JPS6128083A - Tamarind size receiving hydroxyalkyl-carboxymethylation - 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 a sizing agent obtained by converting tamarind seed powder or tamari/dogam into hydroxyalkyl (hereinafter abbreviated as rHAJ)-carboxymethyl (hereinafter abbreviated as rcMJ).

Tamarind seed powder is obtained by removing the outer skin of the seeds of Tamarindus Indica, an evergreen tree of the legume family that occurs in the tropics, and then simply crushing the seeds6. Tamarind e-gum is extracted and purified from the powder.

Conventionally, HA-only reactants and CM-only reactants made from tamarind seed powder or tamari/tofu gum as raw materials have been useful as industrial thickeners, such as printing pastes in the textile industry and adhesives in the paper industry. This is known (see West German Publication No. 1108198, US Pat. No. 3,223,699 and US Pat. No. 4,089,646).

However, these substances as printing pastes can be used as direct dyes,
It reacts with acid dyes and metal complex dyes to form a gel and has extremely poor compatibility with them, and has drawbacks such as reacting with the dyes and poor desizing properties in cotton printing using reactive dyes. Furthermore, although its effectiveness as an adhesive has been recognized, it is inferior to starch that is currently commonly used for this purpose.

The inventors of the present invention have conducted intensive studies and found that these drawbacks can be improved by converting tamarind seed powder or tamarind gum into HA-CM. Further detailed research was conducted and the average degree of substitution per sugar unit (rDS
For example, when HAA S is about 1, CMMCS is 0.35 or more, when HAA S is 05, CMMCS is 0.43 or more, and IJA DS is 0.3.
It has been found that desirable effects can be obtained when CMMCS is 0.48 or more when the CMMCS is 0.48 or more, and when the CMMCS is 0.51 or more when the HA-formed DS is 0.2. Furthermore, when only CM conversion was performed, the expected effect could not be obtained even if the DS was increased to 0.62.

From the above results, when HAA conversion S is y and CMMCS is x, HA is
-I found out that it would be better to make it into a commercial.

y≧6.6−26.4x+35. lx'-15,6x
'(0<x<2.O<y<2) (I) A more preferable effect can be obtained by converting HA-C'M so as to satisfy the following formula (n).

y≧8.6-31.5x+38.4x'-15,6x'
(■) HA-CM formation in the present invention can be carried out by a known method (see the above-mentioned publication). First, 1-TA conversion is carried out under alkaline conditions using alkylene oxide or alkyl halohydrin, such as edile/oxite, propylene oxide, ethylene chlorohydrino, propylene chlorohydrino, etc., and the product is converted into monochlorohydrin under alkaline conditions. CM with acetic acid or its salt, etc. Examples of the alkali used in both reactions include alkali metal hydroxides such as NaOH and KOH.

Usually, HA formation is carried out using the above formula (I), preferably the above formula (I).
As long as I) is satisfied, 0〈y〉2. Preferably, the HA agent is added in an amount of 1 to 200% by weight based on tamarind seed powder or tamarind gum (hereinafter simply referred to as "tamarind gum") so that 0.2≦y≦0.85.
It is preferably used in an amount of 20 to 85% by weight. In addition, CM conversion usually satisfies the formula (■), preferably the formula (II), as long as O<x<2. Preferably 0.45≦X≦0
．． 85, the CM agent is added in an amount of 1 to 160% by weight, preferably 40 to 160% by weight, based on the HA-modified tamarind gum.
It is carried out using 90% by weight.

The sizing agent of the present invention can be made into a sizing agent by adding 1 to 50 times the amount of water and stirring to swell depending on the purpose of use. If necessary, a desired dye,
It is used in combination with an R agent and auxiliary agents (for example, a pH adjuster, a reduction inhibitor, a dye solubilizer, a penetrant, a leveling agent, a deep dyeing agent, an antifoaming agent, a fixing agent, a pretreatment agent, etc.). There is no reaction with these.

Although the sizing agent of the present invention exhibits sufficient performance even when used alone, it can be used with other sizing agents that have been conventionally used (e.g., De/P/, Edenp/, natural gum).

Processed gum, sodium alginate, CMC, etc.) can also be used in combination.

゛In order to explain the present invention in more detail, Examples and Comparative Examples are given below, but the present invention is of course not limited to these. In the following examples, hydroxypropylated DS is
Te5t Method D-2367-72,
Hydroquine ethylation DS was measured according to the same method D-2,364-75, and carboxine methylation DS was measured according to the same method D-1439-65.

Example 1 Production of the thickening agent of the present invention 200 g of tamarind seed powder and 24 g of a 38.5% NaOH aqueous solution were added to a closed reaction vessel equipped with a stirrer and stirred and mixed at room temperature for about 1 hour. - At night, add 80 g of propylene oxide, react at 75-80°C for 4 hours, cool to room temperature, neutralize with concentrated sulfuric acid, crush, dry, crush, and convert tamarind into hydroxypropyl (hereinafter abbreviated as rHPJ). 297 g of seed powder are obtained. The HP DS was 032.

Put 44.3 g of NaOH, 120 g of water, and 609 ml of Impropanol into a three-way flask and dissolve with stirring for 5 minutes. Add 120 g of the above powder and disperse. Add 46.5 g of monochloroacetic acid and reflux for 2 hours. The mixture was cooled to room temperature, neutralized with concentrated sulfuric acid, saturated with suction, washed seven times with about 80% methanol, dried, and ground to obtain 178 g of a product.

The commercial DS was 064.

This product gelatinizes easily when water is added. The viscosity of the 1.5% aqueous solution is 23.4 cps (using a BL Brookfield viscometer manufactured by Tokyo Keiki Seisakusho at 25°C and 30 rpm).
used in Measured under the same conditions below).

Example 2 69.0 g of NaOH, 74.0 g of water,
375.6ml of Improper Tools.

A product is obtained in the same manner as in Example 1 except that 816 g of monochloroacetic acid is used. HP conversion DS is 0.32. Commercialization D
S was 0.85. This product also gelatinizes easily with water.
．． The viscosity of a 5% aqueous solution is 9.2 cps.

Example 3 Production of a thickening agent of the present invention 200 g of coumarinoid seed powder and 36 g of a 38.59 A NaOH aqueous solution were added to a closed reaction vessel equipped with a stirrer, and the mixture was stirred and mixed at room temperature for about 1 hour. - Leave to stand overnight, add 120 g of propylene oxide, react at 75-80° C. for 5 hours, cool to room temperature, neutralize with t5 sulfuric acid, crush, dry and crush to obtain 340 g of HP-modified tamarind seed powder. HP conversion DS
was 0.81.

Put 09 g of NaOH, 74 g of water, and 375.6 ml of Improper Tool into a three-ring flask, dissolve while stirring, and add 120 g of the above powder and disperse. Monochloroic acid a81. Add 3 g of f and reflux for 2 hours. The mixture was cooled to room temperature, neutralized with concentrated sulfuric acid, filtered under suction, washed with about 80% methanol, dried, and ground to obtain 221 g of a product.

CM conversion DS was 0.80.

This product also gelatinizes easily with water, and the viscosity of a 3% aqueous solution is 21.
It is 5 cps.

Example 4 Production of brightening paste A product was obtained in the same manner as in Example 3, except that 52.6 g of NaOH and 62.1 g of monochloroacetic acid were used during commercialization. The HP-based DS was 0.8+, and the CM-based DS was 0.62. This product also gelatinizes easily with water, and the viscosity of a 3% aqueous solution is 330 CpS.

Example 5 Production of a sizing agent of the present invention A product was obtained in the same manner as in Example 3, except that 39.4 g of NaOH and 46.6 g of monochloroacetic acid were used during commercialization. HP version DS is 0.81, CM version DS is 0.45
Met. This product also gelatinizes easily with water, and the viscosity of a 3% aqueous solution is 27.0 cps.

Example 6 Production of a sizing agent of the present invention 200 g of Tumarif 8 seed powder and 18 g of a 38.5% NaOH aqueous solution were added to a closed reaction vessel equipped with a stirrer and stirred and mixed at room temperature for about 1 hour. - After leaving overnight, add 60g of propylene oxide and react at 75-80°C for 4 hours,
After cooling to room 2, it was neutralized with concentrated sulfuric acid, crushed, dried, and ground to obtain 258 g of hydroxypropyl (hereinafter abbreviated as rHPJ) coumarite seed powder. HP converted DS was 0.22.

39.4 g of NaOH, 74 g of water, and 375.6 ml of isopropanol are placed in a trisol flask and dissolved while stirring, and 120 g of the above powder is added and dispersed. Add 46.6 g of monochloroic acid and reflux for 2 hours. The mixture was cooled to room temperature, neutralized with concentrated sulfuric acid, filtered with suction, washed with about 80% methanol, dried, and ground to obtain 150 g of a product.

CM conversion DS was 0.60.

This product also gelatinizes easily with water, and the viscosity of a 15% aqueous solution is 12
．． It is 4cps.

Example 7 Production of a sizing agent of the present invention A product was obtained in the same manner as in Example 6, except that 47.4 g of N'a OH and 55.9 g of monochloroacetic acid were used during commercialization. HP version DS is 0.22, CM version DS is 0.22.
It was 63. This product also gelatinizes easily with water, and the viscosity of a 1.5% aqueous solution is 10·2 cps.

Example 8 Production of a thickening agent according to the present invention 200 g of tamarind seed powder and 30 g of a 38.5% NaOH aqueous solution were added to a closed reaction vessel equipped with a stirrer and stirred and mixed at room temperature for about 1 hour. - At night, add 100 g of propylene oxide and react at 75 to 80°C for 4 hours.
After cooling to room temperature, the mixture was neutralized with concentrated sulfuric acid, crushed, dried, and ground to obtain 307 g of hydroxypropyl (rHPJ) tamarind seed powder. HP converted DS was 056.

Put 19.7 g of NaOH, 37 g of water, and 187.8 ml of Improper Tool into a Mitsuro flask, dissolve while stirring, and add 60 g of the above powder and disperse. Monochloroic acid i! Add 23.3 g of I and reflux for 2 hours. The mixture was cooled to room temperature, neutralized with concentrated sulfuric acid, filtered with suction, washed with about 80% methanol, dried, and ground to obtain 82.5 g of a product. CM conversion DS was 0.50.

This product also gelatinizes easily with water, and the viscosity of a 1.5% aqueous solution is 9.
．． It is 0 cps.

Example 9 Production of a sizing agent of the present invention HP-modified tamarind seed powder was obtained in the same manner as in the first half of Example 1. HP conversion DS was 0.31.

37 days Put 41 g of NaOH and 00 ml of 95% Meta/-Lua in a flask, dissolve while stirring, and add 162 g of the above powder and disperse.

Add 116 g of sodium monochloroacetate and reflux for 2 hours. After cooling to room temperature, neutralizing with concentrated sulfuric acid, and filtering with suction,
Wash with about 80% methanol, dry and crush to produce product 269.
I got g. CM conversion DS was 0.48.

This product also gelatinizes easily with water, and the aging of a 1.5% aqueous solution is 87 cps.

Example 10 Production of sizing agent of the present invention Ethylene oxide 6 was used instead of propylene oxide.
A product was obtained in the same manner as in Example 9 except that 0 g was used. Hydroxyethyl (hereinafter abbreviated as rHEJ) DS is 0
．． 30, CM conversion D・S was 0.50. This product also gelatinizes easily with water, and the viscosity of a 1.5% aqueous solution is 65 c.
It is ps.

Example 11 Production of thickening agent of the present invention Tamarind gum 150 was used instead of tamarind seed powder.
A product is obtained in the same manner as in Example θ except that g is used.

HP-formed DS had θ of 32, and CM-formed DS had a value of 0.52. This product also gelatinizes easily with water, and the viscosity of a 1.5% aqueous solution is 180 cps.

Example 12 Production of a sizing agent of the present invention A product was obtained in the same manner as in Example 6, except that 42.7 g of NaOH and 50.5 R of mono/chloroacetic acid were used during CM conversion. HP DS is 0.22° CM DS is 0.52
Met. This product also gelatinizes easily with water, and the viscosity of a 1.5% aqueous solution is 7.6 cps.

Example 13 Production of a sizing agent of the present invention A product was obtained in the same manner as in Example 8, except that 27.1 g of NaOH and 20.2 g of mo/chloroacetic acid were used during commercialization. HP version DS is 0.58, CM version DS is 0.45
Met. This product also gelatinizes easily with water, and the viscosity of a 1.5% aqueous solution is 10.8 cps.

Comparative Example Production of IHP-formed tamarind paste A HP-formed chestnut/turquoise seed powder was obtained in the same manner as in the first half of Example 1. HP conversion DS was 0.31. 1.5 of this sample
% aqueous solution is 41 cps.

Comparative Example 2 Production of HE-modified Tamarind Seed Powder A HE-modified tamarind seed powder was obtained in the same manner as in the first half of Example 7. The HE conversion DS was 0.30. The viscosity of a 1.5% aqueous solution of this sample is 39 cps.

HP-converted Kumari/Doku gum is obtained in the same manner as in the first half of Example 8. , HPP conversion S was 0.32. 1 of this sample
．． The viscosity of a 5% aqueous solution is 246 cps.

Comparative Example d Production of CMized tamarind paste A CMized tamarind seed powder is obtained in the same manner as in the second half of Example 6, except that simple tamarind seed powder is used instead of the HP-converted tamarind seed powder. CM conversion DS was 0°32. The viscosity of a 1.5% aqueous solution of this sample is 162 Cp!
It is.

Comparative Example 5 Production of CM-modified tamarind paste
9g, instead of 118g of sodium monochloroacetate,
Using 57.9g of monochloroacetic acid, 75g of water instead of 700ml of 95% methanol and Improper Tool 3
CMized tamarind seed powder is obtained in the same manner as in Comparative Example 4, except that 80 ml of the powder is used. CM conversion DS was 0.53. The viscosity of a 1.5% aqueous solution of this sample is 79 cps.

Comparative Example 6 Production of HP-CM tamari/glue NaO
29.6g of H, 35g of monochloroacetic acid, 74g of water
A HP-CM-converted tamari/do paste was obtained in the same manner as in Example 1, except that 375.6 ml of 1 Improper Tool was used. HPP S is 032, CM DS is 0.46.1.5
The viscosity of the 9A aqueous solution is 22.0 cps.

Comparative Example 78 Production of P-CM tamarind paste 21 g of NaOH, 22.8 g of monochloroacetic acid during CM conversion
A HP-CM-converted tamarind paste was obtained in the same manner as in Example 3 except that 74 ml of g1 water and 375.6 ml of isobutanol were used. HP version DS is 0.81, CM version DS
The viscosity of a 0.33.3% aqueous solution is 25 cp's.

Comparative Example 8 Production of HP-CM tamarind paste 34.2 g of NaOH and 40 g of monochloroacetic acid were used for CM conversion.
A product was obtained in the same manner as in Example 6, except that 4 g was used.

The HPP conversion S was 0.22, and the CM conversion DS was 0.42. This product also gelatinizes easily with water, and the viscosity of a 1.5% aqueous solution is 10.0 cps.Comparative Example 9 Production of HP-CM tamarind paste A product is obtained in the same manner as in Example 8, except that 17.5 g of acetic acid is used. HPP conversion S is 0.56, CM (i, DS is 0.4
It was 0. This product also gelatinizes easily with water, and the viscosity of a 1.5% aqueous solution is 12.6 cps.

Example 14 Compatibility, level dyeing, and desizing test Examples 1 to 1
3 or the paste obtained in Comparative Examples 1 to 0, tamarind seed powder alone or HPP-ized malindo seed powder (Comparative Example 1) and C
A base paste having the following concentration is prepared for a 1:1 (weight ratio) mixture (viscosity of a 1.5% aqueous solution is 75 cps) of Mized tamarind seed powder (Comparative Example 4). Only tamarind seed powder does not dissolve in water as it is, so add water for 75 minutes.
Heat for 15 minutes at °C to dissolve (1.5% aqueous solution has a viscosity of 104 cps).

HP-CM modified tamarind seed powder (Example 1)-15
% aqueous solution (〃 2)...-20% 〃 (〃 3)--30% 〃 n (n 4)--2δ% 〃tt
(1) 5)---・25% 〃(〃
6)--22% 〃 (〃 7)--26% 〃 (/I 8)--22% 〃 (// 9)-- 9% 〃 IE-CM-converted tamarinot seed powder Agent (#10) ---
-10% 〃HP-CM tamarind gum agent (#1
1)・-8% 〃HP-CM coumarin doriko powder (
#12) --- 30% 〃(//13)--25
%〃HI) modified tamarind seed powder (Comparative Example 1) ・−
12% IHEized tamarind seed powder (//2)
-12% 〃HE modified tamarind gum (〃
3) −・・−6%〃CMized tamarind seed powder (〃4) −・−・8%〃(n 5)
----12% 〃HP-CM tamarind seed powder (1/'6) -15% NoI (j/
7) -,25% 〃 (II 8) -25% 〃 (II 9) -25% 〃 Tamarind seed powder -9%
//] (P-modified tamarind seed powder (comparative example 1) -cM
Compatible Tamarind Seed Powder (Comparative Example 4) Mixture -・
10%〃In order to check the quickness of each base paste against reactive dyes, we prepared colored pastes with the following formulations and printed them on cotton broadcloth using a test flat screen (100 mesh:,) at 70°C for 5 minutes. Dry for 9B'C, steam for 20 minutes, 1
Wash with water for 5 minutes, wash with hot water at 100℃ for 15 minutes,
100°C using 2git (manufactured by Kogyo Seiyaku) and a bath ratio of 1:50.
After soaping for 10 minutes, washing with water, and drying, the resulting printed fabric was observed.

Revafix Brilliant Red E-4B
2; 0% (manufactured by Bayer) Urine 1L:
5.0% m-Nitrobe/Se/Sodium Sulfonate 1.0% Na1lCOa
2.0% water
30.0
94 base glue 60.0% 100.09A (i) Compatibility test All of the obtained color pastes had good compatibility.

(ii) Level dyeing property/removal property test All color pastes had good level dyeing property, but the size properties of the glues other than the glue of the present invention were remarkable.

On the other hand, the paste of the present invention was extremely good.

Example 15 Compatibility, level dyeing, and desizing test Examples 1 to 8
Or the glue obtained in Comparative Examples 1 to 9, tamarind seed powder alone or HP-modified tamarind seed powder (Comparative Example 1) and CM
1:1 (weight ratio) of tamarind seed powder (comparative example 4)
For the mixture, a base paste similar to that in Example 14 was prepared, a colored paste having the following reactive dye formulation was prepared, and a printed fabric obtained by processing in the same manner as in Example 14 was observed.

Remazol Turquoise Blue 6 2
．． 0% (manufactured by Hoechst) Urea ゛5. θ% m-nitrobe/sensulfo/@sodium
1.0%Na2CO32.0% water
30.0% Original paste 60.0% 100.0% (i) Compatibility test All of the obtained color pastes had good compatibility.

(11) Level dyeing property De-sizing property test All color pastes had good level dyeing properties, but the glues other than the glue of the present invention had extremely poor desizing properties and could not be put to practical use. On the other hand, the glue of the present invention was mossy and had a good quality.

Example 16 Compatibility, level dyeing, and desizing properties test In order to examine the applicability of the base paste prepared in Example 14 to direct dyes,
Prepare colored glue with the following recipe.

Kayaras Supra Ruby 7r3L (Nippon Kayaku Bag)
2.0% thiodiethylene glycol
2.0% boiling water 360% Original glue 60.0% 100.0% (i) Compatibility test When the obtained glues of each color were observed with the naked eye, it was found that the glues other than the glue of the present invention gelled. This resulted in poor compatibility. However, the paste of the present invention produced a uniform colored paste and had good compatibility.

(11) Level dyeing and desizing test Color paste was applied to cotton broadcloth using a flat screen for testing (100
Print using a paper towel (Mesh), dry at 75°C for 5 minutes, and
Steamed at 8℃ for 20 minutes and washed with water for 15 minutes, amylazine D (
(manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 g/l at a bath ratio of 1:50, sawbig was carried out at 60° C. for 10 minutes, washed with water, and dried, and the resulting printed fabric was observed.

All of the colored pastes using the sizing agent of the present invention had excellent level dyeing properties and desizing properties. Since it has already been determined that other color pastes are incompatible, this item was not considered.

Example 17 Compatibility, level dyeing, and desizing properties test In order to investigate the applicability of the base paste prepared in Example 14 to acid dyes,
Prepare colored glue with the following recipe.

Nylosunlet N5BL (SyF tJ)
2.0% thiodiethylene glycol
2.0% ammonium tartrate
3.0% fever $
38.0% original glue
60.0% 100.0% (i) Compatibility test The same results as in Example 16 were obtained.

(ii) Level dyeing and de-sizing test Color paste was applied to nylon jersey for testing Furanoto Scree-7 (
+00 mesh), dried at 75°C for 5 minutes, heated at 98°C for 30 minutes, washed with water for 15 minutes,
Amirazine D (i-industrial pharmaceutical bag) 2g/l, bath ratio l:5
0 for 10 minutes at 60°C, washed with water and dried, and the resulting printed fabric was observed.

All of the colored pastes using the sizing agent of the present invention had excellent level dyeing properties and desizing properties. Other color pastes have already been found to have poor compatibility, so this item was not considered.

Example 18 Compatibility, level dyeing, and desizing test In order to examine the applicability of the base paste prepared in Example 14 to metal complex dyes, a colored paste with the following formulation was prepared.

Iceno Ovalplanoch New Conc Z, 0% (Hodogaya Chemical) Thiodie Dire/Glycol
2.0% a/mon tartrate
3.0% hot water
33.0% original paste 6
0.0% 100.0% (+) Completely the same results as in Compatibility Test Example 16 were obtained.

(ii) Level dyeing property - Desize property test The same treatment as in Example 17 was carried out, and exactly the same results were obtained.

Claims (1)

[Claims] (1) When the average degree of substitution of hydroxyalkyl groups per sugar unit is y (0<y<2) and the average degree of substitution of carboxymethyl groups is x (0<x<2), the relationship between x and y is as follows. A thickening agent whose main ingredient is hydroxyalkyl-carboxymethylated tamarind seed powder or tamarind gum represented by the formula. y≧6.6-26.4x+35.1x^2-15.6x
^3(2) The adhesive according to claim 1, wherein the relationship between x and y is expressed by the following formula. y≧8.6-31.5x+38.4x^2-15.6x
^3(3) Claim 1 in which the paste is a paste for textile printing
Gluing agent at the top.