JPS584041B2 - Manufacturing method for printing paste for reactive dyes - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the use of filamentous sodium glycolate (hereinafter referred to as filamentous sodium glycolate) for printing pastes used as reactive dyes.
(abbreviated as MC).

More specifically, the present invention is such that the total amount of monochloroacetic acid (or its soda salt) used for the cellulose raw material is equal to or less than the carbon content of the cellulose material.
With a small amount of 4.0 mol or less used per mol of 6 basic unit molecules, DS has desizing properties that are comparable to, or even superior to, conventional sodium alginate.
The present invention relates to a method for producing NaCMC as a printing fiber for reactive dyes having a relatively high degree of etherification of 5 or more and a relatively high viscosity.

NaCMC has various uses such as textile glue, emulsified paint, adhesive, builder of synthetic detergents, and food stabilizer.It uses cellulose raw material and adds caustic soda, monochloroacetic acid or its soda salt, and water. The manufacturing methods include an aqueous medium method and an organic solvent method.

However, the NaCNC currently produced generally has a DS (average degree of etherification) of at most 1.5, usually 1.
．． 0 or less, and when it is used as a thickening material for printing with reactive dyes, its desizing properties are poor, so it has hardly been put into practical use to date.

The present invention was completed in order to solve the above-mentioned problem of desizing property.

That is, the present invention is a method for producing NaCMC by using a cellulose raw material and adding caustic soda, monochloroacetic acid or its soda salt, and water, in which the reaction is carried out in two stages. monochloroacetic acid to be added,
Or, the total amount of the soda salt used in the first stage and the second stage is a relatively small amount of 2.0 mol or more and 4.0 mol or less per mol of C6 basic unit molecule of cellulose, and
The amount of addition in each stage is made as equal as possible, and monochloroacetic acid is always added in the second stage without using sodium monochloroacetate, thereby reducing the NaCMC produced in the first stage.
temporarily becomes cellulose glycolic acid (hereinafter abbreviated as HCMC).

Next, after thorough stirring and kneading, caustic soda is added to carry out a conventional alkali medium reaction.

Possible causes of poor desizing properties of NaCMC produced by conventional methods include the formation of water-insoluble substances generated by residual free reactive OH groups in molecules and dye molecules; The present invention has confirmed through many experiments that in general, increasing the DS improves the performance.

However, in the above-mentioned known method, in order to increase the DS, expensive monochloroacetic acid and caustic soda are generally required in extremely large amounts, respectively, per cellulose. It causes oxidation and paste-like formation.

This makes mechanical operations such as stirring, which are necessary for smooth reaction, extremely difficult, and as a natural consequence, the effective utilization rate of monochloroacetic acid also decreases.

Therefore, Na CMC suitable for use as a thickening material cannot be produced by the above method.

In addition, many studies have been conducted on the production method of NaCMC, but in the case of reactive dyes, NaCMC has excellent desizing properties and is comparable to sodium alginate as a sizing agent.
There is currently no information available regarding the manufacture of CMC.

The present invention was carried out to achieve the above-mentioned objective of improving desizing properties, and it uses only a small amount of chemicals, is extremely easy to implement industrially, and is particularly suitable for use in printing with reactive dyes. It exhibits desizing properties and has excellent color value and level dyeing properties.
In addition, it has a high DS that allows for easy mechanical processing operations such as stirring during reaction.
of NaCMC can be produced most efficiently.

The method of the present invention will be explained in further detail.

The total amount of monochloroacetic acid or its soda salt used in the first stage and the second stage is 2.0 mol or more and 4.0 mol or less per 1 mol of C6 basic unit molecule of cellulose.
The amount used in each stage should be as equal as possible, and the difference between them should be small. Specifically, the amount used in the first stage is 1.0 per mole of basic unit molecule.
mol ~ 2.0 mol, same in second stage < 1.0 mol ~ 2.0
The range is in moles.

Regarding caustic soda, the inventor's research (Hayakawa Tokyo Technical Trial Report, 49th No. 9, 10, 365-367, 383-38
5.1954), it is either completely equimolar to the sodium monochloroacetate in the reaction system, or very slightly 0. 1~0
．． It is preferable to have an excess of about 2 moles.

The crude product from the first stage reaction contains a large amount of by-products such as common salt, sodium glycolate, and a small amount of residual free alkali, but in the present invention, this crude product is purified using methanol or sulfuric acid. Of course, the above crude product can also be subjected to the second stage reaction as it is.

Next, the present invention will be explained with reference to Examples and Comparative Examples.

Examples, Comparative Examples Cellulose carboxyl methylation conditions of Examples and Comparative Examples,
The properties of the products are listed in the table below.

Experiment numbers &1 to No3 are examples No.4 to No.1 of the present invention
7 is a comparative example.

No. 4 to No. 9 are just one-stage reactions, No. 10 to No. 12
is a two-stage reaction, but in the second stage, monochloroacetic acid soda is used instead of monochloroacetic acid as in the present invention.

Nos. 13 to 17 are organic solvent methods, and No. 18 is medium-viscosity sodium alginate, which has excellent properties as a glue.

Incidentally, Nos. 1 to 3 and Nos. 10 to 12 were all two-stage reactions, but in No. 1, the first-stage reaction product was directly subjected to the second-stage reaction.

For Nos. 2, 3, and No. 10 to No. 12, the crude products from the first stage reaction were once purified with methanol (washed with 70 to 80% methanol, filtered, and air-dried) to perform the second stage reaction.

The amount of added caustic soda is not listed, but in order to improve the effective utilization rate of monochloroacetic acid and prevent a decrease in the viscosity of the product in both the 1st and 2nd stages, the amount of caustic soda added is equivalent to or equivalent to the sodium monochloroacetate in the reaction system. A slight excess of about 0.1 to 0.2 mol was added.

Also, during the initial 2 to 3 hours of the reaction, cool the temperature to 20 to 30°C.
This is done at a low temperature of 60~3 hours.
The desired reaction was completed by heating to 70°C.

In Nos. 1 to 3 of Ki's invention, monochloroacetic acid in the second stage is added in the form of crystals, powder, or concentrated aqueous solution to convert NaCMC produced in the first stage into HCMC, and then the amount of calculation is reduced. Caustic soda was added to convert alkaline medium into CM using a conventional method.

Next, the column of various properties of the product will be explained.

As a standard test method for the desired textile printing suitability, as a color paste,
Reactive dye Remazol Black B (manufactured by Hoechst) 5%
, base glue 60% (this was prepared at the stated concentration depending on the viscosity of the sample), urea 5%, soda carbonate 1%, water 29%
Rayon and cotton fabrics were screen-printed using the same composition (total 100%), and both were air-dried and steamed under the same conditions. After soaking in water for about 15 minutes, soak for about 2 more minutes.
(The dyed fabric is gently moved vertically and horizontally a total of 320 times in a total of 0 minutes.) After washing, the dyed fabric's desizing properties, texture, hue, etc. are compared and judged visually or by manual touch. Ta.

In either case, almost no difference was observed in hue or other aspects, so all evaluations of suitability for printing were based solely on desizing properties.

The printing results (desizing properties) are the results for purified products after the completion of the CM reaction, except for No. 3, which has been subjected to methanol purification (washing with 70 to 80 methanol, filtration, wind No.) However, Example No. 3 is the result of using the crude product after the second stage reaction as it was for the printing test without completely refining it.

The table shows that increasing the DS of the NaCMC produced, ie, decreasing the number of free reactive OH groups in the molecule, clearly leads to an improvement in desizing properties.

Moreover, the desizing property changes markedly with a limit of DS of approximately 1.5.

In the case of No. 4 to No. 9, which are simple one-stage reactions, DS/C
If the amount of sodium monochloroacetate per mole of cellulose 06 basic molecules is increased in order to increase the amount of
Up to a molar level, the effective utilization rate of monochlorosodium acetate is maintained at about 45 to 50%, but if it increases beyond that, the DS increases and the reactive component loses its swollen fibrous state, causing a paste phenomenon. As a result, the reaction becomes non-uniform and the effective utilization rate of sodium monochloroacetate is also significantly reduced.

Furthermore, even if monochloroacetic acid is used at 5 moles per 061 moles of cellulose basic molecules, the DS only reaches 1.35, and the desizing property is extremely poor as mentioned above, making this method impractical.

Comparative Examples No. 10 to No. 12 are two-stage methods.

The two-stage method has a higher effective utilization rate and DS of sodium monochloroacetate than the one-stage method.

For example, in No. 11 to No. 12, the amount of sodium monochloroacetate used was 2.9 and 3.4 mol, the utilization rate and DS were 48.3%, 45.9%, 1.40, and 1.56, respectively, and the desizing property was also It's improving.

In other words, currently industrially produced in large quantities,
When targeting NaCMC with a low DS of approximately 10 or less, dividing the reaction into two stages will only complicate the operation.
On the contrary, it has been confirmed that at high DS, simply performing the CM conversion reaction in two stages is significantly more effective than a simple one-stage reaction method.

No. 1 to No. 3 are examples of the present invention.

The present invention is also a two-stage reaction like No. 10 to No. 12, but in the second stage, monochloroacetic acid is added in the form of fine powder crystals or concentrated aqueous solution as described in detail above, and the NaCMC after the first stage reaction is After the mixture is once converted into HCMC, caustic soda is gradually added to carry out a conventional alkali medium CM reaction.

Examples No. 1 to No. 3 and comparative examples No. 10 to No.
When compared with No. 12, the effects of the present invention are clear.

That is, No. 11 and No. 2 both use the same amount of sodium monochloroacetate, 2.9 moles, and only differ in the reaction mode, but the DS and viscosity of the products are both the same in No. 2. It is found that it is larger than No. 11 and is also superior in printing suitability (desizing property).

Furthermore, in No. 10, the total amount of monochlorosodium acetate used was 2.6 moles, and the desizing properties of the product were completely poor, but in No. 1 of the present invention, a smaller amount of the CM forming agent, about 2.4 moles, was used. It is also particularly noteworthy that a product with DS and viscosity both greater than No. 10 and excellent desizing properties can be obtained using the above method.

The comparison between the comparative examples No. 10 to No. 12 and the examples of the present invention No. 1 to No. 3 is summarized as follows.

That is, in the second stage reaction, sodium monochloroacetate was added in the comparative example, but monochloroacetic acid was added in the present invention.

In other words, the additive chemical for the second stage reaction is simply CH2ClCO
ONa+NaOH to CH2ClCOOH+2NaOH
In other words, by using the same amount of chemicals in total, it was possible to achieve superior effects with a simple reaction.

In addition, the present invention differs from the comparative example in that the crude NaCM is significantly swollen compared to the raw material fiber used in the first reaction.
The point is that the second stage reaction can be carried out smoothly even if C is not purified.

In other words, in the case of the comparative example, sodium monochloroacetate was directly added to the second stage, so if the first stage reaction product was not purified once, the reactant was gradually converted to a conventional reaction product as NaCMC and DS increased. The original fibrous state, which is easy to process with a crusher, is lost, resulting in a paste that is cake-like or hard candy-like, making subsequent reaction operations extremely difficult.On the contrary, the method of the present invention No1~No3
In this two-stage reaction, monochloroacetic acid is first added to convert the swollen NaCMC from the previous stage into NaCMC+CH2Cl.
Through the reaction of COOH→HCMC+CH2CNoCOONa, HCMC, which is more chemically active, temporarily becomes
(At this stage, the amount of water used can be appropriately adjusted to bring the regenerated HCMC fibers into the optimal physical state for the subsequent reaction.

In addition, by increasing the amount of water used, the solid phase reaction system is temporarily made smooth with relatively low viscosity, resulting in completely homogeneous HCMC.
After thoroughly crushing, stirring, and kneading this HCMC, a calculated amount of caustic soda is gradually added.

Moreover, the method of the present invention allows mechanical operations to be performed easily and in a short time, thereby allowing the reaction to proceed smoothly.

In the case of the comparative example, if the product of the first stage reaction is not purified, it is virtually impossible to carry out the second CM conversion reaction smoothly due to the difficulty of mechanical operation.

Comparative Examples No. 13 to No. 16 are methods using one-stage and two-stage organic solvent methods.

The one-stage method has poor desizing performance, and the two-stage method currently improves the desizing performance, but there are problems such as recovery of the organic solvent, and it cannot be easily applied to practical use.

Comparative Example A17 is a commercially available sodium alginate, which is currently in practical use as a reactive dye printing paste, and is described for comparison.

As is clear from the above description, examples, and comparative examples, the cellulose sodium glycolate produced by the method of the present invention has excellent properties as a printing paste for reactive dyes. Further, the final reaction crude product has the characteristic that it can be used as it is.

As described in detail above, the method of the present invention simplifies the reaction process, facilitates mechanical operations, and requires as little amount of chemicals as possible compared to many other possible methods. In particular, it exhibits particularly excellent desizing properties when used as a printing paste for reactive dyes, which is most efficient from all viewpoints.
NaCMC with relatively large DS and viscosity can be produced.

That is, the present invention uses Na as a printing paste for reactive dyes.
A new and most industrially economical method for the production of CMC.

Claims (1)

[Claims] 1. A method for producing cellulose sodium glycolate by using a cellulose raw material and adding caustic soda, monochloroacetic acid or its soda salt, and water to it, in which the reaction is carried out in two stages, the first stage being In the second stage, monochloroacetic acid or its soda salt is reacted with 1.0 to 2.0 moles per mole of 06 basic unit molecules of cellulose and caustic soda necessary for the reaction, and then in the second stage, the reaction product is added with fibers. Adding 1.0 to 2.0 moles of monochloroacetic acid per mole of the basic C6 basic unit molecule to convert the cellulose sodium glycolate produced in the first stage reaction into cellulose glycolic acid, followed by stirring, kneading, A method for producing a reactive dye printing paste, which comprises adding an amount of caustic soda necessary for the reaction and carrying out a conventional alkali medium reaction.