JPS611367A - Method of color formation of fish-paste product and color former - Google Patents

Abstract

PURPOSE:To impart a color formation effect, having improved flavor and light resistance, and partially resembling D-xylose to a fish-paste product, by adding 2-keto-hexonic acid or a derivative thereof in a specific proportion thereto. CONSTITUTION:2-Keto-hexonic acid expressed by the formula (M is amino acid having added H, Na, K, NH4, 1/2Ca, 1/2Mg or hydrogen ion) or a derivative thereof in an amount of 1.0% or below is added to a fish-paste product. A pH adjustor, e.g. polymerized phosphate, elasticity enhancer, edible surfactant, e.g. lecithin, are used together if necessary.

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 a fish paste product and its development.

(b) Conventional technology "Coloring of fish, meat, and pork products" referred to in the present invention refers to grilled products (
For example, battered products such as grilled kamaboko, grilled chikuwa, atsuyaki, umeyaki, etc.), steamed grilled foods (e.g. steamed grilled kamaboko, etc.), or fried foods (e.g. tempura, fish cakes, fried kamaboko, etc.) are added during the manufacturing process. During heat treatment such as Rokugo-yaki and oil frying, amine compounds such as brown, brown, dark brown, yellow amino acid, and protein react on the surface during heating, causing a so-called Maillard reaction and forming melanoidins. It is understood that this is due to the production of a pigment called. However, in today's common knowledge of food chemistry, the details of this reaction and the structure of the resulting pigment are still not well understood.

In actual manufacturing technology, this coloring or coloring phenomenon is actively utilized. Due to this coloring, the appearance of the paste product]
It is also said to increase appetite and produce a pleasant flavor as the color develops. Currently, in order to intensify such a coloring phenomenon, (△) scolding (+'l) D-glucose (C) D-gi/loose is being used. These three types of coloring agents have different effects and efficacies, and are added singly or in combination depending on the product.

(/I) Of the 13 types of color formers, this one has been used since the earliest times. Normally, when used for minced meat at a level of 1 to 4, it not only acts as a seasoning and flavor improver (especially masking fish odor), but also as a coloring agent that produces a reddish-brown to brownish color. do. However, the color tone and intensity are not constant depending on the type of mirin, and seem to be influenced by its raw materials, fermentation conditions, etc. Therefore, when using it for factory production, it is safe to use the same product from the same manufacturer, and in the event that you change it, please conduct experiments in advance to ensure that the coloring power is 1.
It is necessary to test the color tone.

(B) D-glucose D-glucose is J), 5 = -1% of ground meat
Add degree. However, in the Kansai region, people prefer dark-colored products that use a slightly larger amount, but in the Kanto region, i, io, 1~
It seems that people also like products that have a light brown color by adding about 0.3 treble. High concentration of this stuff (below 0.5)
When added to the oil and heated at high temperature (1 cup above 160°C in oil temperature), it produces a brown to dark brown color with a low concentration (0
, 5% or less), low temperature (oil temperature 145°C to 155°C)
When heated at temperatures (°C), it exhibits a reddish-brown or light-brown color.

This product is highly pure and can be obtained at low cost, and products from various manufacturers are compatible.

However, adding this substance tends to shorten the shelf life of the product and makes it more likely to be contaminated with mold-causing bacteria. The former is because it is the most easily available energy source for all living things, including microorganisms, and the latter is because it is the most easily available energy source for all living things, including microorganisms, and the latter is because it is the most readily available energy source for all living things, including microorganisms.
Nterobacter cloacae 1Achro
mol+acter brunificans SPs
eulomonas fluorescens etc.) is D
-Glucose is oxidized to produce 2-keto-D-gluconic acid, which is further oxidized by microorganisms to produce and accumulate highly reactive 2,5-diketo-D-gluconic acid. . (For example, please refer to the Japanese Society of Fisheries Science, Vol. 39, p. 221, p. 229, etc.) This contamination can occur during the distribution of the product, such as a change in color or black in the white part of the chin row, or a change in the appearance. Although there is no abnormality, the white part is observed to become distorted during heating such as boiling.

(Q D-Kinloose This is the most recently introduced coloring agent and has become widely used in the past few years.The characteristics of this product are: (a) Strong coloring power, usually sanded 0.5% for body
Color develops well when added in small quantities.

(b) Does not adversely affect shelf life.

Although this sugar is derived from natural products, it is difficult to assimilate by microorganisms and is known to be difficult to ferment. To produce this product, corn cobs, wheat straw, etc. are hydrolyzed with acid, yeast is propagated in the neutralized and desalted mother liquor, and the coexisting D-glucose, D-galactose, etc. are assimilated. A method of obtaining it by subsequent concentration and crystallization is known.

It is also said that contamination with fungi will not occur.

(C) The color tone is unique.

The color tone of this product is produced at a low temperature (145-1 at the oil temperature)
55°c1 At low concentrations (less than 0.34), the color is light yellow or yellow, and at high temperatures (055-1600C), and at high concentrations (0.3% or higher), it is golden yellow or golden brown; It is clearly different from anything else.

The pastry products that are colored by adding this substance have a bright yellow to golden color tone, and are particularly well received by consumers in the sub-section.
Something once became popular. Pastry products of this color were unknown until the introduction of D-kinloose.

However, the following drawbacks can be pointed out to D-xylose.

(a) It is expensive.

The current user fee is about 2,000 yen/Kg, which is extremely expensive compared to the 200 yen/Kg of D-glucose, another coloring agent. The causes of this include: ○D-Kijiroses or its raw material xylan.

○There are no known substitutes that have the same effect.

However, the lack of competitive relationship between the latter two seems to be the main factor.

(There is room for doubt about the safety of this product.

It is known that when this substance is administered to rats, it causes white spots, and given the strong suspicion of consumers about food additives, it is difficult to actually use f-1x as this may become a problem. I'm worried that something like that might happen. (For example, please refer to "Carbohydrates" page 94, 3rd edition published in 1960, Breakfast Bookstore.) /2) Structure of the invention (a) Means to solve the problem Based on this, we have been engaged in the search for a D-xylose-like coloring agent that exhibits a yellow color, and have discovered several alternative compounds, and the present invention will be given a position as a part of this research. . However, the coloring effect of the coloring agent of the present invention is not necessarily the same as that of D-xylose, and it takes on a slightly brownish tone in a high concentration range. In the low concentration range, it is similar to that of D-xylose.

The inventor's additive color test (aburachi with tempura).

In the test), the color intensity of the compound of the present invention was about 1/2 that of D-xylose. However, if the amount added is more than 0.5 to 0.6 inches based on the ground meat, it will be D-
The color tone of xylose (yellow to golden yellow to brownish) is slightly different from the yellow cutlet color.
The color tone is similar to that when glucose is used together.

It is well known that the color produced by heating fades due to the light from fluorescent lights in the show window.
According to a fading experiment using a fluorescent light, the ease of fading was comparable to that of D-kinloose.

In the conventional coloring technology for fish paste products, it is preferable to use a coloring agent (particularly D-xylose) and an elasticity enhancer in combination, especially in the production of grilled bamboo shoots, to eliminate uneven grilling and improve grilled gloss and shine. It has been done. Examples of elasticity enhancers include bromate (especially -h lysate), ascorbic acid (salt), polymerized phosphate, calcium salt (chloride, sulfate, acetate, carbonate, bicarbonate, lactate, gluconate, etc.). These are usually added in an amount of 0.1% or less to the ground meat.

It is also well known that the grilled or fried color fades due to the light from fluorescent lamps in the rows in the shop window.
To prevent this, apply a pH adjuster to the ground meat.
．． Add 2% or less. Examples of PH regulators include sodium acetate, phosphates, polymerized phosphates, free acids of edible polycarboxylic acids (e.g. citric acid, co-phosphoric acid, tartaric acid, fumaric acid, malic acid, etc.), monomers, etc. , di-, tri-salts, etc. In addition, edible surfactants (e.g., Shi/Chin, higher fatty acid soyosugar esters, higher fatty acid monoglycerides, etc.) are applied to thin the white areas, increase whitening, and improve the gloss and shine of the surface. It is also done to add a level of ``screamer'' to the upper body. The present invention does not exclude these conventional techniques, but rather uses these in combination and distributes these additives in advance, such as carrots, cabbage, burdock, etc. If mixed, a large amount of water will be liberated during frying, which will interfere with color development, so it is necessary to add a large amount of color former. Therefore, when mixing the ingredients, it is necessary to add the amount to be added to the ground meat after mixing the ingredients. The amount of 2-keto-hexonic acid added in the present invention is such that the upper limit of the amount of D-quinlose added is 0.5 or less (standard addition amount in normal usage), and the color intensity of the former is 1/2. Since it was about 2 pieces, it is less than about 1 piece for Suri T and B pieces.

In fact, in the present invention, the chemical formulas in claims (1) and (5), that is, HOH H20H, are interpreted as follows. In the formula, M is hydrogen, sodium,
Examples of amino acid residues include alanine, lysine, histidine, and methionine. ) is shown.

-Furthermore, 2-kel-hexonic acid represented by this chemical formula may have many structural isomers, but in the present invention, the isomeric structure of L, epimer, etc. does not matter.

For example, examples 1 to 2-D-gluconic acid and 2-keto L-gulonic acid are given.

There is no problem when hexonic acid is added as a neutral salt, but when added as a free acid, edible bases (e.g. hydric soda, hydric potassium, carbonic acid, soda, bicarbonate of soda, potassium carbonate, potassium bicarbonate, cal/rum carbonate, calcium bicarbonate,
hydroxide, magnesium carbonate, ammonium carbonate, etc.), or PHW disodium malate, triphosphoric acid, etc.
(or 2) Preferably, a is used in combination with sodium, polymerized polysodium phosphate, etc.

Gao 4 invention. 2 months 1. In addition to being formulated as a free acid or a salt alone, the -h+77 acid may be formulated as a mixture with the above-mentioned bases and salts. Furthermore, the above-mentioned PH adjuster, elasticity enhancer, and surfactant may also be included in the mixture. In addition to simple powders and liquids, diluents (e.g., starch, dextrin, lactose, etc.) and excipients (e.g., gelatin, gum arabic, xanthan gum, pullulan) are also added to form powders, pellets, and grannies. - It can also be formulated into a liquid or the like.

Furthermore, in order to avoid deterioration due to chemical reactions during storage between 2-ketohexonic acid and other components contained, edible fats and oils (e.g. hydrogenated oil, carnauba wax, miso wax, palm oil, etc.) are coated. It is also possible to apply to the present invention.

As a method for synthesizing the 2-keto-hexonic acids of the present invention, for example, the following industrial methods are known, and there is a possibility that they can be obtained at low cost.

(a) 2-keto-ku gluconic acid According to "Food Engineering Experiment Book (Volume 2) J pages 182-185 (Yokendo Co., Ltd., 1971 edition), this substance is pseudomonas fluorescen.
It is described that it can be obtained in good yield by cell fermentation using s. Also, “Applied Microbiology” 187
According to Page (Koseikan Co., Ltd., 11th edition, 1978), this product is D-Arabo Ascor, and is thought to be currently produced as an intermediate in Japan.

(b) 2-keto-siguulonic acid This is an intermediate in the industrial synthesis method of vitamin C. D''''glucose is added to form D-sorbitol, which is then treated with Acetobacter bacteria to produce L-sorbitol.
Sorbose. If this is condensed with acetone to protect its hydroxyl group, and then chemically oxidized and then hydrolyzed under acidic conditions, it can be obtained in good yield. (e.g. He1v, Chlm-A
cta vol. 17, pages 311-328 (1934
)) This product is also synthesized in large quantities as an intermediate in Japan.

(b) Effect: If the ground meat to which the 2-keto-hexonic acid or salt thereof of the present invention is added (grilled, fried, etc. - Expresses the same coloring effect as when xylose is applied. (However, in the high concentration range, the color tone is slightly brownish, which is slightly different from that of D-xylose.) Also generated when heated. The flavor is mild and unique, unlike the strong and unique flavor of D-xylose (like burning straw. Some people dislike this. This is especially a problem in demonstration sales.) It is something.

Furthermore, the coloration developed by the compound of the present invention is not inferior to D-xylose in terms of light resistance.

Regarding the shelf life when these are added, the growth rate of the general viable bacterial count in a storage test is approximately the same as that of D-xylose, and is not inferior to that of D-xylose.

(Han Examples Example 1 Sken - 100 parts of frozen surimi, 3 parts of common salt, 20 parts of corn starch, 1 part of MVP powder formulation, 1 part of sodium glutamate)
part, 70% 0% Norbit, 5 parts, water 60 parts, turpinoic acid preparation (“Netokira KDNJ, manufactured by Nippon Shinyaku Co., Ltd.) 0
．． Mix 8 parts of the squid in the usual manner and use it as the surimi. To 100 parts of this material, the desired amount of coloring agent is dissolved in 5 parts of water and mixed. After molding into a dry form, the first stage is heated to 125° to 130°C for 2 minutes, and the second stage is heated to the desired temperature for 3 minutes. The mixture was ground in oil for a minute (with stirring every second) and the pH was measured. (Xy is D-xylose, Glu is 2-keto-
Potassium Kugluconate, G]-〇 is used as an abbreviation for 2-keto-sigulic acid, and NaOH is used as an abbreviation for hydric soda. ) No. Color forming agent Addition amount NaOH addition amount Second stage oil temperature (1) Xy O, 1 part -145°
~150°C (2) XY O, 15 parts −
Same as above (3) Xy O, 2 parts - Same as above (4) Xy O, 25 parts - Same as above
Above (5) Xy O, 3 parts - Same as above (6) Glo O, 2 parts 0.041 part
Same as above (7) Glo O, Part 3
0.062 parts Same as above (8) Glo
O, 4 parts 0.082 parts Same as above (
9) Glo o, Ri part 0.103 part
Same as above (10) Glo OJ part 3 0
．． Part 124 Same as above (11) Glo
O, 7 parts 0.144 parts Same as above (1, 2
) Glo, 0.8 parts 0.165 parts
Same as above (13) Glu O, 3 parts −
Same as above (]4) Gl+ 0-4 parts
- Same as above (1,5) Gl+ 0.5 part
- Same as above (161G1u O, 6th part - Same as above)
Top (17) Glu O, 7 parts - same
Above (18) 611098 parts - Same as above (19) Glu O, 9 parts - 1ii Above (20) Glu 1.0 parts - Same as above
Upper (21) Xy o, + section ~ 15
5°~160°C (22) Xy O, +5 parts
- Same as above (7-'3) XyO, 2Y% - Same as above (24) xyO, 25 parts - Same as above
26) Coo, 0.2 parts 0.041 parts
Same as above (27) Glo O, Part 3 0
．． Part 062 Same as above (28) (,lo
0.4 part 0.082 part Same as above (29
) Glo O, 5 parts 0.103 parts (30) Glo 0.6 parts 0
, 124 parts Same as above (31) Glo
O, 7th part o, +44s Same as above (
32) Glo o, s part 0.165 part
Same as above (33) Glu O13f
MS - Same, above (34) Glu O
, Part 4 - Same as above (35) Cfu
0.5 parts - same as above (36) to Iu
0.6 parts - same as above (37) C1u
'0.7fl'5 -
Same J-.

(38) C1u 0.8B too
- Same as above 2 (39) Glu O, 9 parts - Same as above (40) Glu 1.0
Part - Kamigo No. Measured value [Yes] V/C)
Average value (w/c) pH (1) 5Y
9.0015. (X) 5Y 9.0015-0
0 5Y 9-0015.00 6-55(2)
5Y 9.00/6. (X) 5Y 9.00
/6.00 5Y 9.00/6.00 6.55
(3) 2.5M8.00/8.00 2.5Y8.
00/8.00 2.5Y8.00/8. OQ
6.50(4)2. '5Y8. 'OO/10.00
2.5Y8. OO/10.00 2.5Y8.00
/+0.00 6.50 (5) 10YR8,OO/9
．． 00 10YR8,OO/9.00 10Y
R8,00/9.00 6.52 (6) 5Y9,0
01540 5Y? , 00/ri-505Y 9.
00/! 5.5.0 6.60 (7) 2.5Y11.0
0/8.00 2.5Y8. GO/8.00
2.5Y8. OO/8.00 6.58 (8) 2.5Y
8.00/ 10.00 2.5Y 8.00/ 1
0.00 2.5Y g,oo/10. (Xl
6.60 (9) 10YR7,75/9.00 10
YR7,75/9.00 10YR7,75/9.
00 6.58 (10) ]0YR7,75/10.0
0]OYl? 7.75/10.00 10YR
7,75/10. (X) 6.62 (11) 10Y
R7,50/10.00 10YR7,50/10.
00 10YR7,50/10.00 6.60(1
2) 7.5YR7, 5Q/10.00 7.5YR7,
50/10.00 7.5YR7, 50/10. [l
10 6.62 (1,3) 5Y 9.0015-5
0 5Y 9.0015.50 5Y 9-0
015.50 6.40 (14) 5Y9. OO/6
．． 00 5Y9. OO/6.00 5Y9.00
/6.00 6.45(]5) ]0YR7,75/+
0.00 10YR7,75/10.00 10Y
R7,75/+0.00 6.40(],6) 10Y
R7,75/10.00 10YR7,75/10.
00 10YR7,75/+0.00 6.45(1
7) 10YR7,75/If-0010YR7,75
/11.00 10YR7-75/11. fXl
6.58 (18) 10YR7,75/12d10
10YR7,75/12.00 10YR7,75/
12-00 6.50 (19) ]0YR7,50/1
2.00]-0YR7,50/12.00
10YR7-50/+2.00 6.40 (20)7.
5YR6,50/12.00 7-5YR6,50/1
2.00 7.5YR6,50/12.00 6.5
4 (21) 5Y9.0O15,505Y9.0O1
5,505Y9.0015.50 6.48(22)2
．． 5Y8.0Ill/9.00 2.5Y8. OO/
9.00 2.5Y8. (1)/9.00 6.58
(23) ]0YR8,00/! 1.00 10YR
8,00/9.00], 0YR8,00/9.
00 6.50 (24) ]0YR7,50/10.0
0]0YR7,50/10.00 10YF
σ-50/10. (Kl 6.55 (25) 7.5
YR7-00/10-00 7-5YR7,OO/10
．． 00 7-5YR7,00/+0.00 6.52
(26) 2.5Y 8.00/7.50 2.5Y
8.00/7.50 2.5Y 8.00/7.50
6.50 (27) 2.5Y8-00/8.00 2
．． 5Y8.00/8.00 2.5Y8.00/8.
00 6.62 (28) 10YR7,75/8-00
10YR7,75/8.50 10YR7,75/
8.25 6-68(29) 10YR7,75/9
．． 00 10YR7,75/9.00 ], 0YR
7,75/9.00 6.72 (30) 10YR7
,50/9.00 10YR7,50/9.00
]OYr? 7.50/9,00 6.70 (31)
7.5YR6,50/9.007.5YR6,75/9
．． 00 7.5YR6,88/9.00 6.73(3
2)7. ．． 5VR6,51')/10-0[+7.5Y
Department, 50/10. ．． 00 7.5YR6, 50/10.
(Xl 6.82(33) 5Y8.OO/8-(
Xl 5Y, 8. OO/8.00 5Y8.00
/8.00 6.60 (34) 10YR7,75/
8. '00 10m7.75/8.00 10■7
-75/8.00 6.62 (35) ], 0YR7
,75/9.00 10YR7-75/9. (Xl
10Yr? 7.75/9.00 6.62 (36
) ], 0YR7,75/ 10.0010YR7-7
5/ 10-00 10YR7,75/ 10-00
6.60 (37) 7.5YR6,75/10.007
．． 5YR6-75/9.50 7.5YR6-75/
9.75 6.60 (38) 7-5YR6,75/
io, oo 7-5YR6-75/ 10.00,
7.5YR6,75Δ0.00 6.65(39)7
．． 5YR6,75/+1.00 7.5YR6,75/
I1.00 7.5YR6,75/I1.00 6.6
2 (40) 7.5YR6,50/12.00 7.5Y
R6,50/12.00 7.5YR6,50/12.
00 6.65 or more samples were arbitrarily extracted for each treatment category and arranged in order of apparent color depth. Comparison with Glonic acid (a) Two-stage 1 oil temperature 145-150'C treatment section
Y O, 2nd job GIG O, 3 (xy O, 25': ct
o o, ii<Xy O, 3<GIOO, 5<GIOO
,6<Glo o,7(GIOo.8(b) Two stage 1 oil temperature 1550~160°C treatment area xy o,1
<cio O,2(cio o,a <xy O,15
<GIOO,4':,xy O,2(xy O,25
(xy 0.3 (cto o, v <GIOO,
15Xy o, y < 47-0.7 < 4t-a, r
(B) Comparison of D-xylose and potassium 2-keto-D-gluconate (→ treatment area xy O, 1 < Glu O, 3 < Xy o, t !5
=ctu O,4(xy O,2(xy O,25<X
Y O,3< GluO,! 5 :ctu O,fi
((,lu O,'7 < Glu o,,8 (Gt
u 0.9 (clu 1.0 (b) 2-stage 1 oil temperature 155° to 160°C treatment section xy O, 1 < X7
o, iii '5GIu O,3<clu o,4(x
y O,2Glu O,5<xy O,25,(Gl
u O,'6 (Xy O,3(Glu O,7'BG
1 u 0.8 (Glu O, 9 (Glu 1.0) Extract one sample from each treatment area in this example,
After irradiation with a 0 W fluorescent lamp for a certain period of time, the degree of discoloration of D-quinlose and each compound was compared with that of non-irradiated samples, and it was determined that they were approximately the same.

However, the flavor in this example was clearly observed to be a straw-like flavor when the amount of D-xyworth added was 0.2 parts or more in the treatment section where the oil temperature was 155 to 160°C. Regarding 2-keto L-gulonic acid and potassium 2-D-gluconate, no peculiar flavor was observed regardless of the amount added. It was recognized as having a mild and mild flavor.

Example 2 Add a desired coloring agent to 100 parts of the surimi prepared in Example 1 and add 6.5 parts of water.
The mixture was dissolved in 7 parts and added, and mixed uniformly. Form into a dry shape, heat at 125° to 130°C for 2 minutes in the first stage, then fi+
Fry at 5° to 150C for 3 minutes (turning over every second), place on sterilized Japanese paper and leave to cool, then seal in a plastic bag and store in a container at 300C to remove general viable bacteria. The number was measured. In addition, it was ground with 5 times the amount of water and the pH value was measured.

Result number Color former Addition amount NaOH addition amount PH49
After hours - number of killed bacteria (1) xy o, 3 parts
-5,896, I x 10ri (2) Gl
o 0-47 parts 0.103 parts 5.95
6.6 X 10f(3) Gluo
, eo part -5,933, OX 10'Example 3 100 parts of Sukeso Refrigerated Surimi Special Grade, 2.7 parts of common salt, watery part, wheat starch part, potassium bromate preparation ("Gelco", Chiyoda Chemical Co., Ltd.) ) 0.1 part, 1 part of sodium glutamate/sodium guanylate 95:5 mixture, HAP
1.5 parts of preparation, 5 parts of egg white, 0.2 parts of licorice-stevia extract preparation, 0.1 part of calcium carbonate, sorbic acid preparation (
1 (X1
Instead of adding 0 to 10.2 parts of D-quino to the part, add 0.4 part of potassium 2-keto D-gluconate, or 0.4 part of 2-keto-L-gulonic acid, 0.1 part of sodium bicarbonate, A method to obtain yellow bamboo rings by adding 0.1 part of trisodium citrate.

Example 4 60 parts of frozen ground surimi grade 2, 1.8 parts of salt,
2.4 parts of mirin, 0.5 parts of a 95:5 mixture of sodium glutamate and sodium guanylate, 0.2 parts of licorice-stepia extract preparation, 1.5 parts of sucrose, 0.8 parts of glucose, D-
0.15 parts of xylose, 1 part of HAP powder formulation, 6 parts of potato starch, 0 parts of sorbic acid formulation (from Example 1)
．． Mix 6 parts in a conventional manner to make surimi.

Add to this 18 parts water, isolated soy protein curd (1 part protein
:Water 5: Soybean oil 1) Gradually add 90 parts to dilute, mix appropriate amounts of sesame seeds, shredded carrots, and hijiki (dried fish rehydrated), shape into a plate, steam at 90'C for about 15 minutes, and then shape into a circular shape. or cut into triangles. If you fry it in oil for about 3 minutes at an oil temperature of 155-160'C, you can get Ganmodo-style fried kamaboko, but D-
xylose, t2-mo)-D-potassium gluconate 0.
3 parts (or 2" 0.3 parts sodium keto-L-gulonate)
If D-glucose is added to 0.65 parts, a product with a similar color tone (slightly yellowish color) will be obtained.

Example 5 A coloring agent for fish paste products in the form of a liquid solution containing 70 g of sodium 2-keto L-guulonic acid (or 70 g of sodium 2-keto-cooglucuronate).

Example 6 Mix 9 parts of the solution of Example 5, 50 parts of 30 thidextrin solution (Paindex I6.2 solution manufactured by Matsutani Chemical Co., Ltd.), 2 parts of sucrose fatty acid ester, and 4 parts of disodium citrate, A coloring agent for fish paste products made by Sujirei drying.

Example 30 parts of hydrogenated oil was mixed with the powdered color former blade part of Example 6,
A coloring agent for fish paste products obtained by mixing fats and oils while melting when heated, solidifying when cooled, and pulverizing.

Example 8 A granular fish meat paste product coloring agent obtained by mixing the coloring agent of Example 5 with 2 parts of xanthan gum and granulating the mixture.

Example 9 2″ 1.-L-gulonic acid linkage, 15 parts of sodium carbonate, 5 parts of distrium fumarate, 5 parts of sodium acetate, 2 parts of sugar fatty acid ester, 10 parts of sodium L-ascorbic acid,
A coloring agent for fish paste products consisting of 20 parts of lactose.

Example 10 A coloring agent for fish paste products obtained by mixing the coloring agent blade of Example 9 and 20 parts of hydrogenated oil when hot and pulverizing the mixture when cold.

Reference Example 150 g of commercially available L-sorbose (1st grade reagent), 3 parts of acetone, and 21.7 g of sulfuric acid (98%) were mixed in 5 units of 4-Keikolbene and stirred.

The reaction system and the outside air are communicated through a calcium chloride tube, and stirred until L-sorbose is completely dissolved. It became uniform in about 30 minutes. The reaction system gradually becomes dark red. After 20 hours, add sog of strength soda to 11 hours.
Dissolve in methanol and add to neutralize. To the boil: Remove the salt from the mouth and wash with acetone. Combine the washings and oral fluid and concentrate under reduced pressure. Dissolve the residue in 300 ml of ethyl ether.
The remaining red candy-like substance was washed thoroughly with ether. The extract and washing liquid were combined and concentrated to obtain 188 g of a brown oil. Distilled under reduced pressure F to Bp1
29°C/1.5 mm1 (-148°C/2
Diacetone-L-norbose 111 (g) was obtained as a pale yellow oily substance with a temperature of 111 mmHg. This substance crystallized easily if left to stand after seeding, and showed an mp of 77 to 8°C. (Reference value: 77 to 78°C. (He1v, Chim, Acja
Volume 1.7, page 319) Add 120 g of diacetone-L-sorbose and 54 g of potassium to 1.21 g of water, and add permanganate acid under water-cooling and stirring! 1103.2 g was dissolved in 2.61 g of water and the liquid was added over 1 hour. Leave it at room temperature overnight and then put it in a water bath at 600C.
It was heated to. The color of the reaction system became almost colorless. 1.・'Gun in hot water 200 m
Rinse three times with l, then combine the oral fluid and washings and adjust the pH to 8 with hydrochloric acid.
5 and then 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 to the solution under water-cooling and stirring, and after an hour, 75 g of colorless crystals were collected.

Add this paddle to 600 ml of water.
In addition to m1, a small amount of water was removed and the mixture was triturated. 40
After a few minutes, the reaction solution was cooled with water and concentrated under reduced pressure. (Below 50°C) When the total volume is 400 ml, extract with 100 ml of ether three times, and add the aqueous layer to a total volume of 100 ml.
By concentrating the product and air-drying it, 38 g of 2-keto L-gulonic acid was obtained.
Him, Act, a Vol. 17, p. 324) The oral fluid was concentrated under reduced pressure to a total volume of 20 ml, ethanol was added to make it slightly cloudy, and the mixture was cooled to obtain an additional 5 g of crystals.

Reference Example 2 150 g of D-fructose and 217 g of acetone 3''-1 sulfuric acid were reacted in the same manner as in Reference Example 1. After 1 and 24 hours, the reaction mixture was neutralized with 30% sodium hydroxide and placed in an ice-cold refrigerator. The mouthwash was washed twice with 200II11 of acetone, and the mouthwash and washings were combined and concentrated under reduced pressure. A dark brown solid was obtained. 5
The remaining syrup was extracted three times with 200 ml of hot benzene. The benzene layers were combined and roasted and treated with a small amount of activated carbon. A total volume of 500 ml was cooled on ice to obtain 4 g of diacetone-D'''' first crystals of fructose. The mother liquor was further concentrated to a total of 300 ml. Cooled on ice to obtain 15 g of second crystals. Further, the total volume was reduced to !00 ml. Petroleum benzine 20m
1 was added and cooled on ice to obtain 37 g of third crystals.

65.7 g of potassium in 1.51 g of water, diacetono D-
146 g of Norcrux was added, and a solution prepared by dissolving 126 g of permanganate IJ in 31 g of water was added to the water-cooled stirrer F over 1.5 hours. Stir at room temperature for 3 hours,
It was heated to 60°C. After cooling, PH3.5 with hydrochloric acid
Concentrate under reduced pressure to a total of 500 ml and add 15 ml of benzene.
Mioka extraction with 0 ml [,7]. The aqueous layer was completely concentrated, the remaining solid was dissolved in 400 ml of water, and purified with concentrated hydrochloric acid.
It was set as H1. Pour the precipitated oil into 150ml of chloroform.
The chloroform layers were combined, dehydrated with nitric acid, and concentrated under reduced pressure.

Diacetone-2 as 118g pale yellow syrup
-Keto D-gluconic acid was obtained.

This was dissolved in 1 ml of water and refluxed for a few minutes while removing the water little by little. After cooling with water, the mixture was concentrated under reduced pressure to obtain 88 g of crude 2-ke)-D-gluconic acid as a syrup.

A solution of 25 g of potash dissolved in 150 ml of methanol was added to the solution heated to 300"' θv, and the resulting oil was thoroughly washed and solidified.
After dissolving in ml Inopropatool 40ml, methanol 1
20 ml of the mixture was heated and cooled on ice, and the resulting seven-colored crystals were collected. 48.5 g of potassium 2-keto-ku gluconate was obtained. mp152-153°C decomposition (literature value ml) 152
0C decomposition (Chemische Berichte @
BN1164 (1927,) ) (3) Effects of the Invention The effects of the coloring agent of the present invention are as follows: (a) A novel coloring agent, which was hitherto completely unknown, is brought to the field of fish paste product manufacturing.

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

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

(→Furthermore, if (b) and (C) are taken into consideration, a new and useful coloring agent for fish paste products can be provided.

etc. can be given.

1. Display of the case 1ij Wa 1959 patent application No. 1
21594 83. What is the relationship between the person making the amendment and the case? Patent 51 applicant 4. Amendment layer for agent procedure (vinegar) 3. Person making the amendment 4. Agent 6. Number of inventions increased by amendment 0 7. Subject of amendment Details Column for detailed description of the invention in the book (
The number of pages, lines, etc. used were those of the specification that was transcribed based on the written amendment submitted on August 6, 1981. )(】)
Page 7, line 3 [1 “5erratia marcesce”
ns j [serratia marse, cephus (5erra
tia marcescens) Correct to J.

(2) 7th Q 3rd to 4th line 1'-Enterobac
ter cloacae J.
cl.

aCa, e) Correct to J.

(3) Page 7, line 4 iEl [Achromobacterium
r brunificans j as "Achromobacter"
Prunificans (Achromobacter br.
unificans) Correct to J.

(4) Pseu-domonas fl.
Pseudomonas fluorescens (Pseudomonas fluorescens)
ns) Correct to l.

(5) On page 8, line 4, "Difficult to ferment" is corrected to "1 Difficult to ferment."

(6) No.] - Page 2] - Correct 6th line "30chi" to 140% (7) No. 5 Tei Line 17 j Pseudomo
nas fluorescens J [/Needomonas 7 /L', t 7 (= Peeudo
monas fluorescens)-J.

(8) In the 16th line, [Acetobacter j is corrected to [Acetobacter J].

(9) Page 16, line 10 “He1v, clxim,
, Acta j [Helvetica Kimica Acta (He
1v, Chim, Acta) Correct to J.

a0, page 17, line 16, after “Sukeso frozen surimi”, “
Mineshimamaru special grade manufactured by Nippon Suisan Co., Ltd.

Kan (11) 22nd line 4th line “(31) 7,5YR6,50
/ 9.00 '7.5YR6,75/ 9,00
7,5YR6.88/9゜00" to "(
31) 7,5YR6,50/9,00 7,5YR
6,'75/9,00 7,5YR6,68/9. OO
Correct to j.

(12) On page 25, line 2, after "surimi special grade", write "(from Example)".

(13) On page 26, line 15, "glucuronic acid" is corrected to "gluconic acid."

(14) Page 28, line 16 [He1v, Chim, A
cta J as “Helvetica Kimica Acta (He1v
, Chim, Acta) J.

(15) 29th Tei 1'7 line "He1v, Chim,
Acta J is called “Helvetica Kimica Acta (He1
v, Chim, Acta, ) Correct to J.

(Colo) Page 31, line 16 [Chemishe Ber
Ichte 69B J
Volume 0 (Chemisha Bericbte B) Corrected to J.

Claims (8)

[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, or an amino acid with hydrogen ions added. 1. A method for coloring a fish paste product, which comprises adding 1.0% or less of the 2-keto-hexonic acid derivative shown in ) to ground meat prepared from fish meat. (2) In addition to adding the 2-keto-hexonic acid derivative illustrated in claim (1), polymerized phosphate, phosphate, sodium acetate, edible polycarboxylic acid or its salt, etc. A method for coloring a fish paste product according to claim (1), which comprises adding a PH adjusting agent. (3) Claim (1) characterized in that an elasticity enhancer is added together with the addition of the 2-keto-hexonic acid derivative illustrated in Claim (1);
2) Color development method for fish paste products. (4) In addition to adding the 2-keto-hexonic acid derivative illustrated in claim (1), lecithin,
A method for coloring fish paste products according to claims (1), (2), and (3), which comprises adding an edible surfactant such as higher fatty acid sucrose ester or higher fatty acid monoglyceride. (5) 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, or an amino acid with hydrogen ions added. ) is mixed with an edible base if necessary, and formulation aids such as diluents, dispersants, excipients, etc. are added to form a formulation. Characteristic coloring agent for fish paste products. (6) A PH adjuster such as a polymerized phosphate, a phosphate, sodium acetate, or an edible polycarboxylic acid or a salt thereof is added to the 2-keto-hexonic acid derivative illustrated in claim (5). The fish meat paste product coloring agent according to claim (5), characterized in that the coloring agent is added. (7) Color development of fish paste products according to claims (5) and (6), characterized in that an elasticity enhancer is added to the 2-keto-hexonic acid derivative illustrated in claim (5). agent. (8) A patent characterized in that an edible surfactant such as lecithin, higher fatty acid sucrose ester, higher fatty acid monoglyceride, etc. is added to the 2-keto-hexonic acid derivative illustrated in claim (5). Scope of claims (5
), (6), and (7) coloring agents for fish paste products.