JPH03500302A - Polysaccharide from the endosperm of Namurinus seeds, its recovery method and its application - 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] Polysaccharide from the endosperm of Namurinus seeds, its recovery method and its application Mimosacee Prosopis lilyflora (Mimosacee Pros-opi sjuliflora) (also known as Prosopis chyrensis) Or Ceratonia chirensis or Mimosa lilyflora) is a shrub or tree. It thrives in arid regions and is particularly resistant to low concentration salt water and industrial wastewater. For example, in India and Brazil, roads are lined with trees to prevent the movement of sand dunes and provide firewood and water. fruit for camels and cattle) falls when mature, and wandering livestock collect this additional fruit. take food. The pods are not used in any way. Literature article (“Th e Wealth of India” Volume 8, 1969, No. 245-24 According to (p. 9), in the United States, the pods from which the seeds have been removed are ground into powder, which is then mixed into casings. It is said that it can be applied to the production of alcoholic beverages and beverages.

Polysacchucharides from the seed endosperm of Prosopis euryflora are particularly effective chemical It was found that it has various physical properties.

The endosperm cells of seeds of many leguminous plants contain polysaccharides, which are galactoses. It is known to be mannan. These are stored polysaccharides of plants, similar to starch. It's Khalid. During seed germination, these are broken down by enzymes and become nutrients for the young sprouts. It's helpful. The collective concept of galactomannan or polygalactomannan is a constituent component. It is composed of galactose and mannose, and in addition, although the amount is small, other It includes all polysaccharides which may also contain sugar components. The reason A relatively large number of species that differ chemically and in their physical properties depending on their origin. There is lactomannan.

Cluster beans (Guar), which are various leguminous plants (those that produce leafy fruits), locusts Bean (Johannisbrot), Jacket Thorn (Tara), Americana Ikachi (Hon i gbohn e), Hoou Boku (Flamrnenb) aum), Sesbania and Cassi a) Galactomannan, which is present in the endosperm and seeds of the genus, is mainly It is well known and used industrially.

It is known that these polysaccharides are particularly suitable as thickening agents.

Powerful Patent Publication (DE-O3) No. 3335593 is Kawaraketmei-Galactoma Gelling agents and thickening agents based on nanonan are described. Kawaraketmeipolisa Substituted alkyl ether of tucaride and its application as thickener DE-O 3 No. 3347469.

US Patent (US-PS) No. 2,477,544 describes cluster bean rubber.

Carob powder, honey 1ocust, ho-oh Carboxyalkylene of polygalactomannan derived from B. oleracea and similar plants as a thickening agent for printing pastes and their printing pastes (Druckpasten). Applications are listed below.

Figueiredo is Cjenc, Tecnol, Aliment, 3 ( 1) (1983) p., 82-89 from Brosobis euryflora, Galacto of the galactomannan fraction with a ratio of mannose to mannose of l:4.2. Manufacture is described: The isolated polysaccharides are grown in carob (Carob). It is described as being the same as the polysaccharide of cluster bean.

The polysaccharide according to the present invention shears and polishes the endosperm of Prosopis lilyflora seeds. Polygalactoman made by crushing and with a ratio of galactose to mannose of approximately 1 = 1 It's naan. For example, polygalactomannan from India contains 42% galactose. A proportion of 58% and mannose was found in the analysis. There is a bias of about 5% for those from other sources. Similar values were obtained within the range of differences. Surprisingly, this polygalactomannan is well It was confirmed that the viscosity of the solution in cold water was relatively high. Dissolves easily in cold water It is suitable as a thickening agent for aqueous systems. Conventionally known thickeners or clustermas Meat (low-temperature melting, cloudy) Carob (high-temperature melting, cloudy) Jaquet thornbara kernel powder (high-temperature melting, cloudy) (Dissolves only at high temperature, becomes cloudy) and Kawarakekmei nuclear powder (dissolves only at high temperature, becomes cloudy), etc. Unlike other thickeners, Prosopis galactomannan is primarily used to improve solubility. No need for derivatization, galactomannan already dissolves neatly in cold water do.

The 1% aqueous solution of galactomannan according to the present invention has a viscosity of about 3000 mPas at room temperature. It is.

The polygalactomannan according to the invention is obtained from the seed by forming the per se known husk (Schal). e) and the embryo can be recovered by a shelling method to separate them from the embryo. According to the present invention, Pis: Cleaned seeds of lily flora are placed in a rotary tube furnace at a temperature of 200-250°C. Roast for about 1 to 3 minutes, then remove the outer skin and embryo using a sheller. After sieving, endosperm is obtained. Then, in some cases, the shells are subjected to another shelling process to improve the shelling. To the present invention The resulting polygalactomannan can then be removed from the endosperm in a simple manner by grinding. can.

The subject of the invention is therefore Prosopis jul iflora) (also known as Prosopis chirensis, Ceratonia chirensis, Essentially embryoless and integument-free porissa from the endosperm of the seeds of Mimosa (Euroflora) It is Tsukarid. The polygalactomannan according to the present invention contains galactose versus mannol. The ratio of 1:1 to 1:1.5.

These values were determined by IPLC.

The advantage of the polysaccharides according to the invention is that they do not need to be derivatized. Of course, the present invention also covers the ether derivatives and ester derivatives thereof, as well as partial solutions thereof. Also included are polymerized derivatives.

Preferred ether derivatives are CI C4 alkyl ethers and the corresponding substituted ether derivatives. alkyl/ethers such as carboxy-CI C4-alkyl ethers and hydrides Roxy-CI-04-alkyl ether. Particularly suitable ether derivatives are It is hydroxypropyl ether.

The polygalactomannan derivatives according to the invention can be produced according to methods known per se. It is done. The usual method is described for example in European Patent (EP) No. 146911. It is. In this way, highly viscous ether and ester derivatives that are soluble in cold water are obtained. It will be done.

For many applications, the viscosity of an aqueous solution is It is advantageous to produce a product which can be used in an extra quantity even though the values are the same.

This type of depolymerization of polygalactomannans is known per se and includes thermal, oxidative, and hydration. This can be done by decomposition or enzymes. The present invention is based on the seeds of Prosopis lilyflorum. Partially depolymerized forms of polysaccharides from endosperm are also included.

Depolymerization according to the invention is preferably carried out by swelling the endosperm with oxidizing agent-containing water during the milling process. This can be carried out by wet milling while shearing. As an oxidizing agent, especially peracid Hydrogen oxide or sodium peroxide are suitable.

The polysaccharides according to the invention are particularly well suited for use as thickeners for aqueous bases. There is. Therefore, these polysaccharides are used in printing pastes for textile printing and in floating minerals. For thickening during ore beneficiation, as a dispersant during paper manufacturing and paper addition, for thickening foodstuffs, well drilling Very well suited for liquid thickening and for oil well beneficiation ing.

In particular, the polygalactomannan according to the present invention is useful for preparing printing paste and for thickening drilling fluid. They are suitable for beneficiation at oil well sites because they dissolve and leave little residue. . The low solubility of this residue makes it particularly useful for textile printing, especially for rotating film printing. It is possible to avoid blockage of the dye mold. This eliminates costly intermediate cleaning and machine stoppages. disappears.

Low residue solubility is also important during well site beneficiation (enhanced oil extraction). . This is because the thickening agent according to the present invention can penetrate rock pores without clogging them.

The polysaccharides according to the invention are highly soluble in water and therefore do not necessarily need to be derivatized. It has excellent biological degradability because it does not contain any Soluble polysaccharide derivatives i.e. carboxymethyl cellulose, hydroxypropanol It's better than Pirguar etc.

Like other galactomannans, the polygalactomannans according to the invention are also known as “ It is possible to work with "crosslinking" bonding reactions and therefore the invention also encompasses crosslinked products of this type. do.

“Crosslinking agents” include boric acid and its salts, as well as ACSb, Cr, Fe. , Co, Cu, Mg, Mn, Ni, Ti, V, 2n.

Sn, Zr salts and metal compounds are suitable; these have particularly strong crosslinking properties. Lead to reaction. Polygalactomanganese according to the invention compared to other polygalactomanganese Nan is an excellent choice due to its particularly strong ability to form gels in aqueous solution after cross-linking reactions of this type. There is.

The compounds according to the invention can be used as thickening agents, for example for aqueous textile printing and fibrous substrates. It has particularly advantageous properties when used as a thickener for printing pastes for continuous dyeing.

Printing paste (Druekpa, 5ten) can be used for direct dyes, acid dyes and metal complex dyes. dyes, disperse dyes, basic dyes, etc.

However, the use as thickeners for aqueous bases is not limited to textile auxiliaries. Food/pet food In the food sector the natural substances according to the invention can be used for thickening. Its application field is adhesion Floating in agents, oil well fluids, paper coating agents, gunpowder solutions, plant treatment agents, ceramics, and exterior wall materials. This ranges from thickeners used as mineral beneficiation aids.

The polysaccharides according to the invention can be used in combination with others, especially when they are used as thickening agents. Thickening agents such as starch, guar, xanthan, carrageenan, agar, carob kernel powder At the end of the day, Jacket thornbara, American rhinoceros trumpet, Porphyra spp. Kemei, derivatives of this type of polysaccharides, i.e. alkyl ethers, substituted Alkyl ethers, carboxyl alkyl ethers and phosphoric esters and polymers. Used in mixture with one or more thickeners from the group consisting of (meth)acrylates can.

The invention is illustrated by the application of polysaccharides in the following examples.

Example 1 A suction test revealed the low residue filterability of the polygalactomannan according to the present invention. can be done.

The following polysaccharides were compared: 1) Prosopis lilyflora galactomannan 2) Carob (carob kernel) Galactomannan (powder) 3) Galactomannan from cluster beans 4) Hydroxypropylated galactomannan from cluster bean (SG approx. 0.35) 100% of each particle size is less than 100μ. Polysaccharide 1h ( 3.0 g) was dissolved in 297 g of water.

Transfer the viscous solution to 50μ gauze (Switzerland) fabrik High performance filter fabric nylon monofilament NY 48) I manufactured by AG C diameter 100mm) through Harutin Wangel 12 Fu 03 suction filter Filtered with suction.

The following results were obtained: Negative pressure is Kaf Neubergel NO3 with suction filter, manomek and vacuum gauge. It was produced using a 5AN model 18 model vacuum pump. Minimum pressure (approximately 800 mba r) The time taken to reach the target was measured.

Filtration time is about 10 seconds for Prosopis lilyflora and hydroxypropyl class Observed only in egg bean galactomannan.

Neither carob kernel powder nor kraft bean gum could be filtered out (suctioned). boiled 1 % aqueous solution of carob kernel powder and cluster bean gum precipitate cannot be filtered (suctioned). won.

fruit” 1 skinmata Two types of vat-dyed printing pastes were made according to the following recipe: Pre-produced product: combination of two types of thickening agent powders xg potassium carbonate 150g sodium formaldehyde Sulfoxylate 130g Glycerin 60g Printing Nori 2C, 1, Vat-Brown 5 100g Main thickening made for some parts J- 000g The chemical compound consists of a combination of the following thickener powders: carboxymethyl starch 30 g Depolymerized galactomannan from cluster bean substrate 60g-force-coated product■ contains the following components: Combined: Carboxymethyl starch 30g Depolymerized galactomannan of Prosobis substrate 35g powder Despite different concentrations The viscosity of both main concentrates is the same (measuring device Nibbletsu Field RVT 20 -2000-20 times/min・Axis 4).

The printing comparison was carried out using a rotary printing machine (System Storck RD-4 type). This was done on the website.

Fixation of the prints was carried out in saturated steam (102°C for 110 minutes).

Comparison of prints prepared from main concentrates ■ and ■ is based on the print judgment criteria; color strength, uniformity, The printing paste made from the main concentrate ■, which has a lower concentration in terms of luster, luster, and penetration. Same printing results as the printing ink (Druckfarbe) prepared from the main concentrate ■ Indicates that the result has been brought about.

Kanou Wataru Colored paste according to the following recipe for printing on polyamide Lycra using acid dyes Three types were prepared: C, 1, Ac1dBlue 204 15g water 235g Glyecin A11 (BASF) 50g Urea 50g Thickener solution 600g Ammonium sulfate 1:2-4''- 000g The thickener solution for colored glue 1 was prepared at 4%, while thickener solutions 2 and 3 were prepared for colored glue. It had to be adjusted to 8% in order to have the same viscosity as 1.

The thickener solution consisted of the following: Thickener solution 1: Deweighting of Prosobis substrate. combined galactomannan Thickener solution 2: depolymerized galactomannan of cluster bean substrate Thickener solution 3: alkoxylated galactomannan of cluster bean substrate Printed using a Bouzel lithographic printing machine.

Fixation of the print was carried out in saturated steam at 102° C. for 20 minutes.

In a comparison of three types of prints, the print prepared using a low concentration concentrate according to the invention The printing process using the depolymerized galactomannan of the cluster legume substrate is more effective. The sting effect was low. Regarding washability of textile printing, concentrate solution l (in the present invention) The prints prepared using Concentrate Solution 3 (Marco on Cluster Bean Substrate) The results were similar to those obtained with printing using oxidized galactomannan (oxylated galactomannan). One Also, the concentrate according to the present invention is a depolymerized galactomer of the cluster bean matrix. It was superior to both the nannan and the ethoxylated one.

Trap Gohan 1 Printing on polyamide carpet products using acid dyes.

Two main formulations of concentrates were prepared: A. 3% solution of Prosopis lilyflora endosperm powder described in Example 1 in water B, Cyamopsis tetragonoruba described in Example 1 tragonoloba) endosperm powder 3% solution in water Using concentrate A of Prosopis lilyflora substrate according to the present invention, cluster A carpet printing ink was prepared using matrix substrate concentrate B: Water 560g TBLON Echtblau A 36 GL Log Glyecin A 20g Main formula of concentrate 3% 400g 60% acetic acid 000g Carpet printing was carried out using a lithographic printing machine.

The print was steamed at 100° C. for 10 minutes without intermediate drying.

The frosting effect was lower and the dye yield was higher. The results were comparable in terms of uniformity and uniformity.

Kangan five balls Printing of polyamide carpet products using 1:2 metal complex dye Two main formulations of concentrates were prepared: A. Prosopis lilyflora endosperm powder (from Example 1) 3% solution in water B. Cluster bean endosperm powder (from Example 1) 3% solution in water Using the concentrate A according to the invention of the Prosopis euryflora substrate, the cluster polymer was also used. Two types of carpet printing inks were prepared using Concentrate B for comparison of the matrix substrate.

Water 560g l5OLAN Ge1li NW 250% 1.0gGlyecin A 2 0g Main formula of 3% concentrate 400g 60% acetic acid 000g Carpet printing was done on a lithographic printing machine.

The prints were steamed for 10 minutes at 1.00°C without intermediate drying. Both printing In comparison, the frosting effect of the one using concentrate A according to the present invention was higher. The dye yield was high. The results were comparable in washability, gloss and uniformity.

Copy and translation of written amendment) Submission (Article 184-8 of the Patent Law) March 31, 1990 Yoshi, Commissioner of the Patent Office 1) Takeshi Moon 1. Display of 8 patent applications PCT/DE 88100608 2. Name of the invention Polysaccharide from the endosperm of Namurinus seeds, its recovery method and its application 3. Patent applicant Address: 50° Georgkurei, Daygooo, Munich, Federal Republic of Germany Smüllerstrasse, 32-36 Name: Diamart Akchengese Luschaft 4, deputy manager Address: 1-1-15-5 Nishi-Shinbashi, Minato-ku, Tokyo 105, Japan Date of submission of amendment Scope of claim dated September 7, 1999 Prosopis juliflora (Prosopis juliflora) A species of the genus Ligusa, also known as: Prosopis chirensis, Ceratonia chirensis, Mi It is obtained from the seed endosperm of Moza lilyflora and is essentially embryoless and integument-free. Satucharide and its ether and ester derivatives and their partially decomposed A polymerized derivative in which the ratio of galactose to mannose is 1=1 to 1:1. Polysaccharide which is 5.

2. Rotate the cleaned Prosopis lilyflora seeds at a high temperature of 200 to 250°C. Roast in a tube furnace for about 1 to 3 minutes, then remove the outer skin and embryo with a sheller. , the cleaned endosperm is ground and optionally etherified or etherified in a manner known per se. is characterized by being esterified and/or depolymerized in a manner known per se. The method for recovering polysaccharide according to claim 1.

3. Application of the polysaccharide according to claim 1 as a thickening agent for aqueous bases.

4. Application of polysaccharide according to claim 1 to thickening printing paste in textile printing .

5. Application of the polysaccharide according to claim 1 to food thickening.

6. Polysaccharide according to claim 1 for enrichment of drilling fluid and for beneficiation (strengthening) at oil well site. Application to oil extraction).

7. Boric acid, A1. Sb, Cr, Fe, Co, Cu, Mg, Mn, Ni.

Cross-linked with Ti, V, Zn + Sn, Zr salts or organometallic compounds The polysaccharide according to claim 1.

8. Starch, guar, xanthan, carrageenan, agar, carob kernel powder, jacket Twibara, American rhinoceros beetle, Po'oubok, Hornwort, Kawaraketmei, Derivatives of this type of polysaccharides, i.e. alkyl ethers, substituted alkyl ethers, ethers, carboxyalkyl ethers and phosphoric esters, and poly(meth)a Polymer according to claim 1 or 7 in a mixture with a thickening agent from the group consisting of acrylates. Satucarid.

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Claims (9)

[Claims] 1. Prosopis juliflora (Prosopis juliflora) A species of the genus Ligusa, also known as: Brosopis chirensis, Ceratonia chirensis, Mi Essentially embryo- and integument-free polysperm obtained from the seed endosperm of Mosa lilyflora) Saccharides and their ether and ester derivatives and their partially decomposed Polymerized derivative. 2. Characterized by a galactose to mannose ratio of 1:1 to 11.5. The polysaccharide according to claim 1. 3. The cleaned Prosopis lilyflora seeds are heated to a high temperature of 200 to 250℃. Roast in a rotary tube furnace for about 1 to 3 minutes, then use a sheller to remove the husk and embryo. The removed and cleaned endosperm is ground and optionally etherified in a manner known per se. and/or depolymerization in a manner known per se. The method for recovering polysaccharide according to claim 1 or 2. 4. Application of the polysaccharide according to one of claims 1 to 3 as a thickener for aqueous systems. . 5. Printing paste density in printing polysaccharide textiles according to one of claims 1-3. Application to . 6. Application of the polysaccharides according to one of claims 1 to 3 in food concentrates. 9 7. Polysaccharide according to one of claims 1-3 for thickening well fluid and at oil well site. Application to ore beneficiation (enhanced oil extraction). 8. Nitric acid, Al, Sb, Cr, Fe, Co, Cu, Mg, Mn, Ni, Ti, V , Zn, Sn, Zr in a cross-linked form with a salt or an organometallic compound. The polysaccharide according to one of 33. 9. Starch, guar, xanthan, carrageenan, agar, carob kernel powder, jacket Twibara, Honigbohne, Honigbohne, Horned oak Sanem, Kawaraketsumei, derivatives of this type of polysaccharides, namely alkyl ethers. esters, substituted alkyl ethers, carboxyalkyl ethers and phosphoric esters. Claimed as a mixture with a thickening agent from the group consisting of The polysaccharide according to one of items 1-3 or 8.