JPS6144997B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a sodium salt of carboxymethylcellulose (hereinafter abbreviated as CMC) for textile printing, which has improved size liquid fluidity and has unprecedented printing suitability. One of the dyeing methods for textile products is printing, which allows pattern dyeing. A sizing agent is used for this printing, except in special cases such as transfer printing using sublimation dyes. Commonly used thickening agents include starch, bristle gum, guar gum, locust bean gum,
There are natural, semi-synthetic and synthetic thickeners such as tamarind, sodium alginate, CMC and their derivatives, emulsions consisting of mineral oil and emulsifiers, polyacrylic acid sodium salts, and polyvinyl alcohol. The main performance required of printing pastes such as these is to make the mixture of dye and other necessary chemicals and auxiliary agents viscous and to faithfully print the desired pattern or design on the printed fabric. It can be printed on, and it has an adhesive action that prevents the dye from separating from the fabric after printing and drying. Furthermore, in the next dye fixation process, it is necessary to have good dyeability without inhibiting the dyeing action, and after dyeing, it is easier to wash with water than the dyed fabric.
It needs to be removed. The main items for evaluating stainability include surface color density, permeability, level staining, sharpness, and sharpness. However, these performances are not required for all purposes, and may not be required depending on the purpose of dyeing, and the degree of importance differs depending on the content of dyeing. This dyeability changes depending on the type of adhesive used. For example, when a glue having a large fluidity, such as sodium alginate, is used, it has good permeability, but it is difficult to obtain a surface color density. on the other hand,
In the case of a plastic-flowable sizing agent such as etherified starch, a high surface color density can be obtained, but the permeability is poor. Therefore, depending on the type of fabric to be printed, the design, pattern, and color of the print, the use and purpose of the dyed fabric, the most suitable sizing agent is used alone or in combination of two or more types. CMC can greatly change the fluidity of size liquid by changing the degree of etherification and substituent distribution. That is, the dyeing properties such as the surface coloring density, permeability, and sharpness can be arbitrarily changed over a wide range. Moreover, CMC is a high-temperature and atmospheric continuous steaming method (hereinafter abbreviated as HTS method), which is becoming the mainstream dye fixing process.
It is said to be second only to the expensive sodium alginate sizing agent in terms of desizing properties, which are a particular problem, and is suitable for the synthesis of polyester fibers, polyacrylic fibers, polyamide fibers, etc. using dyes that can be continuously fixed using the HTS method. It has an important position and is widely used as a sizing agent for printing textile products. The degree of etherification of CMC is theoretically possible up to 3 moles/anhydroglucose unit (hereinafter abbreviated as M/C ₆ ). However, as the degree of etherification increases, the production cost of CMC increases because the amount of expensive monochloroacetic acid or its sodium salt used as an etherification agent increases and its effective utilization rate decreases. Conventionally, CMC used as a printing paste with a degree of etherification of 1.5M/ _C6 or higher was considered impractical due to its high manufacturing cost. However, in recent years, the textile printing industry has requested CMC size agents with greater fluidity and demand for better desizing properties when using reactive dyes.
The demand for CMC with a high degree of etherification of 1.5M/C ₆ or higher has become stronger, and along with efforts by CMC manufacturers to reduce the cost of CMC with a high degree of etherification, the practical range of degree of etherification has reached around 2.0M/C ₆ . It has been expanded. Highly etherified CMC has good film-forming properties and is flexible under moderate humidity, so it is used as a film enhancer after printing and drying, and its good fluidity allows it to penetrate into the fabric. It is preferably used for brushed textile products, thick materials, or when dyeing is required to the back side. In addition, when printing with reactive dyes, CMC with a high degree of etherification does not cause any reaction between the size agent and the dye, has good desizing properties, and does not impair the texture of the dyed fabric, so it is actively used as a substitute for sodium alginate. It is used in many ways. Dye is the most expensive material for textile printing, and the surface color density is proportional to the amount added. If permeability is not required and only surface color development is an issue, use plastically fluid starch or its derivatives that have poor permeability but high surface concentration, or CMC with a low degree of etherification to increase the amount of dye added. This reduces the amount of printing and makes economical printing possible. On the other hand, when both permeability and surface dye density are required, dyes can be added using thickening agents such as sodium alginate, guar gum, tamarind, or CMC with a high degree of etherification, which have high fluidity and good permeability. Alternatively, the surface color density can be increased by adding starch or CMC with a low degree of etherification at the expense of permeability. In recent years, various materials have been developed and called differentiated materials.
As it has become more commercialized, the printing process has also become more difficult. Among these materials, materials with extremely poor permeability, such as polyester palace cloth, have been developed, and there is a need for a sizing agent that has good permeability and can provide high surface color density even with a small amount of dye. Sodium alginate is expensive, and guar gum and tamarind have problems with desizing properties in HTS and rotting of the size solution, so CMC with a high degree of etherification and improved surface color density is desired. Conventional
It was considered difficult to achieve both permeability and surface coloring density using only CMC, but in the present invention, this problem was solved by specifying the degree of etherification and particle size. The inventors of the present invention have conducted extensive studies in response to such requests, and as a result, the degree of etherification is 0.9M/C ₆ ~ 2.0M/
C ₆ , preferably 1.2M/C ₆ - 2.0M/C ₆ The total amount of high etherification degree CMC powder particle size is 61 μ or less, and the particle size of 37 μ or less is finely divided so that it is 95% or more, preferably 97% or more. By pulverizing, the fluidity is improved and the permeability is improved without reducing the degree of CMC polymerization.Moreover, when printing and coloring are performed with a screen of 150 mesh or less, the surface coloring density decreases. There is no difference, but I invented that the price will be higher for high mesh screens of 150 meshes or more. For CMC with a degree of etherification of 0.9 M/C ₆ or less, the fluidity was improved by finely pulverizing it, but at the same time the color density did not increase. Conversely, CMC with a lower degree of etherification had less fluidity and became plastic, resulting in a slight increase in surface concentration.
CMC of 2.0M/C ₆ or higher is expensive to manufacture and is impractical as a printing paste. The present invention
The degree of polymerization and purity of CMC are not particularly limited. Furthermore, the pulverization method is not particularly limited. The effects of the present invention will be explained below using Examples. Example 1 Degree of etherification with normal particle size shown in Table 1
CMC A ₀ with a high degree of etherification of 1.55M/C ₆ was ground in a vibrating ball mill at different times to produce different particle size distributions.
Three types, A ₁ , A ₂ and A ₃ were obtained. No decrease in the degree of polymerization due to fine pulverization was observed in the degree of polymerization of these materials. Dissolve each of these in water to prepare a base glue so that the color paste becomes 4000±200 cp, and add 65% by weight of this base glue (% indicates weight% below) and the disperse dye Kayalon.
A colored paste was prepared by mixing and dissolving 2% Polyester Navy Blue R-SF, 1% sodium chlorate, 0.5% malic acid, 11% concentrated dye Hiacurase PE-7, and 30.5% warm water (approximately 50°C). This product was printed on polyester palace cloth using a flat auto screen test machine with a rubber cage and a screen speed of 20 m/min with 100, 150, 180, and 200 mesh screens, and after air drying, HTS was used at 175℃-5 It was steamed for a minute and washed with water. After washing with water, a part was air-dried to prepare a sample cloth for desizing performance evaluation, and the remaining part was heated to 80% with a mixed solution of 0.2% sodium alkylbenzenesulfonate, 0.1% caustic soda, and 0.1% hydrosulfite.
℃ for 10 minutes and then washed with water. After air drying, it was finished with an iron and used as a sample for measuring surface color density and permeability. Desizing property was evaluated by texture, and surface color density was quantified using a reflectance meter, and the value for sample A ₀ of each screen was set as 100 and compared. The permeability was determined by measuring the density on the back side of the dyed fabric using a reflectance meter in the same way as on the front side, and using the following formula. Permeability (%)=Back side dyeing concentration/Surface dyeing concentration×100 The fluidity of the paste was measured as follows by using a rotational viscometer to determine the n value (Newton index). Adjust the viscosity of the glue liquid to 10000±1000 cp (B8M type rotational viscometer, manufactured by Tokyo Keiki Co., Ltd., 30 rpm, 25 °C) and read the guideline value (0 to 100) when changing the rotation speed of the viscometer. The values were entered on a log-log graph, and the n value was determined from the slope of the straight line based on the following equation. θ=K・η・W ⁿ …(1) θ: Guideline value of the viscometer K: Instrument constant of the viscometer η: Viscosity coefficient w: Viscometer rotation speed n: Newtonian index The closer the n value is to 1, the more Newtonian flow is. , indicates high fluidity, and the closer it is to 0, the less fluidity and plastic flow.

【table】

[Table] As shown in Table 2, the total powder particle size is 61μ
CMC samples A ₂ and A ₃ , in which 95% or more of the particles are 37μ or less, have higher n values, greater fluidity, and increased permeability compared to the parent CMC A ₀ . Moreover, the surface concentration is higher for screens with 150 meshes or more. In addition, no effect of particle size was observed on desizing properties, which was good.

【table】

[Table] *Surface color density for each mesh
The concentration of _A0 was set to 100.
Example 2 Each CMC of B ₀ , C ₀ , D ₀ , and E ₀ with different degrees of etherification and having the general particle size shown in Table 1 was milled in a vibrating ball mill so that the total amount was 61μ or less and 95% was 37μ or less.
Re-grinding is carried out until B ₁ ,
C ₁ , D ₁ , and E ₂ were obtained. A colored paste was prepared and printed in the same manner as in Example 1, and the surface color density and permeability were measured. As a result, as shown in Table 3, when the degree of etherification is 0.91M/ _C6 or more, it is found that n
The higher the value, the greater the fluidity and the more permeability.

[Table] The surface concentration was also higher than that of each parent in screens with 150 meshes or more. By finely pulverizing the printing paste, the same effect as that of increasing the degree of etherification can be obtained in terms of permeability, and the surface coloring density does not decrease, and on the contrary, it can be obtained with a screen of 150 mesh or more. A revolutionary improvement in the performance of the drug was observed. Example 3 Having the typical particle size shown in Table 1,
High etherification degree with different CMC purity and polymerization degree
Examples of F ₁ , G 1 , and H ₁ obtained by crushing CMC, Fo, Go, and Ho CMC to a total amount of 61μ or less using an air flow mill, and pulverizing 95% or more of the CMC of 37μ or _less Printing was carried out in the same manner as in 1, and the surface color density and permeability were measured. As shown in Table 4, F ₁ , G ₁ , and H ₁ , which were finely pulverized even though their purity and degree of polymerization were different, had higher permeability than their respective base materials, and even with a screen of 150 mesh or more, A high surface color density was obtained.

【table】

[Table] Example 4 In Example 2, printing was performed on cotton lawn cloth using a reactive dye instead of a disperse dye. Color paste: 60% base paste, 15% urea, 1.5% sodium bicarbonate, reactive dye Mikaci on Brilliant
It was prepared using 4% Red5BS and 19.5% hot water (approximately 50°C), and printing was performed using the screen of each mesh in the same manner as in Example 1. Dye fixation is done using a dry heat method at 160°C.
I did it in 5 minutes. The results are shown in Table 5, and the degree of etherification is
CMC of 1.2M/C ₆ or less reacted with reactive dyes, resulting in poor desizing properties and residual dyes and sizing agents, making it impossible to measure correct surface color density and permeability. In the case of 1.2M/C ₆ or higher, the permeability of the micronized powder as in Example 2 increased, and the surface coloring density increased on screens of 150 meshes or higher.

【table】

[Table] Shown.

Claims (1)

[Claims] 1. A paste for printing, in which the particle size of sodium carboxymethyl cellulose having an etherification degree of 0.9 to 20 mol/anhydroglucose unit is 61 μm or less, and 95% by weight or more of the particle size is 37 μm or less.