JPS58197383A - Printing size for reactive dye and production thereof - 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 provides a printing paste for reactive dyes containing carboxymethyl cellulose ether alkali salt (hereinafter abbreviated as CMC).
and its manufacturing method KpA.

Demand for CMC as a printing paste has increased in recent years.

However, it is almost impossible to put it into practical use due to poor desizing properties in printing with reactive dyes, and even today, sodium alginate is almost the only printing paste used for reactive dyes.

The present invention was completed by conducting research on CMC that has excellent desizing properties when used as a printing paste for reactive dyeing and pasting, and a manufacturing method for efficiently producing the CMC.

Currently, the CMC generally produced has a higher degree of substitution (
The DS (hereinafter abbreviated as DS) is at most 1.6, usually 1.0 or less, and when it is used as a sizing agent for printing with reactive dyes, its desizing property is good.

Although it has been suggested that desizing properties can be improved by increasing the DS of CMC, no attempt has been made to manufacture CMC with a DSI of 8 or higher because it is difficult to manufacture.

However, the inventors of the present invention have made efficient production possible by the method described later, and have found that a product comparable to that of sodium alginate, which was previously unattainable, can be obtained when a desizing property test is conducted.

CMC is produced by applying an etherification agent to a cellulosic raw material in the presence of an alkali, and monochloroacetic acid or its alkali salt has been used as the alkali and sodium hydroxide as the etherification agent. It is well known that

CMC manufacturing methods are broadly divided into three methods: the aqueous method, which uses an aqueous medium as the reaction medium, and the solvent method, which uses a Nanki solvent. Compared to the aqueous method, the solvent method uses a small amount of alkali The etherification reaction can be achieved in a relatively short time, the effective utilization rate of the etherification agent is high, only a small amount of the etherification agent can be used, and the quality of C.
Since MC can be obtained, it has been put into practical use industrially.

In the production of CMC using this solvent method, cellulose is first treated with sodium hydroxide in a water-containing organic solvent to prepare alkaline cellulose, and then monochloro-F acid is added to carry out the etherification reaction. Generally adopted, after adding sodium monochloro 1+) acid to cellulose and impregnating it in a water-containing organic solvent,
A method of carrying out the etherification reaction by adding sodium hydroxide (Japanese Patent Publication No. 46-2112) is also possible. However, conventionally, in any reaction, the molar ratio of [alkali] in the system to the number of moles of the charged etherifying agent during the etherification reaction is 1.0 or more, and is usually maintained at about 1.10. Regarding this molar ratio, Mr. Hayayo et al.
．． aO is reported as -d appropriate ratio (Tokyo Industrial Research Institute Report, No. 55, No. 6, 1960) This is shown by the +11 formula in the lower i pi when the molar ratio becomes smaller than 1.80. This is because side reactions of sodium monochloroacetate such as When the alkali in the reaction system is consumed, glycolic acid is produced by a side reaction as shown in equation (2) in Section 1, and the reaction system becomes acidic, attacking the carboxyl/al group of CMC and forming a monomer. This is thought to be because the solubility of the produced CM and C is significantly reduced by making the part into an acid form.

(1) Formula Cl7CH,,COONal-Na
0H-cH,2(OH)COONa+NaCe(
2) Formula Ct+CH2COONa+H2O-CH2(O
H) COOH4-NaCe For this reason, normal CMC0 J
In this report, a method is adopted in which the molar ratio is set to about 1.10, the etherification reaction is always carried out under the condition of excess alkali, and after the reaction is completed, the excess alkali is neutralized with acetic acid to produce CMC.

However, as a result of research, the present inventor found that when producing carboxymethyl cellulose ether alkali salt by reacting an alkali IJ (7) presence-F etherifying agent to a cellulosic raw material in a water-containing organic solvent, The etherification reaction is started in a system with an excess of etherification agent by setting the molar ratio of [alkali]/[etherification] in the reaction system after addition of the agent, that is, the number of moles of the etherification agent charged, to 0.10 to 099. Then, in order to prevent the reaction system from becoming rS9 due to the consumption of alkali as the etherification progresses, the etherification reaction is carried out by further adding alkali, and finally the mole of [alkali]/diether stopper] It has been found that by completing the etherification reaction with a ratio of 1.0 or more, CMC with a uniform substituent distribution can be obtained with a significantly higher effective utilization rate of monochloroacetic acid than in conventional production methods.

In other words, according to 9■, the first jυ of the etherification reaction [
The molar ratio of alkali J/C ether stopper J is H4Hj, i.e., the number of moles of charged ether stopper is 011 to 0, which is lower than 10 to 1.80 in the conventional manufacturing method.
．． 99, preferably with an excess of ether stopper of 0.80-0.70, ntl i+L Il
In order to suppress the l + III reaction of l + III and to maintain the monochloroacetic acid self-effect 1j usage rate, it has been found that monochloroacetic acid [#sodium], which has a lower affinity for cellulose than alkali, diffuses into cellulose fibers. In the CMC reaction where (or osmosis) is considered to be rate-determining, the temperature is 60 to 80'C in an alkaline permeation system like the conventional ff J opening method!
Etherification reaction with %θ, A-cho? In this case, before sodium monochloroacetate uniformly diffuses or permeates into the cellulose fibers, the etherification reaction force due to the alkali present in the cellulose fibers (1.
This was the cause of the non-uniformity of the undershirt + S '4 distribution, but
To the present invention. By carrying out the etherification reaction from the start of the reaction to completion in a system containing excess sodium monochloroacetate, diffusion or penetration into the cellulose fibers is promoted. a. It is thought that CMC having a uniform substituent distribution can be obtained by reacting with a small amount of alkali that has penetrated into the fibers. In the present invention), it is necessary to initiate the reaction in a system containing an excess of ether stopper as described above, and it is desirable that at least 80% or more of the etherification reaction be carried out within the above molar ratio range. . In addition, when producing CMC with a DS of 2.00 or more, it is possible to produce with a higher effective utilization rate of monochloroacetic acid by repeating the above method two or more times.

In the production method of the present invention, reaction solvents include ethyl alcohol, n-propyl alcohol, inglobil alcohol (hereinafter abbreviated as 1 pA), tXn-glyal alcohol, isopropyl alcohol, tert-glycyl alcohol,
Water-containing 4-fi solution such as acetone and ethyl alcohol
Water-containing mixed solvents such as benzene, ethyl alcohol-toluene, and ethyl alcohol-n-hexane7 can be used. In addition, sodium hydroxide and potassium hydroxide are suitable as alkalis, and monochloroacetic acid, monochlorosodium vinegar, and monochloroacetic acid are suitable as ether stoppers. Esters of potassium acid and monochloroacetic acid, such as ethyl, n-propyl, inopropyl, n-)ethyl, inophthyl and tert-butyl esters, can be used.

The effects of the present invention as a printing paste for reactive dyes will be explained below using Examples and Comparative Examples. In addition, the part is the heavy vertical part, op
Indicates i't@it%.

In the example, 2160 parts of Inglobil alcohol (hereinafter abbreviated as ipA) was charged into a 51 reactor having a stirring blade on the shaft, and 286.8 parts of sodium chloride (purity 9896) was dissolved in 1663 parts of pure water. After cooling to 20-80°C, 200 parts of powdered cellulose (average degree of polymerization, 600, purity 95%) was added and stirred and mixed at 20-80°C for 60 minutes to produce alkali cellulose P4. Next, 4509 parts of monochloroacetic acid (98% pure) was added to i p A 450
．． Dissolve in 9 parts and add while cooling to 8 parts at 20-80℃.
Perform part-to-part agitation mixing. Thereafter, the temperature was raised to 60"CK in about 10 minutes to carry out the etherification reaction for 60 minutes.Next, 95.4 parts of sodium monohydroxide was dissolved in 68.7 parts of pure water and added, and the mixture was heated at 60 to 70°C. After stirring and mixing for 15 minutes, the temperature was raised to 70°C and the etherification reaction was carried out for 90 minutes.Then, the slight remaining sodium hydroxide was neutralized with acetic acid.

After the reaction is complete, take out the reaction mixture from the reactor and
It was separated to remove the reaction solvent ipA, and then washed 8 times with 4000 parts of a 75% methyl alcohol aqueous solution to remove the by-products of salt, sodium glycolate, and sodium acetate, and then centrifuged to remove the methyl alcohol aqueous solution. The purified product was heated in a dryer at 80-100'C for about 6 hours to obtain the carboxymethyl cellulose ether alkali salt of the present invention.

In a comparative example, 2160 parts of Ip^ was charged into a reactor No. 51 having a shaft stirring blade, and 881.7 parts of sodium hydroxide (purity 9) was charged.
8%) in 280 parts of pure water.
After cooling to "C", 200 parts of powdered cellulose (average degree of polymerization,
6001 (purity 95q6) and stirred and mixed at 20 to 80°C for 60 minutes to prepare alkali cellulose.

Next, 450.9 parts of monochloroacetic acid (purity 9.8'96)
was dissolved in 450.9 parts of IP A, added while cooling, and stirred and mixed at 20 to 80°C for 80°C. After ten
The temperature was raised to 70°C in about 15 minutes, and the etherification reaction was carried out for 90 minutes. Next, the slight remaining sodium hydroxide is neutralized with acetic acid.

Thereafter, washing and drying were carried out in the same manner as in Example 1 to obtain calhokitsum methyl cellulose ether alkali salt by the conventional method.

Example 2 Isopropyl alcohol (hereinafter abbreviated as ipA) (575 purity 98%) dissolved in 126.2 parts of pure water was charged into a 51 reactor equipped with a twin-shaft stirring blade, and after cooling to 20 to 80°C. , 200 parts of powdered cellulose (hardness 95%, average degree of polymerization 800) was charged and mixed with stirring at 20 to 80°C for 60 minutes to prepare alkali cellulose. Next, 172.0 parts of monochloroacetic acid (98% pure) was added to i p A I72
．． 0 parts, added while cooling, and stirred and mixed at 20 to 80°C for 80 minutes. After that, in about 10 minutes, 60
The temperature was raised to .degree. C. and the etherification reaction was carried out for 60 minutes.

Next, 26.2 parts of sodium hydroxide was dissolved in 16.8 parts of pure water, added, stirred and mixed at 60 to 70°C for 15 minutes, and then heated to 70°C and subjected to an etherification reaction for 90 minutes. After completing the reaction, the slight remaining sodium hydroxide is neutralized with acetic acid to complete the first stage reaction.

Next, the reaction mixture was taken out from the reactor, centrifuged to remove the reaction solvent 1p^, and then washed 8 times with 1 part of 75% methyl alcohol aqueous solution 41Q) to remove the regular product, salt. After removing sodium glycolate and sodium acetate, CMC was obtained by drying at 80 to 100° C. for about 4 hours.

Next, using this CMC, a second stage reaction was carried out using the same reactor as in the first stage reaction and under the same reaction conditions, and the CMC of the present invention was obtained by drying the product manufactured by fpI.

Example 8 In a 51 reactor with two-shaft stirring blades, 1 pA 1687
2552 parts of sodium hydroxide (purity 98%) was dissolved in 166.2 parts of pure water and the mixture was prepared at 20 to 8 parts.
0゛'CK After cooling, powder -t = Nyl -2200 parts u
Alkali cellulose is prepared by stirring and mixing for 0 minutes at 20-3°C.Next, 448.9 parts of monochloroacetic acid (purity 9) is prepared.
8% of the mixture was dissolved in 448.9 parts of r p A, added while cooling, and stirred and mixed at 20 to 80° C. for 80 minutes. After that, the temperature was raised to 60℃ in about 10 minutes, and the temperature was increased to 80℃ at 60℃.
Perform the etherification reaction for minutes. Next, 68.7 parts of sodium hydroxide dissolved in 42.5 parts of pure water is added, followed by an etherification reaction at 60° C. for 80 minutes. Thereafter, 82.9 parts of sodium hydroxide dissolved in 55.8 parts of pure water was added, stirred and mixed for 15 minutes, and then heated to 70° C. for 90 minutes to complete the etherification reaction. The slight remaining sodium hydroxide is neutralized with acetic acid to complete the first stage reaction.

Next, the reaction completed mixture was purified and dried in the same manner as in Example 1, and then the CMC was used for the second stage reaction using the same reactor and under the same reaction conditions as in the first stage reaction. The CMC of the present invention was obtained by further purification and drying.

Table Note (1) Viscosity was measured using a BL type viscometer at 50 rpm for a 1% aqueous solution at 25°C.

Note (2) To evaluate the desizing property, prepare a colored paste with the following composition using Remazol Blue G (Hex lt[)r as a reactive dye, and perform screen printing on cotton cloth and rayon cloth. Both were air-dried under the same conditions, and the steam heat was (10% for cotton cloth)
104+ at 0℃, rayon cloth at 100℃ for 80 minutes) 26
Immerse in water at ℃ for about 80 minutes, then move up, down, left and right (821)
Comparison-1 Almost no difference was observed in the desizing properties, texture, hue, etc. of the dyed fabrics after washing them with water by gently moving the dyed fabrics with the naked eye or by touching them by hand.

The preferred criteria were as follows.

◎Excellent ○Good △Slightly inferior
Part 10 parts 1 part 2 parts 36 parts 48 parts 10
0 parts or more, as shown in the examples and comparative examples, the present invention +7
)D31.8-3.0. When using a reactive dye composition composed of C'MC with a value of L < 1-1.2.0 or more, it is found that this material has desizing properties equivalent to that of sodium alginate.

In addition, commonly used sodium alginate is a natural product and has the drawbacks of unstable quality and high price.
Enables the use of MC.

that's all

Claims (1)

[Scope of Claims] ++) Printing paste for reactive dyes consisting of an alkali salt of carboxymethyl cellulose ether having a degree of substitution of 1.8 to 8.0) 2) Adding ether to a cellulosic raw material in the presence of an alkali in a water-containing organic solvent system When producing carboxymethylcellulose ether alkali salt by the action of a curing agent, the alkali is added at the initial stage and the alkali is expressed as the following formula [alkali].
The etherification reaction is started in a system with an excess of ether stopper so that the molar ratio of [alkali]/[etherification agent] is 010 to 099, and then the alkali is added in portions to achieve [alkali]/[etherification] in the final stage. carboxylic acid with a degree of substitution of 18 to 8.0, characterized in that the etherification reaction is carried out so that the molar ratio of the agent] is 1.00 or more, and the above reaction is repeated two or more times as necessary. Manufacturing method for printing paste for reactive dyes consisting of methylcellulose ether alkali salt [alkali]/[ether as stopper] Number of moles of etherifying agent charged