JPS63230702A - Aldehyde group-containing starch ethers, their production method and their uses - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to aldehyde-containing synthetic heterogeneous compounds and methods for their production.

Many 1! These compositions are used in many different industrial applications, such as thickeners, adhesives, sizes, etc.

Polysaccharides such as starch and cellulose that have been modified to contain aldehyde groups are particularly used in the paper and textile industry.

Both oxidative and non-oxidative methods have been used to introduce aldehyde groups into polysaccharides. The oxidation methods used are periodic acid, periodate salts, alkali metal ferrates or the methods described in US Pat. No. 3,086,969 (1963).
(issued to J. SIager on April 23, 2013)
; Specification No. 3.553.193 (January 5, 1971)
No. 3,632.802 (issued January 4, 1972 to J. BeMiller et al.); Alkali metal - promise (broa+i
te).

The non-oxidation method used is U.S. Pat. No. 3.519.6
Specification No. 18 (July 7, 1970 by S. Palmer
ter); and Id. 3.740,
Specification No. 391 (dated June 19, 1973, Will
iass et al.) with polysaccharides.

Polygalactomanan gums (i.e., guar gum) and other natural galactose-containing polymers modified to have aldehyde groups are useful as crosslinking agents and in the formation of self-supporting films in various film manufacturing applications. It is used as an adhesive or binding agent. Such aldehyde gum derivatives can be prepared by similar oxidative and non-oxidative methods as described above or in US Pat. No. 3,297.6.
Specification No. 04 (F. January 10, 1967).

(published for Germino) and a galactose sequence at position 04 that can be selectively oxidized at the C4 position of the sugar unit by the enzyme galactose-oxidase to obtain an aldehyde group. Other natural polysaccharides (i.e. growths) with
It can be manufactured by

Although commercially available useful polyclass Ii aldehydes are obtained by a variety of oxidative and non-oxidative methods, new polysaccharide compositions that also have aldehyde functionality and have unique flow properties are in high demand in a wide range of industries. requested.

Therefore, there is a need for aldehyde-containing heteropolysaccharides that can withstand crosslinking reactions alone or with other organic compounds. No such products are disclosed or suggested in any of the above-mentioned documents.

The present invention C, R-0-CHz-CHz-0-@ powder [in the formula,
Starch-〇 is a starch molecule and R is a monosaccharide with an oxygen attached to the monosaccharide. ] and wherein the starch is bonded to the glycoside carbon atom of a monosaccharide by an acetal- or ketal bond and to the starch molecule by an ether bond. It is. Representative monosaccharides include hexoses such as glucose, mannose, galactose, gulose, gulose, allose, aldrose, idose, fructose and sorbose, and pentoses such as xylose, arabinose, ribose and lyxose. Corn and wheat starch ether derivatives in aqueous solution after gelatinization exhibit suitable cooking properties. Such cooking stability allows such derivatives to be used, for example, in various food and thickening applications.

The present invention also provides starch with the formula R°-0-810-starch (wherein 8 is -CH, -CH, -0- or -CHt-CH-CHz
-H, starch -〇 is a starch molecule, and R゛ has a structure represented by C4 with an oxygen atom that binds a monosaccharide, and starch forms a glycoside carbon atom of a hexose by an acetal bond. An object of the present invention is to provide an aldehyde-containing starch ether which is bonded to starch through an ether linkage.

The aldehyde-containing starch ether derivative has a) formula R”-0
-A-0-A mixture of an aqueous dispersion of starch ether represented by starch and b) galactose-oxidase enzyme is reacted in the presence of oxygen, during which the C6 position of the monosaccharide is oxidized to form a carbonyl group. It is manufactured by

The present invention also provides a method for producing a flavor additive in which a mixture of at least one amino acid and a monosaccharide is heated together in an aqueous medium, in which at least a portion of the monosaccharide is
This improvement method is also characterized by replacing the starch aldehyde with starch aldehyde having a structure of "-0-A-0-starch."

Glycosides are mono- and poly-IR containing reducing carbon atoms.
It can be manufactured from This carbon atom located on the terminal sugar ring can react with an alcohol to form a glycoside product, linked by an acetal or ketal linkage, depending on the monosaccharide or polysaccharide used.

8. Halohydrin and Glycidyl Glycoside Reactants One type of glycoside suitable for use as a reactant in preparing the glycoside starch ethers useful in the present invention includes those having the formula: It is a monosaccharide having the above meaning and having a galactose sequence at position 04, and an oxygen atom (0) is bonded to the glycoside carbon atom of the monosaccharide □, that is, CI position □
and A and A' are a hydroxyl group or a halogen atom selected from the group consisting of chlorine and bromine. ].

Halohydrin- or glycidyl glycosides are described in U.S. Pat. No. 3,931,148 (W.
, published to Langdon). In the process, monosaccharides are converted to 3-chloro-1 in the presence of about 0.01 to 2.0% by weight of a strong acid catalyst, based on each reaction component, at a temperature of about 94°C to 108°C.
, teaches that glycosides can be produced by reacting with 2-propanediol.

Halohydrin or glycidyl glycosides are advantageously prepared by reacting monosaccharides in an excess of 3-halo 1,2-propanediol in the presence of a cationic exchange resin. By using cationic exchange resins, glycosides can be prepared at mild temperatures without the carbonization often caused by strong acids of low molecular weight at the high temperatures mentioned above. The reaction is carried out under stirring for about 3 to 20 hours at a temperature of about 55 to 80°C. After the reaction is complete, the mixture is filtered to separate it from the cationic exchange resin. Excess diol was then removed by vacuum distillation or washing with an organic solvent to obtain the 3-halo 2-hydroxypropyl glycoside.

Possible halogenated propane diols that may be used include 3-chloro-1,2-propanediol and 3-bromo-1,2-propanediol.

It is advantageous to use chlorinated derivatives because they are readily available and inexpensive on the market. 1:1.4
Although smaller monosaccharide to diol ratios have been used,
Advantageously, the ratio is at least 1:3 to 1:6, especially 1:5.

Any cationic exchange resin can be used to produce glycosides. Suitable ion exchange resins include sulfonated crosslinked polystyrenes, such as Amberlite IR-120 from Rohm and Haas, Doex from Dow Chemical, etc. (Dowex) 50 and palmtite (Permu
Permutit Q,
Diamond Shamlot ivy (Diao+ond Sc
hamrock Duolite
Sulfonated phenols such as C-3 and Zeo Carb (Z) from Permutit.
There are sulfonated coals such as
It is. The amount of resin used in the present invention is about 1 part resin to 2 to 8 parts by weight of sugar, especially 1 part to 4 to 5 parts by weight of sugar.

The glycidyl-glycoside used in the present invention is 3-hero-2-
It can be prepared by reacting hydroxypropyl-glycosides with alkali metal hydroxides to form epoxy groups. Typically, the glycoside is mixed with an alkaline aqueous solution during cooling. This mixture is neutralized with acid and then dissolved in alcohol in order to precipitate the metal salts formed. After filtration, alcohol and water are removed from the glycidyl glycoside by vacuum distillation.

B. Haloethyl glycoside reactant Other types of glycosides that are useful reactants in producing the glycoside starch ether of the present invention are represented by the formula % [wherein R-0 is a single W] class, in which oxygen atom (Q)
is bonded to the glycoside carbon atom of the monosaccharide, and
is chlorine or bromine.

It is expressed as Any monosaccharide with a reducible carbon can be reacted with haloethanol in the presence of a strong acid catalyst or cationic exchange resin by methods similar to those described above to obtain haloethyl glycosides. Typical monosaccharides include
Examples include glucose, fructose, sorbose, mannose, galactose, talose, xylose and lipose.

Particularly useful haloethyl-glycosides for producing starch ethers that are oxidized by treatment with enzymes are 2R''-0-CIhCHzχ, where R''-0 and X are defined as above. ]
It is expressed as

In some instances, haloethylene glycosides are advantageously used to prepare the starch ethers used in the present invention.

This is because the impurities (i.e., 1,3-dichloro-2-propanediol) present in 3-halo-1,2-propanediol used in the production of haloethylene glycosides are extremely difficult to remove from the glycosides. This is because it is difficult to use and reacts with starch itself as a crosslinking agent.

Halohydrins, glydecyl and haloethyl-glycosides can be used, for example, with starch and starch conversion products derived from any plant source, starch ethers and monoesters, cellulose and cellulose derivatives and various plant-gums and gum derivatives with etherification reaction conditions. can react under

Applicable starch bases that can be used when producing the glycoside starch ether derivatives of the present invention include corn, potato, sweet potato, wheat, rice, sago, tapioca, waxy corn, sorghum, high amylose corn. or can be derived from plant sources containing analogs thereof.

Furthermore, conversion products derived from any of the bases mentioned above, such as dextrins produced by acid and/or thermal hydrolysis reactions, oxidized starches produced by treatment with oxidizing agents such as sodium hypochlorite. Also included are free-flowing or weak-boiled starches made by enzymatic conversion or mild acid hydrolysis, and derived starches such as ethers and esters.

This starch base can be a granular starch or a gelled starch, ie a non-granular starch.

Methods for producing modified starch bases according to the invention are well known to those skilled in the art and disclosed in the literature. For example, R,
L. Histler, “Methods in Carbochtler Chemistry”
dSin Carbohydrate Chemist
ry)” Volume ■, 1964, pp. 279-311, R,
L., Whistler et al., 1 Starch Chemistry and Technology
-Chesistry and Technology)
', Volume ■, 1967, pp. 293-450; and R
, Davidson and N. Sittig, "Water Soluble Reins," 2nd edition, 1968, Chapter 2.

The starch etherification reaction in the present invention is represented by the following reaction formula: R"-0-'CHzCHJ+starch-OR4R"-0-C
HtCHz-0-starch (U) [where starch-OH means a starch molecule and R'', A
, A' and X have the above meanings. It should be noted that using glycidyl glycosides in the present invention results in similar starch reaction products (see Scheme I) as using halohydrin glycosides. The etherification reaction proceeds only under alkaline conditions after the halohydrin group has first been converted to the epoxide form.

Reaction formula (2) shows a special reaction for producing starch ether used in the production of the novel starch aldehyde in the present invention. However, this is one embodiment of a reaction for producing new starch derivatives from halohydrin glycosides and starch, which can be represented by the following reaction equation:
R-0-ClbCHtX+starch-0H-+R-0-CI
hCHz-0-i19 powder [wherein starch-OH, R and X are defined as above. ] It appears that the haloethyl group reacts with the starch molecule by a mechanism involving nearby groups, even though in theory no binding is desired.

Those skilled in the art will appreciate that starch molecules are composed of many anhydroglyose units. Each unit has three free hydroxyl groups (excluding the non-reducing terminal glucose unit which has four hydroxyl groups) that can react with the glycoside reactant. The number of such substituents or the degree of substitution (D, S) therefore varies with the particular starch, the ratio of reactants to starch, and to some extent with the reaction conditions.

Furthermore, it is also known that the relative reactivity of each hydroxyl group in anhydroglucose units is not equal, so that some are likely to react better with reactants than others.

The monosaccharide moiety of the glycoside reactant also contains free hydroxyl groups.

Therefore, during the etherification reaction, there is also the possibility that the glycoside reactant reacts with other reactant molecules. In such a reaction,
A sugar-containing molecule will be obtained which still contains a saccharide unit containing a galactose sequence in the C4 position and unreacted glycidyl or haloethyl groups capable of reacting with starch. This reaction does not result in crosslinking because there is only one reactive site for molecular light.

The starch reaction can be carried out using many conventionally known techniques, such as using an aqueous reaction medium, an organic solvent, or a heat drying reaction technique in which a wet starch cake is impregnated with a glycoside reactant and then subjected to heat drying. This can be done by

In a particularly advantageous process, the reaction is carried out in an aqueous medium using a starch-based aqueous slurry or dispersion. The glycoside reactant is added to the reaction mixture in solid form or as an aqueous solution. be able to. Advantageous concentrations of the solution are from 20 to 50% by weight, based on the weight of the reaction. In another method, the glycoside reactant solution is brought to the desired pH value prior to addition to the starch base. This is done by adding sufficient alkali. In yet another variant,
Dry starch is added to an alkaline solution of glycoside reactant.

The amount of glycoside reactant used in the reaction with starch in the present invention will depend on factors such as the underlying starch used, the glycoside reactant used, the degree of substitution desired in the final product, and to some extent the reaction conditions used. Depending, it can generally vary from about 0.1-100% by weight based on dry starch.

The starch reaction is carried out under alkaline conditions, 11-13, especially 11.
It is carried out at a pH value of 4 to 12.4. The alkali can be added to the starch slurry or monodispersion before or after adding the glycoside reactant.

The pH value is customarily adjusted by adding sodium hydroxide, potassium hydroxide, calcium hydroxide, tetramethyl-ammonium hydroxide, etc. A particularly preferred base is sodium hydroxide.

When the reaction is carried out with granular starch, it is often preferred to carry out the reaction in the presence of a salt, for example sodium sulfate in an amount of about 10 to 40 parts by weight, based on dry starch.

The presence of sodium sulfate suppresses starch swelling and results in a product that is well filterable. Sodium sulfate is not used in calcium hydroxide reactions.

The reaction mixture is stirred under desired reaction conditions.

The reaction time depends on the amount of glycoside reactant used, reaction temperature, and pH.
It can vary between 0.5 and 20 hours, depending on factors such as value, scale of reaction and degree of substitution desired. Generally advantageous reaction times are from 6 to 16 hours.

The reaction is carried out at a temperature of 20 DEG to 95 DEG C., especially 25 DEG to 45 DEG C. It will be appreciated by those skilled in the art that using granular starch in an aqueous medium using temperatures above about 60° C. will result in swelling of the granules and difficulty in filtration or gelling of the starch.

If high reaction temperatures are desired, water-miscible aqueous solutions can be used to prevent expansion.

After completion of the reaction, the pH value of the reaction mixture is adjusted to a value of 3 to 7 with any commercially available acid, such as hydrochloric acid, sulfuric acid, acetic acid, etc. Such acids can generally be added as dilute aqueous solutions.

Recovery of the derivative can be easily carried out with the particular method used depending on the starch-based form. Therefore,
The granular starch is recovered by filtration, optionally washed with water to remove any residual salts, and dried. The granular starch product can be drum dried, spray dried or gelled and isolated by alcohol precipitation or lyophilized to form a non-granular product (ie, gelatinized). If the starch product is non-granular, it is purified by dialysis to remove residual salts and isolated by alcohol precipitation or freeze-dried or spray-dried.

D. Aldehyde-containing starch derivative "'" The aldehyde-containing starch derivative of the present invention is based on the above and reaction formulas I and (
In the formula, the glycoside substituent (R'') is a monosaccharide with a galactose sequence at the C4 position. Galactose and talose are exemplified as monosaccharides containing: 110 Hz CHO Hz C Galactose Oxidation of the talose glycoside substituent at the C position results in starch ether derivatives dispersed in an amount of buffered aqueous solution determined by the solubility of each component. The reaction is carried out at a pH range of 4 to 9, especially 5 to 8, at a temperature of about 10 to 60°C, preferably at room temperature, in the presence of oxygen. is carried out in the presence of the enzyme catalase, which is capable of reducing hydrogen peroxide (a byproduct of oxidation) to water and oxygen.

After the greenhouse, the enzymes are inactivated (ie, inactivated by removing the oxygen source, heating or lowering the pH). The starch aldehyde is then isolated in known manner or left in solution.

Starch is reacted with 2-haloethyl-galactoglycoside and then oxidized with galactose oxidase to obtain starch derivatives with randomly occurring aldehyde-containing galactose side chains, e.g. -Glu -Glu -Hz HOH [wherein -Glu-Glu-Glu-Glu- is a starch chain. ] The presence of aldehyde functionality in the starch derivatives of the present invention makes the products useful as, for example, paper strengthening additives. This aldehyde functional group is
This makes starch derivatives useful as co-reacting components in the Maillard reaction, the well-known browning and flavor additive forming reactions that occur in foods; this reaction is described in U.S. Pat. , Hon. Botelsberge de U. Botelle (
von Potters-berghe de la
Potterke) on February 13, 1973)
and U.S. Patent Nos. 3,615,600 and 3,761,287 (C, H, T, T.
Zevennar and Jaeggi
) on October 26 and 19, 1971, respectively.
issued on September 25, 1973) and British Patent No. 1,285
, 568 (J.L., Godman)
), published on August 16, 1972).

A typical process for making artificial flavor additives using the Maillard reaction includes water, sugars, one or more amino acids, and optionally other ingredients such as hydrogen sulfide (UK Patent No. 1,28
5.568), succinic acid and hydrocarboxylic acids (see U.S. Pat. No. 3.615.600)
, polyhydric alcohols (see U.S. Pat. No. 3,761,287) or lower carboxylic acids or fatty acids (see U.S. Pat. No. 3,716,380). .

Suitable amino acids include glycine, alanine, proline, hydroxyproline, threonine, arginine, glutamic acid, aspartic acid, histidine, lysine, leucine, isoleucine, serine, valine and taurine. Minor amounts of tyrosine, tryptophan, cystine, phenylalanine and methionine may not be objectionable, depending on the flavor additives desired.

G, tri, or higher peptides or proteins that provide essential amino acids can also be used. Protein hydrolysis products are an advantageous source.

Commonly used tINs also include monosaccharides or ni-, tri-, or polysaccharides that yield monosaccharides under the conditions of the Maillard reaction. The above aldehyde-containing heteropolysaccharides are these P! It is used as a replacement substance for part or all of a class.

Factors that influence the nature and quality of the flavor additives produced include I! and the nature and relative amounts of the amino acids and optionally other ingredients used, as well as the amount of water, reaction temperature and reaction time.

All parts and χ in the following examples are by weight and all temperatures are in °C unless otherwise indicated. The carbonyl content of starch aldehydes was determined by the ``Quantitative Organic Analysis Via Functional Groups''.
ve OrganicAnalysis via Fu
nctional Groups)” 3rd edition, Sidney 51gg1a (John
Riley & Sons Inc. (J
Ohn Wiley & 5ons, Inc.)
New York, 1949, p. 73.

This example demonstrates the method for producing halohydrin and haloethyl glycoside, which are the starting materials used in the present invention.

0,5 equipped with cooler, mechanical stirrer and heating means
80 g (0.44 mol) of galactose, 237 g (2.15 mol) of 3-chloro-1
, 2-propanediol and 20 g H.

Add type cationic exchange resin (Dowex 50W-X8). The mixture is heated to 60-63°C and stirred at this temperature for 16 hours. The reaction mixture is cooled and then filtered through gauze cloth to remove the resin. The reaction mixture is clear and pale yellow in color. Unreacted diol was distilled under reduced pressure (2
mm Hg) at 80°C. The wet solid product is suspended in acetone, filtered three times to remove residual impurities, and then dried in a vacuum desiccator.

b. 2-Chloroethyl-Gagt Arrangement 80 g of galactose, 217 g (2,69 mol) of 2-chloroethanol and 20 g of Doevex 50W-X8 are added to the same apparatus as described in a.

The mixture is stirred at 55°C for 16 hours and at 80°C for a further 4 hours. Remove the cationic exchange resin as described above. Then remove unreacted 2-chloroethanol under reduced pressure (0,
1 mm Hg) removed by distillation at 30-35°C,
Then dry in a vacuum desiccator.

This practical example demonstrates the method for producing ethyl-galactoglycoside starch ether.

A total of 100 parts of corn starch and 10 parts of 2-chloroethyl-galactoglycoside (untreated) were combined with 3.0 parts of sodium hydroxide and 30 parts of sodium sulfate in 1 part.
Add to the solution in 50 parts of water. Add this mixture to 4
Stir at 0-45°C for 16 hours. Then the pH was adjusted to 9.3.
The concentration is lowered to 5.5 by adding aqueous hydrochloric acid. :R powder derivative (A) is recovered by filtration, washed three times with distilled water and air dried.

For comparison, an aqueous suspension containing 96 parts water and 8 parts of the derivatized starch product or the underivatized base itself is cooked in a boiling water bath for 20 minutes. Leave the gelled preparation overnight at room temperature before experimenting.

The base corn-cooked product forms a gel-film.

On the other hand, starch derivative cooked products do not gel and are stable.

[3] This example demonstrates a method for producing ethyl-galactoglycoside ether of cationic free-flowing starch.

Corn starch hydrolyzed to a final water fluidity of 75 was first treated with 2.7z diethylaminoethyl-chloride-hydrochloride [US Pat. No. 2,876,217 (E, Paschall)]. March 1959
(published on the 3rd of the month). Thereafter, the cationic fluid starch is reacted with 2-chloroethyl-galactoglycoside at a concentration of 3°x in the same manner as in Example 2. In addition, starch derivatives (B
) is recovered by filtration, washing three times with distilled water and air drying.

Various starch-based hydroxypropyl-galactoglycoside ethers are prepared according to the method described in Example 2. The reaction data are shown in Table 1.

Table 1 E Corn 7420 *Starch base is not hydrolyzed.

Comparative sample G was mixed with 85 ridges of waxy corn and 20 ridges of waxy corn.
It is produced by reacting 3-chloro-1,2-propanediol at a concentration of χ.

Example 5 This example demonstrates the preparation of aldehyde-containing starch derivatives by enzymatic oxidation of the ethyl-galactoglycoside starch ether of Example 3.

A total of 6.0 g of derivative (B) was added to 90 m 12 containing 0.15 g of Dowicide A (a preservative obtained from Dow Chemical Corporation).
of pH 7 phosphate buffer solution (0.68 parts of potassium phosphate □-basic □ and 0.16 parts of sodium hydroxide)
00 parts of distilled water).

The suspension is cooked in a boiling water bath (81B) for 20 minutes to gel, then the starch is cooled to 35°C. The Prutsk field viscosity of the sample with 30χ solids content is then (20 revolutions/min, spindle #5) 0.
45 Pas (450 cps).

1, 7 mg (225 units) of galactose-oxidase and 30 mg (60,000 units) of catalase are all dissolved in 5 ml of additional buffer solution and then added directly to the starch dispersion. The mixture is stirred at 37° C. for 4 days with continuous oxygen exclusion, after which the reaction is stopped by stopping the oxygen exclusion. After oxidation, the starch dispersion with a solids content of 6.4.chi. increases its Plutz field viscosity to more than 200 Pas (200,000 cps). This material has a carbonyl content of 0.54X.

Example 6 Hydroxypropyl-galactoglycoside starch derivative C,
A starch aldehyde derivative is obtained by oxidation in the same manner with galactoxidase.

14.0g of C and 0.25g of Tobishito total 286m! 2 in phosphate buffer solution and cook as in Example 5. This 4.5χ solids content dispersion has an initial Plutz field viscosity (at 20 revolutions/min, spindle #5) of 3.8 Pas.

(3,800 cps, ). 0.57 mg (7
5 units) of galactose-oxidase and 10 mg
(20,000 units) of catalase in 21ml
Dissolve in buffer solution. This enzyme solution is added to the starch dispersion and the reaction is then carried out under the conditions described in Example 5 for 24 hours. After oxidation, a starch dispersion with a solids content of 4.9χ has a Prutsk Field viscosity of approximately 5.9 Pas (at 20 revolutions/min, spindle #5), (5,900 cps).
,) or more. This material has a carbonyl content of o,32χ.

A unique thixotropy is observed in this particular starch aldehyde product in aqueous dispersion.

That is, the product is in a dilute liquid state during stirring, but forms a gel state when stirring is stopped.

Starch galactoglycosides E and F and comparative starch sample G are also oxidized with galactose-oxidase as described in Example 5.

The reaction conditions and results are shown in Table 2.

Temperature ('C) 37 37 37
37 hours 16:00 4 days 4 days
4-day results: Starting at 20 revolutions/min, spindle #5° In the same manner, starch was mixed with 2-chloroethyl-taloglycoside or 3-chloro-
Reaction with 2-hydroxypropyl-taloglycoside as in Example 2 yields ethyl or hydroxypropyl-taloglycoside starch ether. These starch ether derivatives are treated with galactose-oxidase in the same manner as above to obtain starch aldehyde derivatives.

This example demonstrates the use of ethyl-galactoglycoside starch ether in a pourable sauce preparation.

Corn starch is treated with 20 x a degrees of 2-chloroethyl-galactoglycoside as described in Example 2. Ethyl-galactoglycoside starch ether (H) is added to a barbecue sauce preparation and compared to a similar sauce using an underivatized corn starch base. The following recipe is used: starch derivative 2.5 sand [3.0 coffee 0.3 paprika 0.2 chili powder 0.2 cinnamon 0.2 ground clove 0.2 tomato puree 47.4 finely chopped onion 5 .3 Worcestershire sauce 6.6 Water 26.2 Vinegar
7.9 Heat this sauce to 85℃ (1
Heat to 85"F), hold for 15 minutes and cool at room temperature overnight before observing.

This sauce containing starch glycosides (H) is smooth and pourable. This is in contrast to sauces made with underivatized corn starch, which are obtained as very heavy lumpy products.

This example illustrates the use of the starch aldehyde of the present invention as a paper strengthening additive.

Acid-hydrolyzed corn starch was first added to the final needle of 70,
As in Example 3 <3. React with diethylaminoethyl-chloride hydrochloride of OX. Thereafter, a control cationic fluid starch (J) is reacted in the same way as in Example 2 with 2-chloroethyl-galactoglycoside at a concentration of 20.

A 10 g sample of ethyl-galactoglycoside was treated with 250 units of starch ether galactose oxidase at 60,00
Oxidation in the presence of 0 units of catalase gives starch aldehyde (K) with an aldehyde content of 0.40x.

The unbleached softwood craft is rated at 550 Canadian 5 standard free.
ness). Add all of the 3.3 x light and dark to mix and adjust the pt+ value to 5.5. Working up the formulation by adding starch derivatives and adding 4 g of handmade paper (ha
ndsheet)
Mold (Noble and Wood 5sheets)
Mold), compressed and heated to 149°C (300°C)
Dry at °F). The Z-unidirectional strength of this sheet is measured using a Scott Bond device. The strength of the sheet in the dry state is 0.0138m-k
Record as g(foot-pound)/1000. The amount of starch added is 13.6kg/902゜2kg (30lb
/1on). The test results are shown in Table ■: Table ■Blank test 234 Control test (J) 293 Starch aldehyde (K) 323 The results show that starch aldehyde has an improved drying time compared to the control test article prepared on a starch basis. It has been shown to provide strength.

Example 10 This example describes #H used in the Maillard reaction.
A method for producing an artificial flavor additive using the starch aldehyde of the present invention as a substitute for the same is described.

Histidine (0.75g), Tyrosine (0.63g)
, glutamic acid (14,21g), glycine (0,1
4g), alanine (1,10g) and leucine (1
, 03g) dissolved in water at pH 6.
(NaOH). Starch aldehyde of Example 5 (
3.6 g), glucose (4.5 g) and sodium sulfide non-hydrate (2.68 g), and the volume was made up to 76 g with water.
mj! and heat the mixture under stirring and reflux in a 130° C. bath for 6 hours. After cooling, corn flour (55.2 g) is added and the product is lyophilized to obtain a powdered flavor additive.

In summary, the present invention provides ethyl-glycoside starch ether derivatives. Additionally, starch aldehydes are provided that are useful in conventional applications where starch aldehydes produced by other chemical oxidative or non-oxidative means are advantageously employed, namely in sizing and fiber sizing. This starch aldehyde is also useful as a crosslinking agent. Often, when self-crosslinking, the starch exhibits a significant increase in viscosity, making it useful as a thickening agent in a variety of applications, including food systems.

Claims (1)

Claims: 1) R-O-CH_2-CH_2-O-starch, where starch-O is a starch molecule and R is a monosaccharide with oxygen that binds the monosaccharide. ] and the starch is attached to the glycoside carbon atom of the monosaccharide by an acetal or ketal bond and to the starch molecule by an ether bond,
Starch ether derivative. 2) The starch ether derivative according to claim 1, wherein the monosaccharide is selected from the group consisting of glucose, fructose, sorbose, mannose, galactose, talose, xylose and ribose. 3) R-O-CH_2-CH_2-O-starch where starch-O is a starch molecule and R is a monosaccharide with an oxygen that binds the monosaccharide. ] and the starch is attached to the glycoside carbon atom of the monosaccharide by an acetal or ketal bond and to the starch molecule by an ether bond,
In producing starch ether derivatives, a) the starch base has the structural formula R-O-CH_2-CH_2-
at a pH of 11 to 13 in an aqueous medium with 0.1 to 100% by weight (based on starch) of a glycoside reactant represented by 20-9
A method for producing starch ether derivatives as described above, characterized in that the reaction is carried out at a temperature of 5° C. for 0.5 to 20 hours, and b) the resulting starch ether is isolated. 4) a) R″-O-CH_2-CH_2-O-starch or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Starch [In the formula, starch -O- represents the starch molecule and R″ binds monosaccharides Hexose has a galactose sequence at C_4 position with oxygen ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ And starch is bonded to the glycoside carbon atom of hexose by an acetal bond, and is bonded to starch by an ether bond. b) an aqueous dispersion of a starch ether selected from the group consisting of b) a mixture of galactose-oxidase enzymes is reacted in the presence of oxygen, whereby the C_6 position of the monosaccharide is oxidized to a carbonyl group. An aldehyde-containing starch ether characterized by 5) The aldehyde-containing starch ether of claim 4, wherein the reaction is carried out at about 10-60° C. and at a pH of about 4-9 in the presence of catalase enzyme. 6) The aldehyde-containing starch ether has the formula R'-O-A-O-starch [where A is -CH_2-CH_2-O- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and starch -O is is a starch molecule and R' is a hexose containing a galactose sequence at the C_4 position with an oxygen atom bonded to the glycoside carbon atom of the hexose by an acetal bond and to the starch by an ether bond ▲Math, chemical formula, There are tables etc. ▼. ] The aldehyde-containing starch ether according to claim 4, which has a structure represented by the following. 7) The aldehyde-containing starch ether according to claim 6, wherein the hexose is galactose. 8) the starch is selected from the group consisting of corn, waxy corn and tapioca, their conversion products and products derived therefrom, said derived products being derived from an etherification agent or an esterification agent; and 8. The aldehyde-containing starch ether of claim 7, wherein the starch aldehyde contains at least 0.25% carbonyl. 9) A method for producing an artificial flavor additive in which a mixture of at least one amino acid and a monosaccharide is heated together in an aqueous medium, wherein at least a portion of the monosaccharide is of the formula R'-
O-A-O-starch [where A is -CH_2-CH_2-O- or ▲mathematical formula, chemical formula, table, etc.], starch -O is a starch molecule, and R' is a starch molecule by an acetal bond. Glycoside of hexose ▲There are mathematical formulas, chemical formulas, tables, etc.▼ which is a hexose containing a galactose sequence at the C_4 position with an oxygen atom attached to the carbon atom and to the starch by an ether bond. ] The above-mentioned method, characterized in that the aldehyde-containing starch is substituted with an aldehyde-containing starch having a structure represented by the above.