KR20040021385A - Textile printing polysaccharide and manufacture method of thereof - Google Patents

Abstract

PURPOSE: A polysaccharide for printing and its preparation method are provided, to obtain the polysaccharide used as a thickener which has compatibility with various dye used in textile printing and no reactivity with various chemicals for printing. CONSTITUTION: The polysaccharide is such that it is substituted with a carboxymethyl group by 30-40 % and a hydroxyalkyl group by 5-15 %, by adding sodium monochloroacetate and propylene oxide. Preferably the polysaccharide is selected from corn starch, guar gum and its derivative. The method comprises the steps of putting 100 parts by weight of a polysaccharide to a reactor; mixing 27-36 parts by weight of 50% sodium hydroxide aqueous solution and 20-30 parts by weight of methanol to prepare a mixture solution; spraying the mixture solution to the reactor by using a nozzle provided with a chopper of 2,000 rpm or more, and homogenizing it; dissolving 20-30 parts by weight of sodium monochloroacetate to 30-40 parts by weight of water, adding the obtained solution to the reactor, and carboxymethylating the reaction mixture at a temperature of 55-60 deg.C to prepare the carboxymethylated polysaccharide; putting 5-15 parts by weight of propylene oxide to the reactor and hydroxyalkylating the reaction mixture at a temperature of 55-60 deg.C; and adding 0.005-0.02 parts by weight of hydrogen peroxide to the reactor after the reaction is terminated to cut the polysaccharide molecule.

Description

Printing polysaccharide and manufacturing method thereof

The present invention relates to a polysaccharide for printing and a method for manufacturing the same, and more particularly, to a polysaccharide having a carboxy methyl group and a hydroxy alkyl group in a polysaccharide molecule by simultaneously applying a carboxy methylation method and a hydroxy alkylation method in preparing a polysaccharide used as a flavoring agent. It is compatible with various dyes (direct dyes, reactive dyes, disperse dyes, acid dyes, cationic dyes, etc.) used in textile printing, and has various printing auxiliary chemicals (organic acid, inorganic acid, alkaline agent, urea, chloride). It is not reactive with 1 stone, aluminum sulfate, and decroline, and it does not solidify, so various printing methods can be applied to various fabrics (sponge, cotton fabric, polyester fabric, nylon fabric, acrylic fabric, acetate fabric, T / C fabric, etc.) It relates to a printing polysaccharide and a method of manufacturing the same that can be applied (direct printing, balsamitis, burn out, etc.).

The materials currently used for printing work are as follows.

First, a material used for cellulose-based fiber printing such as cotton, rayon, and hemp using reactive dyes includes sodium alginate. The alginosa soda is a natural polysaccharide additive extracted from seaweed and has an -COONa group and two -OH groups in its molecular structure as an anionic colloid material. This can be seen as a polysaccharide whose substitution degree of the carboxymethyl group is one. General physical properties can be used for printing polyester fabrics using disperse dyes, and no other work is possible.

Next, sodium alginate and carboxymethylated polysaccharides are used for the polyester fiber printing using a disperse dye.

And, silk using acid dye, nylon fiber printing, printing dye using first grade chloride, acrylic fiber printing using cation dye, T / C fiber printing using direct dye, sulfuric acid or aluminum sulfate For burn out printing, hydroxy alkylated polysaccharides (raw polysaccharides: guar gum and starch) are used as ingredients.

As described above, the paint used in the work for various printing on a variety of fabrics in each printing factory is different depending on the dye, fiber or printing method, and is used to prepare a variety of suitable paints for each printing. This leads to economic losses, such as difficult management of the hory, to discard the remaining hory used.

On the other hand, Korean Patent No. 312,999 invented by the present inventors discloses a method for preparing hydroxy alkylated polysaccharides, and the patent presupposes using a conventional reactor which does not attach any device for homogenization of the product during the reaction. And a polysaccharide generated from the preceding patents [US Pat. Nos. 2,496,670, 3,326,890, Japanese Patent Publication Nos. 53-39386, 58-109501] and agglomerates with no deterioration in physical properties of the final reactants due to heterogeneous reactions. Disclosed is a method for preparing a hydroxy alkylated polysaccharide paste for printing. The paints prepared by the above methods include silk fabric printing using acid dyes, nylon fabric printing, acrylic fabric printing using cationic dyes, polyester fabrics using first salt chloride, printing printing of acetate fabrics, and sulfuric acid. Or burn out printing using aluminum sulfate, printing of T / C fabrics using direct dyes, or printing using dechlorin. However, direct printing of polyester fabrics using high temperature steam generators cannot be used because they are not called. In addition, direct printing of cotton fabrics, rayon fabrics, and hemp fabrics using reactive dyes is not possible because it is not called.

In addition, Korean Patent No. 332,215 invented by the inventors discloses a method for preparing a high viscosity carboxymethylated polysaccharide, and in the patent, a method for producing a homogeneous material having a homogeneous degree of reaction using a minimum amount of water and methanol. Is disclosed. The paste prepared in this way is used for direct printing of polyester fabrics using disperse dyes. However, this paste is not usable due to entangled with the kinds of metal ions that occupy most of the acid dyes, and gelled by combining with the first chlorine chloride, and by the sulfuric acid, sodium ions are separated into sodium sulfate and lose viscosity. If severe, it becomes insoluble and precipitates.

In this way, various kinds of paints must be prepared for various printing works in the prior art, and if the wrong printing is selected at the production plant, if the printing does not wash with water or changes color, defects such as color change and recoloring are applied. There is an economic loss such as printing or selling cheap as a defective product, so to solve this situation, it is necessary to develop a paint that can be used in any printing method.

Thus, the present inventors simultaneously apply the carboxy methylation method and the hydroxy alkylation method in the preparation of the polysaccharide used as a feed to solve the above problems, if the carboxy methyl group and the hydroxy alkyl group in the polysaccharide molecule at the same time a variety of printing It was found that work is possible to complete the present invention.

Therefore, the present invention is compatible with various dyes (direct dyes, reactive dyes, disperse dyes, acid dyes, cationic dyes, etc.) used in textile printing and has various printing auxiliary agents (organic acid, inorganic acid, alkaline agent, urea, chloride). It is not reactive with 1st class stone, aluminum sulfate, and decrine, so it does not solidify, so it can be printed on various fabrics (sponge, cotton fabric, polyester fabric, nylon fabric, acrylic fabric, acetate fabric, T / C fabric, etc.) It is an object of the present invention to provide a printing polysaccharide and a method of manufacturing the same that can be applied to the method (direct printing, balconitis, burn out, etc.).

The present invention is characterized by a printing polysaccharide in which sodium monochloroacetate and propylene oxide are added to a polysaccharide to which a carboxymethyl group is substituted by 30 to 40%, and a hydroxy alkyl group is substituted by 5 to 15%.

The present invention is a method for producing a polysaccharide for printing,

1) adding 100 parts by weight of polysaccharides to the reactor,

2) preparing a mixed solution by mixing 27 to 36 parts by weight of a 50% caustic aqueous solution separately from 1 and 20 to 30 parts by weight of methanol,

3) mixing and homogenizing the mixed solution of 2 through a micronozzle under a high speed mixing condition in which chopper is provided at 2000 rpm or more;

4) dissolving 20-30 parts by weight of sodium monochloroacetate in 30-40 parts by weight of water, adding the mixture to the reactor, mixing the mixture, and raising the temperature inside the reactor to 55-60 ° C. to obtain a carboxymethylated polysaccharide,

5) injecting 5-15 parts by weight of propylene oxide to the reactor to hydroxy alkylation reaction at a reactor temperature of 55 ~ 60 ℃,

6) After the reaction is finished, a method for producing a printing polysaccharide, which comprises the steps of cleaving polysaccharide molecules by adding 0.005 to 0.02 parts by weight of hydrogen peroxide, is another feature.

Referring to the present invention in more detail as follows.

The present invention relates to a polysaccharide used as a printing paste for having various carboxymethyl groups and hydroxy alkyl groups in the polysaccharide molecule to enable various printing operations with one type of paste.

Referring to the printing polysaccharide of the present invention as described above in more detail by each manufacturing step as follows.

In the present invention, in order to have a carboxy methyl group and a hydroxy alkyl group in the polysaccharide molecule at the same time, the carboxy methylation reaction first, and then the hydroxy alkylation reaction.

Therefore, in order to carboxymethylate the polysaccharides, 100 parts by weight of polysaccharides are added to the reactor, and separately, 27 to 36 parts by weight of a 50% caustic soda solution and 20 to 30 parts by weight of methanol are prepared to prepare a mixed solution. Under high-speed mixing conditions equipped with a Chopper at 2000 rpm or higher in the reactor, the mixture is sprayed through a micronozzle and homogenized. Then, 20 to 30 parts by weight of sodium monochloroacetate is dissolved in 30 to 40 parts by weight of water, added to the reactor, mixed, and the temperature inside the reactor is raised to 55 to 60 ° C for carboxy methylation to obtain carboxymethylated polysaccharides.

At this time, if the amount of caustic soda is out of the above range, the polysaccharide is heated for a long time under strong alkali conditions, so the viscosity decreases severely and a modified polysaccharide is produced. There is a problem in that the content of the solvent in the reactant becomes self-solidifying during the reaction. In addition, if the rotational speed of the reactor chopper does not fall within the above range, there is a problem such as uneven mixing or agglomeration. If the amount of sodium monochloroacetate is less than 20 parts by weight, there is a problem in printing properties (chromic desorption penetration) when printing in the field, and if it exceeds 30 parts by weight, the viscosity decreases. If the reaction temperature of the carboxymethyl reaction is less than 55 ° C there is a problem that the reaction time is long, and if it exceeds 60 ° C there is a problem that the viscosity of the reactants decreases. In addition, the polysaccharide may be used alone or in combination of tamarind gum, corn starch, guar gum and derivatives thereof.

The polysaccharide which has undergone the carboxy methylation reaction as described above has a high degree of substitution of 0.7 to 1.1 and has excellent de-defogging properties. This is equipped with a high-speed rotary blade in the reactor to increase the degree of substitution by homogeneously mixing polysaccharides, caustic soda and sodium monochloroacetate.

Next, in order to hydroxy alkylate the carboxymethylated polysaccharide, 5-15 parts by weight of propylene oxide was injected into the reactor subjected to the carboxymethylation reaction, and hydroxyalkylated at the reactor temperature of 55-60 ° C. After completion of the reaction, hydrogen peroxide 0.005-- The polysaccharide molecule | numerator is cut | disconnected by adding 0.02 weight part and the polysaccharide for printing is obtained.

At this time, if the amount of propylene oxide used is less than 5 parts by weight, there is a problem that the chemical resistance is inferior, and if it exceeds 15 parts by weight, there is a problem that the viscosity falls. In addition, if the reaction temperature of the hydroxy alkylation reaction is less than 55 ℃, the reaction time is long, and if it exceeds 60 ℃, there is a problem that the deformation of the physical properties due to the abnormal reaction. In addition, when the amount of hydrogen peroxide used is less than 0.005 parts by weight, there is a problem that the viscosity decrease does not occur, and when it exceeds 0.02 parts by weight, there is a problem that the viscosity decrease is severe.

As described above, the polysaccharide according to the present invention which has undergone the carboxy methylation reaction and the hydroxy alkylation reaction is substituted with 30 to 40% of the carboxy methyl group and 5 to 15% of the hydroxy alkyl group.

In this way, the present invention by having a carboxy methylation reaction and a hydroxy alkylation reaction to the polysaccharide at the same time to have a carboxy methyl group and a hydroxy alkyl group in the polysaccharide molecule, various dyes (direct dyes, reactive dyes, disperse dyes, acid dyes used in textile printing) It is compatible with various printing auxiliary chemicals (organic acid, inorganic acid, alkaline agent, urea, stannous chloride, aluminum sulfate, decroline, etc.) and is not solidified. It is possible to apply a variety of printing methods (direct printing, balming, burn out, etc.) to silk fabric, cotton fabric, polyester fabric, nylon fabric, acrylic fabric, acetate fabric, T / C fabric, etc.

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.

Example

A 15 L reactor equipped with Chopper with rotational power of 2000 rpm or more was used.

5000 g of guar gum was added to the reactor. A homogeneous high speed stirring was carried out while spraying a solution of 1500 g of 50% caustic soda solution and 1000 g of methanol in the stirrer. After dissolving 1500 g of sodium monochloroacetate in 1900 ml of water, the mixture was stirred at high speed while spraying the reactor again. The temperature inside the reactor was raised to 60 ° C and reacted for 3 hours. After the reaction, the reactor temperature was cooled to 25 ° C. (injection was difficult at high temperatures because the propylene oxide boiling point was 34 ° C.).

A small amount of sample was taken to determine the degree of substitution.

500 g of propylene oxide was injected into the cooled reactor, and the reaction temperature was raised to 60 ° C. for 3 hours. After completion of the reaction, 1 g of hydrogen peroxide was injected and subjected to molecular cleavage at the same temperature for 1 hour. After cooling to room temperature the residual caustic soda was neutralized with 530 g of phosphoric acid.

Comparative Example 1

As in Example, caustic soda solution was homogenized. 500 g of propylene oxide was injected and reacted at 60 ° C for 3 hours.

A small amount of sample was taken to determine the degree of substitution.

After homogenizing by spraying the same amount of sodium monochloroacetic acid solution as in Example, it was reacted for 3 hours at 60 ℃.

After the reaction, 1 g of hydrogen peroxide was injected and molecularly cleaved for 1 hour at the same temperature. After cooling to room temperature it was neutralized with 530 g of phosphoric acid.

Comparative Example 2

In the same manner as in Example, sodium monochloroacetate and propylene oxide were simultaneously added and homogenized, followed by reaction at 60 ° C. for 3 hours.

A small amount of sample was taken to determine the degree of substitution.

It was made to react at 60 degreeC again for 3 hours.

Thereafter, the molecule was cut and neutralized in the same manner as in Comparative Example 1.

Comparative Example 3

It was carried out by the manufacturing method of Korean Patent No. 332,215.

5000 g of guar gum was charged to a 15 L closed reactor. A solution obtained by mixing 10 g of epichlorohydrin as a crosslinking agent in 300 g of methanol was injected into the reactor and stirred homogeneously. 1500 g of sodium monochloroacetate was added to the powder and mixed.

A solution of 1500 g of 50% caustic soda solution and 1000 g of methanol was injected and homogenized. The reactor temperature was maintained at 70 ° C. for 3 hours. The reactor temperature was lowered to 25 ° C.

Samples were taken to determine the degree of substitution.

500 g of propylene oxide was injected and reacted at 70 ° C for 3 hours. 1 g of hydrogen peroxide was injected and molecularly cut at the same temperature for 1 hour. After cooling it was neutralized with phosphoric acid.

Comparative Example 4

The manufacturing method of Republic of Korea Patent 312,999.

5000 g of guar gum was added to a 15 L sealed reactor. 1070 g of 70% caustic soda flakes were added thereto, followed by homogeneous stirring. 500 g of propylene oxide was added and reacted at 75 ° C. for 3 hours. Cool to 25 ° C.

The same amount of sodium monochloroacetate solution as in Example was homogeneously mixed and then reacted at 75 ° C. for 3 hours. In the same manner, molecular cleavage and neutralization were performed.

Comparative Example 5

As in Comparative Example 4, sodium monochloroacetate was added as a powder, and the reaction was performed in the same manner.

Test Example

In order to measure the viscosity of the polysaccharides of Examples and Comparative Examples 1 to 5 prepared above, the viscosity of a 10% aqueous solution was measured at 20 rpm 25 ° C with a viscometer from Rheology.

The degree of substitution of carboxymethylation was measured by FOOD CHEMICALS CODEX: Sodium Carboxymethylcellulose, and the degree of hydroxyalkylation was measured by ASTM D2363-79: Hydroxypropylmethylcellulose.

The results are shown in Table 1 below.

Using the polysaccharides prepared in Examples and Comparative Examples 1 to 5 as a forge, cotton fabrics were printed in the following manner.

First, dissolve the polysaccharide at 40000 ~ 60000 cps, then take an appropriate amount (about 70 parts), add 2 parts of sodium bicarbonate, 10 parts of urea, 1 part of reactive dye (Oyoung Industries SUNCION RED P-2B), and 13 parts of water I made a color.

After drying, the steam was dried at 100 ° C. for 5 minutes. After marching, an appropriate amount of detergent was added to water at 90 to 100 ° C., followed by 10 to 15 minutes, followed by cold water. The results of the printing are shown in Table 1 below.

division Viscosity (cps) Appearance ¹ Printing Carboxymethyl Substituted Degree Hydroxy Alkyl Substitution Example 57000 Status Great 0.9 0.16 Comparative Example 1 134000 A lot of lump A disability problem 0.35 0.1 Comparative Example 2 62000 A lot of lumps A disability problem 0.35 0.12 Comparative Example 3 5700 Status A disability problem 0.3 0.08 Comparative Example 4 5000 Status A disability problem 0.35 0.09 Comparative Example 5 21300 Too dry A disability problem 0.2 0.05 Appearance is determined by visual observation to determine the goodness of powder. Substitution degree is 3 when polysaccharide is 100% substituted.

As shown in Table 1, it can be seen that the Example according to the present invention has excellent desorption property because the degree of substitution is higher than that of the comparative example. In addition, when printing using the polysaccharide according to the present invention was confirmed that it can be used for direct printing of cotton fabric using a reactive dye.

As described above, the present invention has a carboxy methyl group and a hydroxy alkyl group in the polysaccharide molecule at the same time to enable a variety of printing operations with one paste.

Claims (4)

A polysaccharide for printing, in which sodium monochloroacetic acid and propylene oxide are added to a polysaccharide, the carboxy methyl group is substituted by 30 to 40%, and the hydroxy alkyl group is substituted by 5 to 15%. The printing polysaccharide according to claim 1, wherein the polysaccharide is selected from corn starch, guar gum and derivatives thereof. In the method for producing a polysaccharide for printing, 1) adding 100 parts by weight of polysaccharides to the reactor, 2) preparing a mixed solution by mixing 27 to 36 parts by weight of a 50% caustic aqueous solution separately from 1 and 20 to 30 parts by weight of methanol, 3) mixing and homogenizing the mixed solution of 2 by spraying it through a micronozzle under high-speed mixing conditions in which the Chopper is equipped with 2000 or more choppers; 4) dissolving 20-30 parts by weight of sodium monochloroacetate in 30-40 parts by weight of water, adding the mixture to the reactor, mixing the mixture, and raising the temperature inside the reactor to 55-60 ° C. to obtain a carboxymethylated polysaccharide, 5) injecting 5-15 parts by weight of propylene oxide to the reactor to hydroxy alkylation reaction at a reactor temperature of 55 ~ 60 ℃, 6) cutting the polysaccharide molecule by adding 0.005 to 0.02 parts by weight of hydrogen peroxide after the reaction Method for producing a polysaccharide for printing, characterized in that consisting of. The method of claim 3, wherein the reactor is equipped with a high speed rotary blade.