JPH09136991A - Alkali salt of carboxymethylcellulose - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an alkali salt of carboxymethylcellulose which can exhibit an excellent textile printing performance involving color development and printing paste removal even with a low degree of ether substitution, and is endowed with an improved aq. soln. forming performance by incorporating thereinto a specific component. SOLUTION: This alkali salt of carboxymethylcellulose(CMC) contains at least 4wt.% carboxymethyletherification product of a polysaccharide having pentose constituent units. Examples of the alkali salt include sodium salt, potassium salt, and ammonium salt. Specific examples of the polypentasaccharide include arabinan and xylan. Accordingly, a carboxymethyletherification product of a polyhexasaccharide and the unreacted polysaccharide account for smaller than 96wt.% of this CMC. This CMC is obtd. by selecting pulp contg. at least 4wt.% in total of arabinan and xylan as polypentasaccharides, and carboxymethyletherifying the pulp.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a printing paste, an additive for liquid seasoning, petroleum oil, which is one of the performances of an aqueous solution of carboxymethylcellulose alkali salt (hereinafter referred to as “CMC”) and has a small thixotropic property and a small structural viscosity. The present invention relates to CMC suitable for use as a mud preparation for boring, etc., especially as a printing paste.

[0002]

2. Description of the Related Art CMC, which is used as a printing paste for rayon and cotton, is required to have an effect of effectively using a dye to enhance color developability and a performance of excellent desizing in a desizing process after dyeing. To be done. For this reason, conventionally, as a printing paste, the manufacturing cost is higher than that of a commonly used CMC having an ether substitution degree of CMC (hereinafter referred to as “DS”) of 1.3 or more, but a CDS having a high DS is used. Has been used.

[0003]

However, in such a conventional CMC for a printing paste, since a dissolving pulp having a high-purity cellulose composition is used as a raw material to produce the CMC, the CMC is made of rayon or cotton. When applied to textile printing pastes, the sixth residue of glucose residue in the structure of CMC
When the hydroxyl group bonded to the carbon at the position is not etherified, the utilization efficiency of the dye at the time of dyeing tends to decrease, and it is necessary to use more dye. Therefore, as a method for carboxymethyl etherification (hereinafter referred to as "CMization") of more hydroxyl groups bonded to the 6th carbon of a glucose residue, a means for increasing DS has been adopted.

In dyeing applied to a printing paste, for example, when dyeing cotton, the dye is a glucose residue, which is the minimum unit that constitutes cotton, and a hydroxyl group bonded to the 6th carbon of this glucose residue. It is said that the dye reacts. For this reason, it is said that the CMC used in the printing paste will react with the dye in the same manner as cotton and deteriorate the use efficiency of the dye unless the hydroxyl group bonded to the 6th carbon of the glucose residue is converted to CM. ing. Therefore, as the CMC used for the printing paste for cotton, CMC having a DS of 1.3 or higher, preferably 1.4 or higher has been used.

At present, sodium alginate, which is used as a printing paste for cotton, does not have a hydroxyl group bonded to the carbon at the 6th position, so that the dye is used efficiently and is often used. When CMC is used in place of this sodium alginate, the DS of this CMC is 2.0 to 2.8, and a high DS product in which the hydroxyl group bonded to the 6th carbon is more CM-modified is used. The reality is that

However, in the method for producing a high DS CMC, for example, as shown in Japanese Examined Patent Publication No. 60-42242, the effective utilization rate of the etherifying agent increases as the DS increases, no matter what method is adopted. Was extremely worse than that of the low DS product, and the cost was high.

The present invention has been made in view of the above circumstances, and has an improved aqueous solution performance that exhibits excellent printing performance such as color developability and desizing property even with a low DS. The purpose is to provide CMC.

[0008]

In order to achieve the above object, the CMC of the present invention is configured to contain the following (A) in an amount of 4% by weight or more. (A) A CM product of a polysaccharide containing pentose sugar as a constituent unit.

The present inventors pay attention to the conventional problems,
The research was repeated in order to obtain a CMC excellent in the above performance even with a low DS. Then, focusing on the CM compound of the polysaccharide excluding the glucan contained in the CMC, the research was repeated focusing on the correlation between the composition of the CM compound of the polysaccharide and the printing performance. As a result, among the CM products of the polysaccharides contained in the CMC, the content of the CM product of the polysaccharide having a pentose as a constituent unit (hereinafter referred to as “pentose polysaccharide”) is 4% by weight of the whole CMC. The present inventors have found that the use of a CMC having a C% of at least 100% (hereinafter abbreviated as “%”) provides extremely good results as compared with a conventional CMC, and has reached the present invention. Generally, from the pulp used as a raw material for CMC, examples of the five-carbon polysaccharide include arabinan and xylan.

[0010]

Next, an embodiment of the present invention will be described.

The CMC of the present invention contains CM compounds of pentacarbon polysaccharides in a total amount of 4% or more of the total amount of CMC. Examples of the alkali salt include sodium salt, potassium salt and ammonium salt. . Specific examples of the 5-carbon polysaccharide include arabinan and xylan. Therefore, in the CMC of the present invention, the remaining less than 96% excluding the CM compound of the above-mentioned five-carbon polysaccharide is the CM compound of the six-carbon polysaccharide, for example, each of the CM compounds of glucan, mannan, and galactan, and , Becomes unreacted polysaccharide. More preferably, the total content of CM compounds of the above-mentioned five-carbon polysaccharide is 6% or more of the total CMC, though it depends on the kind of the raw pulp containing the five-carbon polysaccharide. That is, when the content is less than 4%, the effect of improving the printing performance and the like in low DS cannot be obtained.

Conventionally, as linter pulp or dissolving pulp used as a raw material for CMC, pulp having a pentan polysaccharide content of less than 4% and high glucan purity has been used. This is because when the content of the 5-carbon polysaccharide increases, the amount of insoluble components increases and the water solubility deteriorates. Usually, CMC is produced by converting pulp containing the most glucan, which is a polysaccharide, into CM. And, since the pulp of CMC raw material also contains hexacarbon polysaccharide and pentacarbon polysaccharide excluding glucan, CM
At the time of C production, these polysaccharides are also converted into CM. The present inventors usually focus on chemical pulp and papermaking pulp that are not used as CMC raw materials for the above reasons, and mainly select the content of pentose polysaccharides to select the type of pulp. However, a CM compound having a content of each of the hexacarbon polysaccharide and the pentacarbon polysaccharide different from the conventional one was obtained.

The CMC of the present invention is obtained by selecting, from among various raw material pulps, pulp containing 4% or more of the total amount of five-carbon polysaccharide arabinan and xylan, and converting the pulp into CM. is there. The method for converting the CM is not particularly limited and is a conventionally known method (for example, Japanese Patent Publication No. 43-23000 and Japanese Patent Publication No. 46-19).
4 and Japanese Patent Publication No. 46-2112). And, as a specific example of the raw material pulp,
JACKSON GULFBRIT (manufactured by BOISE CASCADE CORP, content of pentose polysaccharides 22.26%), ASTRCEL (FEDERAL PAPER BO
Made by ARD CO. INC, 5-carbon polysaccharide content 21.21%), CA
RIBOO (CARIBOO PULP. & PAPER, pentacarbon polysaccharide content 9.27%), ELKPRIME (FRECHER CHALLENG, pentacarbon polysaccharide content 5.13%), TEMBEST (TEMBEC,
Pentacarbon polysaccharide content 5.14%) and the like.

Next, examples will be described together with comparative examples.

[0015]

[Examples 1 to 3] In a one-step reaction, 1104 parts by weight of isopropyl alcohol (IPA) (hereinafter abbreviated as "part"), 96 parts of water, and a predetermined amount of solid NaOH were added to a separable flask, and after stirring and dissolving, the inside of the flask was stirred. The liquid temperature was cooled to 20 to 30 ° C. while purging with nitrogen. Then, 60 parts of finely pulverized pulp shown in Table 1 was charged and alkali cellulose was formed at 30 ° C. for 60 minutes. Then, a predetermined amount of monochloroacetic acid was added as a solution (50% monochloroacetic acid solution) dissolved in the same amount of IPA, and after homogenization, the temperature was raised to 78 ° C.
The reaction was carried out at 8 ° C for 60 minutes. Then, while cooling, excess NaOH was neutralized with acetic acid, the reaction solvent was drained, washed with water-containing methanol several times, dried and ground.

The two-step reaction is the same as the above-mentioned one-step reaction.
After reacting for 60 minutes at ℃, cooled to 30 ℃, solid N
Then, aOH was added and the mixture was accelerated at 30 ° C. for 30 minutes. Subsequently, a 50% monochloroacetic acid solution was added dropwise at the same temperature, and the temperature was raised to 78 ° C. Again, the second reaction was carried out at 78 ° C. for 60 minutes. After that, the same procedure as the one-step reaction was performed.

The physical properties (DS, 2% viscosity, 1% transparency) of each CMC obtained were measured and calculated. In addition, the composition ratio of the CM-modified polysaccharide in each CMC was measured. The results are shown in Table 1 below.

[Measurement of DS] About 1.0 g of a sample (CMC) to be measured, which was vacuum dried at 75 ° C. for 3 hours, was precisely weighed and ashed in a crucible. Then, after cooling this, the ash was eluted in warm water, and 50-80 ml of N / 10-sulfuric acid was added to acidify the mixture and the mixture was boiled and cooled. Then, the excess acid is N / 1
Back titration with 0-sodium hydroxide was performed to determine the degree of etherification from the amount of sulfuric acid consumed for alkali neutralization in the ash.

[2% Viscosity] Prepare a 2% aqueous solution at 25 ° C.
Was measured using a B-type viscometer.

[1% transparency] Length 700 mm x inner diameter 25
A cylindrical glass made of optical glass having a thickness of 2 mm and a bottom thickness of 2 mm was filled with an aqueous solution having a CMC concentration of 1%. Cylindrical glass having different inner diameters (15 mm inner diameter) was inserted into this. And, on the bottom of the outer cylindrical glass, spread a black parallel line with a width of 1 mm and an interval of 1 mm,
The inner cylindrical glass was moved up and down. Then, the height (cm) of the liquid was measured when the black parallel lines at the bottom became indistinguishable visually, and the value was taken as the transparency.

Further, the composition ratio of the CM-modified polysaccharide in each CMC and the composition ratio of the pulp used in each example were measured as follows. That is, pulp or CMC to be measured is hydrolyzed with sulfuric acid to obtain monosaccharides and CM.
After conversion into monosaccharides, trifluoroacetic acid was added and reacted. The reaction solution was further reduced with sodium borohydride, and then N. O. Bis (trimethylsilyl)
Acetamide (BSA) and trimethylchlorosilane (TMCS) were used for silylation reaction, and then inositol was added as an internal standard, followed by gas chromatographic analysis to analyze the composition of each polysaccharide (CM in CMC).
The composition ratio of the modified polysaccharide and the composition ratio of the raw pulp) were quantified.

[0022]

[Table 1]

[0023]

Comparative Examples 1 to 3 The type of pulp used in the above examples was replaced with the pulp shown in Table 2 below. And nitrogen substitution was not performed. CMC was obtained in the same manner as in the example except for these.

The physical properties (DS, 2% viscosity, 1% transparency) of each CMC thus obtained were measured and calculated in the same manner as in the above examples. Further, the composition ratio of the CM-modified polysaccharide in each CMC and the composition ratio of the polysaccharide in the raw material pulp were quantified and measured by the same method as described above. The results are also shown in Table 2 below.

[0025]

[Table 2]

Using each of the CMCs thus obtained, an aqueous solution having a viscosity of 10,000 mPa · s was prepared and subjected to the dyeing test (coloring property, de-gluing property, sharpness, coating amount of color glue) shown below. I served.

[Dyeing Test] As a prescription for the aqueous solution of the color paste having the viscosity of 10,000 mPa · s, regarding the desizing property, the sharpness, and the coating amount, 15 parts of urea, MNBS (methyl nitro benzene sodium sulfonate: 2 parts reduction agent, 8 reactive dyes
Parts, 14 parts of water, 1 part of baking soda, and 60 parts of an aqueous solution in which CMC is dissolved at a high concentration, and the viscosity is 10,000 ± 50.
An aqueous solution of color paste of 0 mPa · s was prepared. Regarding the color developability, a color paste aqueous solution was prepared in the same manner as above except that the reactive dye was changed to 2 parts and water to 20 parts. Next, a rayon cloth was printed and a dyeing test was conducted. With respect to the test cloth, the color developability, de-pasting property, sharpness, and amount of color paste applied were determined, and the suitability of the printing paste was evaluated. The evaluation method was performed by the method shown below, and the evaluation results are shown in Table 3 below. The CMC used for the blank was a commercial printing paste (DS1.4, 2% viscosity 2500 mPa · s) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

(1) Color developability The colorimetric property was measured at 1001 ZP using a colorimetric color difference meter (manufactured by Nippon Denshoku Co., Ltd.). As a result, a numerical value lower than the blank was indicated as x, a value equivalent to the blank was indicated as Δ, and a value higher than the blank was indicated as o.

(2) Desizing property In the handling test, those softer than the blank were evaluated as ○,
△ is equivalent to the blank, × is harder than the blank
Displayed as

(3) Sharpness The portion dyed in a thin linear shape was visually judged. Then, the one in which the linear portion is not broken as compared with the blank is indicated as ◯, the one equivalent to the blank is indicated as Δ, and the one in which the linear portion is more broken as compared with the blank is indicated as ×.

(4) Amount of color glue applied: The amount larger than the blank was indicated as ◯, the equivalent to the blank was indicated as Δ, and the amount smaller than the blank was indicated as x.

[0032]

[Table 3]

From the results of Table 3 above, it is understood that the comprehensive evaluation of the dyeing test of the example product is superior to that of the comparative product, and the example product is useful as a printing paste agent. That is, Example 1 and Comparative Examples 1 and 2 having substantially the same DS
When compared with each of Comparative Example 2 and Example 3 and Comparative Example 3, the dyeing test results of Examples 1, 2, and 3 are obviously excellent, and the printing performance is excellent while having a low DS. I know there is.

[0034]

EFFECTS OF THE INVENTION As described above, the CMC of the present invention contains 4% or more of a CM compound of a 5-carbon polysaccharide. For this reason, conventionally, satisfactory physical properties in printing performance could not be obtained without using a high DS CMC. However, the CMC of the present invention, even with a low DS, has excellent coloring properties and de-pasting properties. C with an aqueous solution capable of exhibiting excellent printing performance
MC. Therefore, the CMC of the present invention is most suitable as a printing paste, especially as a printing paste, an additive for liquid seasoning, a mud-preparing agent for petroleum boring, and the like in view of its aqueous solution characteristics.

Claims (2)

[Claims] 1. An alkali salt of carboxymethyl cellulose, which contains 4% by weight or more of the following (A). (A) A carboxymethyl ether compound of a polysaccharide having pentose as a constituent unit. 2. The carboxymethyl cellulose alkali salt according to claim 1, wherein the (A) is at least one of an arabinan carboxymethyl ether compound and a xylan carboxymethyl ether compound.