KR950004196B1 - Preparation method of carboxy methyl cellulose alkali salts for textile printing - Google Patents

Abstract

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Description

Carboxymethyl Cellulose Alkali Salt for Printing Inhibitor and Manufacturing Method Thereof

The present invention relates to a CMC having excellent physical properties as a printing agent and a manufacturing method thereof.

Conventionally, printing starch, starch gum, guar gum, sodium alginate, carboxymethylated starch (CMS) and carboxymethylcellulose alkali salt (CMC) are generally used, but CMC is most frequently used in terms of function and stable supply. .

CMC is roughly classified into those having a DS of 0.05 to 1.00 and those of 1.30 to 1.80. The CMC of DS 0.05-1.00 is mainly used as an adjuvant when printing the cloth of polyester with a disperse dye. CMCs having a DS of 1.30 to 1.80 are used as printing agents for printing rayon or cotton cloth with reactive dyes, and for printing polyester cloths with disperse dyes.

An important function as a printing agent is that there is little insoluble residue that causes the screen to be clogged during screen printing, transferability from screen to cloth, that is, dyes containing dyes are applied to the cloth, etc. It is excellent in being rinsed out in the form of a screen, etc., and having a sufficient amount of entrained water, and completely washed off when dye is unnecessary after dyeing is applied to a fabric by heating.

It is well known that the transferability of the agent is correlated with the printing activity index (PVI) of the arc (having a viscosity of 80,000 to 100,000 cps in an aqueous solution of 3 to 20% by weight). That is, the CMC of DS 1.30-1.80 is excellent in transferability with larger PVI.

On the other hand, in terms of deodorization, when printing polyester cloth with disperse dyes, DS is 0.05 ~ 00 00 CMC and 1.30 ~ 1.80 CMC, which is excellent, but when dyeing rayon or cotton cloth with reactive dye, DS The higher the CMC, the better the deprotection. This is because the reactive dye reacts with and reacts with the primary hydroxyl group of rayon or cotton as well as insoluble by reacting with the primary hydroxyl group of CMC. Therefore, by increasing the DS, the number of primary hydroxyl groups is reduced and the reactivity with the reactive dye is suppressed to improve the deprotection property.

CMC is produced by reacting NaOH, monochloroacetic acid, sodium monochloroacetic acid or monochloroacetic acid ester with cellulosic raw materials such as linter or pulp. The reaction is carried out in the purchase method of using water as a medium and the solvent method in a hydrous organic solvent, but in recent years, the solvent method is overwhelmingly increasing.

In any of the production methods, a method of producing an alkali cellulose by reacting NaOH with a linter or a pulp to prepare an alkaline cellulose, followed by addition-mixing of monochloroacetic acid, sodium monochloroacetic acid, or monochloroacetic acid ester (Alcel method) and linter Alternatively, a method (monochlor method) in which pulp is impregnated with sodium monochloroacetate, followed by addition-mixing with NaOH, followed by etherification reaction.

Both reactions are carried out in a solid-liquid heterogeneous system. For this reason, it is extremely difficult to convert all the insoluble cellulose raw materials into the water-soluble CMC in water and this is an eternal problem for those skilled in the art. Also in any reaction method, the molar ratio of [NaOH] / [sodium monochloroacetate] in the reaction system immediately before the start of the etherification reaction is common to the prior art.

The CMC produced in these prior arts has a low PVI value, poor transferability, and more rayon due to reactive dyes because the CMC is insoluble, has many residues, is easy to cause clogging of the screen, is a printing problem, and has a heterogeneous substituent distribution. Or when printing the cloth of cotton, there is a problem such as insufficient deodorization.

MEANS TO SOLVE THE PROBLEM The present inventors regard the CMC which has the outstanding physical property as a printing agent, and its manufacturing method.

1) In order to prevent clogging, water-insoluble is very small.

2) Increase the PVI value to improve the transferability.

3) In order to minimize the reactivity with reactive dyes, the distribution of substituents in the molecule and between molecules (hereinafter referred to as DS distribution) should be very uniform.

As a result of intensive studies, 2 liters of a 0.1% by weight aqueous solution of CMC was leaked by screening used for screening printing of 165 mesh (110 ° C). CMC for printing agents having a substitution degree of 1.30 to 1.80 having a specific relationship between the viscosity of 1% by weight aqueous solution of CMC and the printing activity index (PVI) of CMC, after 4 hours of drying). Was found to be excellent as a CMC for printing inhibitors and came to complete the present invention.

That is, in the present invention, when 2 liters of a 0.1% by weight aqueous solution of CMC was leaked into a screen used for screen printing of 165 mesh, the amount of residue of CMC dissolved in the screening phase residue (110 ° C. after 4 hours drying) was dissolved. It is 0.01% by weight or less, and provides the printing agent CMC having a substitution degree of 1.30 to 1.80 in which the viscosity of 1% by weight aqueous solution of CMC and the printing activity index (PVI) of CMC are as follows.

Viscosity Printing Viscosity (PVI) of 1 wt% aqueous solution of CMC

0.60 or more at 10 to 30 cps

0.55 or more at 31 to 50 cps

0.50 or more when 51 to 100 cps

0.45 or more at 101 to 200 cps

0.40 or more at 201 ~ 400cps

0.35 or more at 400 to 600 cps

The viscosity of the 1 weight% aqueous solution of CMC and the printing activity index (PVI) of CMC which are used by this invention are measured by the following method.

* Measurement method of viscosity of 1 wt% aqueous solution of CMC

25 ° C, 60rpm with BL Viscometer

* Measurement of Printing Activity Index (PVI)

Using a rotor No. 7 as a BH viscometer, a concentrated aqueous solution of CMC was prepared so that the viscosity after 10 minutes at 25 ° C. and 1 minute was 80,000-120,000 cps. Next, the viscosity of the rich aqueous solution of CMC was measured at 25 ° C. using a BH viscometer at 25 ° C., and the PVI values were calculated by the following equation.

PVI value = viscosity of 20 rpm / viscosity of 10 rpm

In the printing agent CMC of the present invention, the viscosity of the lwt% aqueous solution and the printing activity index (PVI) of the CMC are in the above relationship, and the CMC in the following relationship is particularly preferable for the printing agent.

Viscosity Printing Viscosity (PVI) of 1 wt% aqueous solution of CMC

0.80 or more at 10 to 30 cps

0.70 or higher at 31 to 50 cps

0.60 or higher at 51 to 100 cps

0.50 or more at 101 to 200 cps

0.45 or more at 201 ~ 400cps

0.40 or more from 400 to 600cps

In addition, the CMC for printing inhibitor of the present invention has a screening amount of residue (110 DEG C, after 4 hours drying) when 2 liters of its 0.1 wt% aqueous solution is leaked into a screen used for screen printing of 165 mesh. It is necessary to be 0.01 wt% or less of the amount of dissolved CMC. If the amount of residue exceeds 0.01% by weight, the screening of the screenin becomes remarkable, inferior in color development, leveling, and printability. Moreover, DS of CMC of this invention is 1.30-1.80 range.

There are three types of DS distributions of CMC: distribution of three hydroxyl groups at the 2nd, 3rd, and 6th positions in the anhydrous glucose unit, intramolecular distribution, and intermolecular distribution. These three types of DS distribution are thought to be closely related to the physical properties of CMC, but the amount of undissolved wastes in which intramolecular and intermolecular distributions are important for practical use, or fluidity and aqueous reactivity with aqueous solutions It seems that it has a big influence on the suppression of the. In general, the smaller the amount of glucose produced by hydrolysis by cellulase, the higher the DS distribution uniformity is. The printing agent CMC of the present invention preferably has a low amount of glucose. The amount of CMC benefit glucose for printing inhibitors of the present invention is about 0.4-1.4 / 1000 AGU.

In addition, the present invention is to prepare a CMC by operating an etherification agent in the presence of alkali in the cellulosic material in the water-based organic solvent system, the edering agent is added to the initial amount, and the alkali is represented by the following formula: The molar ratio of / [etherification agent] is adjusted so that the molar ratio is 0.20 to 0.80, the etherification reaction is started in the system of excess etherification agent, and then the alkali is added separately to add the molar ratio of [alkali] / [etherification agent] in the final step. It is to provide a method for producing the printing agent CMC characterized in that the etherification reaction to be at least 1.00.

Molar ratio of [alkali] / [etherification agent] = (A-B) / C

A: [the total moles of alkali injected up to that time in each step]

B: [moles of alkali neutralized with etherification agent]

C: [moles of ether etheration added]

MEANS TO SOLVE THE PROBLEM The present inventors examined from the point of view that it is essential to improve reaction uniformity in order to simultaneously improve the above-mentioned three subjects. As a result, the manufacturing method of CMC of this invention was reached as mentioned above.

In order to uniformize the reaction, first, it is important to sufficiently destroy the crystal structure of the cellulose with alkali such as NaOH, and the alkali cellulose is prepared by reacting the alkali in the pulverized pulp in an aqueous organic solvent. At this time, the amount of alkali was used below the stoichiometric amount, and the study was performed to facilitate the diffusion of the etherification agent into the alkali cellulose fiber in the next step. Next, an etherification agent is added at low temperature, and it fully stirs and mixes. After sufficient stirring and mixing, it is essential for the uniformity of the reaction to set the molar ratio of [alkali] / [etherification agent] to 0.20 to 0.80 in the system.

Next, the temperature is raised to 40 ° C or higher to perform an etherification reaction. When the reaction is almost finished, the remaining alkali is added in whole or several times to continue the reaction. After the last alkali is added, the molar ratio of ([the total amount of alkali added-alkalinized with etherification agent]) / [incorporated etherification agent] in the system is made to be 1.00 or more, and the etherification reaction is finally performed. The excess alkali is then neutralized with acetic acid or the like. Thereafter, the tablets are dried and pulverized according to a conventional method to obtain the CMC of the present invention.

By producing the CMC according to the above method, the CMC of the present invention that satisfies all the necessary functions as a printing agent is obtained.

Furthermore, isopropyl alcohol, ethyl alcohol, n-propyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, acetone, ethyl alcohol / benzene mixture, ethyl alcohol / toluene mixture in the production method of the present invention. Etc. can be used. Moreover, esters, such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, of monochloroacetic acid, sodium monochloroacetic acid, and monochloroacetic acid can also be used as an etherification agent, As alkali, sodium hydroxide, hydroxide Potassium and the like are used.

(Example)

In the following Examples, the present invention will be described, but the present invention is not limited to these Examples. In the examples, parts represent parts by weight and% denotes by weight.

(Example 1)

996 parts of isopropyl alcohol (hereinafter abbreviated as IPA) were introduced into a 5-liter reactor with two-axis stirring blades, and 136.8 parts of NaOH (98% purity) was dissolved in 163.6 parts of pure water, and the mixture was charged at 20 to 30 ° C. After cooling, 200 parts of powdered cellulose (purity 95%) was added and stirred and mixed at 20 to 30 ° C. for 60 minutes to prepare alkaline cellulose.

Next, 215.5 parts (purity 98%) of monochloroacetic acid is melt | dissolved in IPA 215.5 parts, and it adds in small amounts at 10-20 degreeC for 60 minutes, cooling. After addition, the mixture is further stirred at 10 to 20 ° C. for 30 minutes. Thereafter, the temperature was raised to 60 ° C. for about 10 minutes to effect etherification for 60 minutes. Next, 45.6 parts of NaOH were dissolved in 30.4 parts of pure water, and the mixture was stirred and mixed at 60 to 70 ° C. for 15 minutes, and then heated to 70 ° C. for an etherification reaction for 90 minutes.

Thereafter, some remaining NaOH is neutralized with acetic acid.

After completion of the reaction, the reaction mixture is removed from the reactor and centrifuged to remove the IPA of the reaction solvent. Then, washed three times with 4000 parts of 75% beta alcohol solution to remove the by-product salt, sodium glycolate, and sodium acetate, and the purified CMC was dried at 80 to 100 ° C. with a rolling machine for about 6 hours. Got.

The result of analyzing and evaluating this CMC was as follows.

DS: 1.35

1% aqueous solution: 152 cps

Glucose production amount: 1.4 pcs / 1000 AGU

165 Mesh screen lift residue: 0.006%

Printing Activity Index (PVI): 0.57

(Example 2)

Into a 5-liter reactor with two-axis stirring blades, IPA 032 parts was added, and 180.8 parts (purity 98%) of NaOH was dissolved in 158.0 parts of pure water, and then cooled to 20 to 30 ° C, followed by 200 parts of powdered cellulose (purity). 95%) is added and stirred and mixed at 20 to 30 ° C for 60 minutes to prepare alkali cellulose.

Next, 277.5 parts (purity 98%) of monochloroacetic acid is melt | dissolved in IPA 277.5 parts, and it adds in small amounts for 60 minutes at 10-20 degreeC, cooling, and after addition, stirring and mixing at 10-20 degreeC for further 30 minutes. Thereafter, the mixture was heated at 60 ° C. for about 10 minutes, and then subjected to etherification reaction. Then, 63.5 parts of NaOH were dissolved in 42.3 parts of pure water, and then mixed and stirred at 60-70 ° C. for 15 minutes, and then heated at 70 ° C. for 90 minutes. Reaction. Thereafter, slightly remaining NaOH is neutralized with acetic acid.

After completion of the reaction, the reaction mixture is removed from the reactor and centrifuged to remove the IPA of the reaction solvent. Next, the resultant was washed three times with 4000 parts of 75% aqueous methyl alcohol solution to remove by-product salt, sodium glycolate and sodium acetate, and the purified CMC was dried at 80 to 100 ° C. for about 6 hours using a dryer to obtain a CMC of the present invention.

The result of analyzing and evaluating this CMC was as follows.

DS: 1.54

1% aqueous solution viscosity: 74cps

Glucose production amount: 0.8 / 1000 AGU

165 mesh screen lift residue: 0.002%

Printing Activity Index (PVI): 0.66

(Example 3)

IPA 1124 was charged into a 5-liter reactor with two-axis stirring blades, and 163.2 parts (purity 98%) of NaOH was dissolved in 126.0 parts of pure water, and then cooled to 20 to 30 ° C, followed by 200 parts of powdered cellulose (purity). 95%) is added and stirred and mixed at 20 to 30 ° C for 60 minutes to prepare alkali cellulose. Next, 286.2 parts of monochloroacetic acid (purity 98%) is dissolved in IPA 286.2 parts and added for 60 minutes in small portions at 10 to 20 ° C while cooling. After addition, the mixture is further stirred and stirred at 10 to 20 ° C for 30 minutes. Thereafter, the temperature was raised to 60 ° C. in about 10 minutes, followed by an etherification reaction for 60 minutes. Then, 42.0 parts of NaOH were dissolved in 28.0 parts of pure water, and then, an etherification reaction was carried out at 60 ° C. for 30 minutes. Further, 42.0 parts of NaOH were dissolved in 28.0 minutes of pure water. And the mixture was stirred for 15 minutes at 60 to 70 ° C., and then heated at 70 ° C. to carry out an etherification reaction between 90 parts. Then washed three times with 4000 parts of 75% aqueous methyl alcohol solution to remove the by-product salt, sodium glycolate and sodium acetate, and the purified CMC was dried in a drier for about 6 hours at 80 to 100 ℃ to obtain a CMC of the present invention .

The result of analyzing and evaluating this CMC was as follows.

DS: 1.75

1% aqueous solution viscosity: 46cps

Glucose production amount: 0.4 pcs / 1000AGU

165 mesh screen lift residue: 0.002%

Printing Activity Index (PVI): 0.74

(Example 4)

Into a 5-liter reactor with two-axis stirring blades, IPA 032 parts was added, and 180.8 parts (purity 98%) of NaOH was dissolved in 158.0 parts of pure water, and then cooled to 20 to 30 ° C, followed by 200 parts of powdered cellulose (purity 95). %) Is added and stirred and mixed at 20 to 30 ° C for 60 minutes to prepare alkali cellulose.

Next, 277.5 parts of monochloroacetic acid (purity 98%) is dissolved in IPA 277.5 parts and added for 60 minutes in small portions at 10 to 20 ° C while cooling. After addition, the mixture is stirred and mixed at 10 to 20 ° C. for 30 minutes. Thereafter, the temperature was raised to 60 ° C. in about 10 minutes, followed by an etherification reaction for 60 minutes. Next, 63.5 parts of NaOH was dissolved in 42.3 parts of pure water, and the mixture was stirred and mixed at 60 to 70 ° C. for 15 minutes, and then heated at 70 ° C. to etherification for 90 minutes. Then, the mixture was cooled to 45 ° C, and 20 ml of hydrogen peroxide (30% concentration) was added thereto, followed by stirring and mixing for 30 minutes.

Then washed three times with 4000 parts of 75% aqueous methyl alcohol solution to remove the by-product salt, sodium glycolate and sodium acetate, and the purified CMC was dried at 80 to 100 ° C. for about 6 hours to obtain a CMC of the present invention. .

The result of analyzing and evaluating this CMC was as follows.

DS: 1.53

1% aqueous solution viscosity: 22cps

Glucose production amount: 0.7 / 1000AGU

165 mesh screen lift residue: 0.002%

Printing Activity Index (PVI): 0.83

(Comparative Example 1)

969 parts of IPA were introduced into a 5-liter reactor with two-axis stirring blades, and 211.5 parts of NaOH (purity 98%) was dissolved in 194.0 parts of pure water, and then cooled to 20 to 30 ° C, followed by 200 parts of powdered cellulose (purity 95). (C) is added and stirred and mixed at 20 to 30C for 60 minutes to prepare alkali cellulose.

Next, 242.5 parts of monochloroacetic acid (purity 98%) is melt | dissolved in IPA 242.5 parts, and it adds for 60 minutes by small amounts at 10-20 degreeC, cooling. After addition, the mixture is further stirred at 10 to 20 ° C. for 30 minutes. Thereafter, the temperature was raised to 70 ° C. for about 15 minutes, followed by etherification for 90 minutes. Next, 75% methyl alcohol was washed three times with 4000 parts of an aqueous solution to remove by-product salt, sodium glycolate, and sodium acetate, and the purified CMC was dried at 80 to 100 ° C. for about 6 hours using a dryer to obtain a comparative CMC.

The result of analyzing and evaluating this CMC was as follows.

DS: 1.35

1% aqueous solution viscosity: 148cps

Glucose production amount: 6.2 pcs / 1000 AGU

· 165 mesh screen impression residue: 0.146%

Printing Activity Index (PVI): 0.48

(Comparative Example 2)

Into a 5-liter reactor with two-axis stirring blades, IPA 1009 parts were added, and Na7.2 257.2 parts (purity 98%) was dissolved in 200.3 parts of pure water, and then cooled to 20 to 30 ° C., followed by 200 parts of powdered cellulose (purity 95). %) Is added and stirred and mixed at 20 to 30 ° C for 60 minutes to prepare alkali cellulose.

Next, 300.8 parts of monochloroacetic acid (purity 98%) is dissolved in 300.8 parts of IPA and added in small portions at 10 to 20 ° C. for 60 minutes while cooling. After addition, the mixture is further stirred at 10 to 20 ° C. for 30 minutes. Thereafter, the mixture was heated to 70 ° C. for about 15 minutes, followed by etherification for 90 minutes. The resultant was washed three times with 4000 parts of 75% aqueous methyl alcohol solution to remove the by-product salt, sodium glycolate, and sodium acetate, and then purified CMC was prepared. It dried at 80-100 degreeC for about 6 hours, and obtained the comparative CMC.

The result of analyzing and evaluating this CMC was as follows.

DS: 1.54

1% aqueous solution viscosity: 72cps

Glucose production amount: 4.4 / 1000 AGU

165 Mesh screen lift residue: 0.082%

Printing Activity Index (PVI): 0.44

(Comparative Example 3)

2138 parts of IPA were introduced into a 5-liter reactor with two-axis stirring blades, 400.1 parts of NaOH (98% purity) was dissolved in 230.0 parts of pure water, and then cooled, and cooled to 20 to 30 ° C, followed by 200 parts of powdered cellulose (purity). 95%) is added and stirred and mixed at 20 to 30 ° C for 60 minutes to prepare alkali cellulose.

Next, 472.6 parts of monochloroacetic acid (purity 98%) is dissolved in 472.6 parts of IPA and added thereto in small portions at 10 to 20 ° C. for 60 minutes while cooling. After addition, the mixture is further stirred at 10 to 20 ° C. for 30 minutes. Thereafter, the temperature is raised to 70 ° C. for about 15 minutes and etherification is performed for 90 minutes.

Next, the resultant was washed four times with 4000 parts of 75% aqueous methyl alcohol solution to remove by-product salt, sodium glycolate and sodium acetate, and the purified CMC was dried at 80 to 100 ° C. for about 6 hours in a dryer to obtain a comparative CMC.

The result of analyzing and evaluating this CMC was as follows.

DS: 1.74

1% aqueous solution viscosity: 48cps

Glucose production amount: 3.2 / 1000AGU

165 Mesh screen lift residue: 0.038%

Printing Activity Index (PVI): 0.52

(Comparative Example 4)

The results of analyzing and evaluating the commercially available printing inhibitor CMC were as follows.

DS: 1.53

1% aqueous solution viscosity: 176cps

Glucose production amount: 4.3 / 1000AGU

165 Mesh screen lift residue: 0.044%

Printing Activity Index (PVI): 0.48

(Examples 5-8 and Comparative Examples 5-8)

Using the CMC of the present invention of Examples 1 to 4, the CMC of Comparative Examples 1 to 3, and the commercial product of Comparative Example 4, stamping was performed under the conditions shown below, and a printability evaluation was performed, and the results are shown in Table 2. .

(1) Amount of glucose produced by hydrolysis by cellulase (uniformity evaluation method of DS distribution)

In the present invention, the uniformity of the DS distribution is reported by MGWirick et al., Which is said to be hydrolyzed by cellulase which is a hydrolytic enzyme of cellulose when three or more unreacted anhydroglucose units are linked in the molecule of CMC. Polymer Science: Part A-1, vo1.6, 1965), 5 mg / (CMC lg) of cellulase (Amano Seiyaku Co., Ltd. Cellulase AP) was added to an aqueous solution of 1% CMC to 25 ° C for 140 hours. After digestion, glucose was analyzed by the glucose oxytase method. The smaller the amount of produced glucose, the higher the uniformity of the DS distribution.

Therefore, in the present invention, the DS distribution is an intramolecular distribution and an intramolecular distribution. Furthermore, the glucose production amount was expressed as the number (1000 pieces / 1000 AGU) per 1000 anhydroglucose units of CMC.

(2) Evaluation method of printability

① The test process and conditions are as follows.

Assisted preparation → Assisted measuring of physical properties → Coloring aid → Inner [Use screen: 160 mesh (plain), Fabric: Rayon → Drying (preliminary drying; 100 ℃ × l minutes) → Heating (100 ℃ × 10 minutes) → Washing [80 ° C x 10 min, mayinol SR-30 (non-ionic surfactant) 2 g / L] → finish → evaluation

② color code prescription

Table 1 shows the prescription of color code used for the evaluation of printability.

TABLE 1

* ¹ ; Diamira Black B (Reactive Furnace)

* ² ; Sodium meta-Nitrobenzene Sulfomate

* ³ ; The amount of arc arc X is shown in Table 2.

* ⁴ ; The quantity Y of water was made into Y = 100- (6 + 1 + 5 + 2 + X).

③ printing sample cloth

In the test conditions described above, the same color code was used to perform the inner printing 10 times without washing the screen, and the first and 10th rough fabrics were dried, heated and finished.

(Evaluation item)

Color development: The color density of the fabrics of the first and tenth printing days was visually determined and evaluated in ten steps. If this evaluation is less than 5, it cannot be used as a printing inhibitor.

-Bacteriality: The number of undyed white small spots of the cloth which printed successively by the 10th squeegee was visually judged, and the evaluation criteria similar to the above evaluated.

Deodorization: The fabric that was printed by the first squeegee was rubbed with a finger, and judged by its touch, and evaluated by the same evaluation criteria as described above. In other words, if you do not fall off and wash the stiffness.

The above results are shown in Table 2.

TABLE 2

The evaluation results shown in Table 2 are summarized below.

1) color development

The printing agent CMC of the present invention exhibits high color development because of excellent transferability since the PVI value of the screen-in-favoring agent is high, but shows low color development in the comparative example. In the case of 10 consecutive prints, the CMCs of Comparative Examples 1 to 3 having a large amount of residues of 165 mesh screens and Comparative Examples 5 to 8 using commercially available products are significantly worse due to clogging of screens.

2) Leveling

Although the CMCs of Comparative Examples 1 to 3 and many commercially available products having a large amount of residue on the screen of the stains are recognized, many small white spots which are not dyed due to screening clogging are recognized, but the CMC for printing inhibitor of the present invention In Examples 4 to 7, the small spots were hardly recognized and the leveling property was excellent.

3) Defrostability

Although both the CMC for printing inhibitors and the CMCs of Examples 1 to 3 of the present inventions of Examples 1 to 4 tended to have better desorption property as the DS is increased, the uniformity of DS distribution is high, that is, the amount of glucose produced by enzymatic degradation Examples 5 to 8 using few of Examples 1 to 4 are particularly excellent.

Claims (3)

The amount of residue on screening (110 ° C, 4 hours drying) when 2 liters of 0.1% by weight aqueous solution of carboxymethyl cellulose alkali salt (hereinafter abbreviated as CMC) was leaked with screening used for screening printing of 165 mesh. C) for printing inhibitors having a degree of substitution of 1.30 to 1.80, in which the viscosity of the dissolved CMC is 0.01% by weight or less, the viscosity of the aqueous solution of 1% by weight of CMC and the CMC blade printing activity index (PVI) are as follows. . Viscosity Printing Viscosity (PVI) of 1 wt% aqueous solution of CMC 0.60 or more when 10 to 30 cps 0.55 or more at 31 to 50 cps 0.50 or more when 51 to 100 cps 0.451 or higher at 101 to 200 cps 0.40 or more at 201 ~ 400cps 0.35 or more at 400 to 600 cps The printing agent CMC according to claim 1, wherein the viscosity of the 1 wt% aqueous solution of CMC and the printing activity index (PVI) of the CMC are as follows. Viscosity Printing Viscosity (PVI) of 1 wt% aqueous solution of CMC 0.80 or more at 10 to 30 cps 0.70 or higher at 31 to 50 cps 0.60 or more when 51 to 100 cps 0.50 or more at 101 to 200 cps 0.45 or higher at 201 ~ 400cps 0.40 or higher at 400 to 600 cps In the method for producing CMC by applying an etherification agent to the cellulosic raw material in the presence of alkali in a water-containing organic solvent system, the etherification agent initially adds the whole amount, and the alkali is represented by [alkali] / [etherification system] ] Is added so as to adjust the molar ratio of 0.20 to 0.80, and the etherification reaction is started in the system of excess etherification crab, after which the alkali is added separately, and the molar ratio of [alkali] / [etherification agent] in the final step is 1.00 or more. The method for producing CMC according to claim 1, wherein the etherification reaction is carried out as possible. Molar ratio of [alkali] / [etherification agent] = (A-B) / C A: [the total moles of alkali added up to that time in each step] B: [moles of alkali neutralized with etherification agent] C: [moles of ether etheration added]