery manufacturing.

(b) Moreover, its action is similar to the coloring action of D-xylose, for which no alternative compound has been known until now, and it will enrich the technology in this field.

(C) Flavor generating ability is completely different from D-xylose and can impart a mild and pleasant flavor.

(d) Furthermore, if ('b) and (C) are taken into consideration, it is possible to provide a new and useful additive that can be used in the production of confectionery.

- and so on.

Claims (4)

[Claims] (1) The following chemical formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, M is H, Na, k, NH_4, 1/2Ca, 1/
2Mg, a hydrogen ion adduct of an edible amino acid, etc. ) 2-keto-hexosecarboxylic acid or its salt represented by 1.5% or less is added to the dough prepared from flour, together with a food-acceptable base if necessary, and added to the dough for roasting, frying, etc. A method for coloring confectionery, which is characterized by coloring a confectionery yellow or brownish yellow by heating means. (2) The following chemical formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, M is H, Na, k, NH_4, 1/2Ca, 1/
2Mg, a hydrogen ion adduct of an edible amino acid, etc. 2-Keto-hexosecarboxylic acid shown in ) or a salt thereof; and, if necessary, a base that is acceptable for food addition. (3) The 2-keto-hexose carboxylic acid described in claim (2) or its salt, and if necessary, a base acceptable for food addition, a diluent, an excipient, and further, if necessary. The coloring agent for confectionery according to claim (2), which is formulated by adding an oil-based coating agent. (4) The coloring agent for confectionery according to claims (2) and (3), characterized in that an amino acid having a flavor enhancing effect is added.