JPH1060215A - Agent for improving dyeability of disperse dye - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agent for improving the dyeability with disperse dye to make a fiber undyeable with disperse dye such as regenerated cellulose fiber to be dyeable with disperse dye and to enable the one-stage dyeing of a blended fiber of the fiber undyeable with disperse dye and a synthetic fiber dyeable with disperse dye such as polyester fiber in one bath. SOLUTION: This dyeability improving agent is composed of fine particles of a crosslinked polymer produced by the emulsion polymerization of a monomer mixture consisting of (a) 45-95wt.% of at least one kind of an alkyl methacrylate monomer having a 1-12C alkyl group, (b) 1-50wt.% of an aromatic vinyl monomer, (c) 1-20wt.% of a polyfunctional monomer and (d) 0-10wt.% of a vinyl monomer copolymerizable with the above monomers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer composition, and more particularly, to a polymer composition which is capable of dyeing a fiber exhibiting insolubility or difficulty in dyeing a disperse dye with a disperse dye or improving the dyeability. It relates to a combined composition.

[0002]

2. Description of the Related Art Fibers are dyed by dyes such as direct dyes, reactive dyes, slender dyes, disperse dyes, cationic dyes, reactive dyes, vat dyes, naphthol dyes, sulfur dyes, mordant dyes and chromium dyes. There are a variety of dyeing methods such as a dyeing method and a dyeing method using a coloring pigment. Above all, dyeing with a disperse dye is a very excellent dyeing method because it shows good dyeing properties for synthetic fibers such as polyester and nylon, and also has good dyeing fastness. However, fibers made of natural materials such as viscose rayon and cotton could not be dyed with a disperse dye. On the other hand, due to the growing needs of the market in recent years, by blending two or more kinds of fibers with different properties, such as blending rayon fiber and polyester fiber, high-performance fiber with the characteristics of each fiber Development is underway. However, when dyeing such mixed fiber products, it is necessary to perform multi-stage dyeing with different dyes due to the difference in dyeing properties depending on the type of fiber, which makes the process complicated and disadvantageous in terms of dyeing cost. However, there is a drawback that it is difficult to enhance the same color because it is dyed with different dyes.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to make fibers which are not dyeable by a disperse dye such as regenerated cellulose fibers dyeable by a disperse dye and mix them with synthetic fibers which are dyeable by a disperse dye such as polyester fibers. It is an object of the present invention to provide a disperse dye improver for enabling one-stage dyeing in the same bath as an article.

[0004]

That is, the present invention provides:
At least one alkyl methacrylate monomer (a) having an alkyl group having 1 to 12 carbon atoms (a) 45 to 95
% By weight, 1 to 50% by weight of an aromatic vinyl monomer (b) and 1 to 20% by weight of a polyfunctional monomer (c). Preferably, monomer (a), monomer (b) and monomer (c)
Is a disperse dyeing improver comprising crosslinked polymer fine particles obtained by emulsion polymerization of a monomer mixture consisting of

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. C1-C1 constituting the crosslinked polymer fine particles of the present invention
2, at least one methacrylate monomer (a) includes methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, etc. And methyl methacrylate is preferably used. Two or more of these methacrylates may be used in combination, and the weight ratio of the methacrylate ester monomer (a) in the monomer mixture is 45 to 95% by weight, more preferably 50 to 90% by weight. %, More preferably 60 to 9%.
0% by weight.

[0006] As the aromatic vinyl monomer (b), styrene, p-methylstyrene, o-methylstyrene, m-
Methyl styrene, α-methyl styrene, vinyl naphthalene and the like can be mentioned. The weight ratio of the aromatic vinyl monomer (b) in the monomer mixture is 1 to 50% by weight, preferably 5 to 30% by weight, more preferably 10 to 20% by weight.
It is. If the amount of the aromatic vinyl monomer (b) is less than 1% by weight, the types of disperse dyes that can be used are limited, so that it is not preferable. If the amount exceeds 50% by weight, the weather resistance of the crosslinked particles themselves deteriorates. .

In the fiber dyeing which is a typical example of the use of the dispersing dye improving agent of the present invention, dyeability is also important.
The resistance to discoloration and discoloration after dyeing, i.e. the fastness, is also important. In the present invention, in order to balance both dyeability and fastness, the ratio (a) / (b) of the alkyl methacrylate monomer (a) to the aromatic vinyl monomer (b) is determined. 1.5-20, preferably 2-1
5, and more preferably in the range of 3 to 10. If it exceeds this range, the dyeability and the fastness, especially the light fastness, cannot be balanced, and the practicality tends to be reduced.

Further, it is important to introduce a crosslinked structure by the polyfunctional monomer (c) into the crosslinked polymer fine particles of the present invention. This is because it is effective in improving the heat resistance of the fine particles themselves and expanding the range of dispersible dyes that can be dyed. As the polyfunctional monomer (c) used in the present invention, known ones can be used, for example, allyl (meth) acrylate, isocyanuric (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate. ) Acrylate, polyethylene glycol di (meth)
Acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, ethylene oxide di (meth) acrylate, propylene oxide di (meth) acrylate, dicyclopentenyl ( (Meth) acrylate polyfunctional monomers such as (meth) acrylate and trimethylolpropane tri (meth) acrylate; and aromatic polyfunctional vinyl monomers such as divinylbenzene, among which (meth) acrylic A system polyfunctional monomer is preferably used.

The weight ratio of the polyfunctional monomer (c) in the monomer mixture is from 1 to 30% by weight, preferably from 5 to 25% by weight, more preferably from 10 to 20% by weight. is there. The crosslinked structure in the polymer particles may be uniform throughout the polymer particles, or may be introduced such that the crosslinked structure continuously increases or decreases from the inside to the outside of the particles.

If necessary, a vinyl monomer (d) copolymerizable with the above-mentioned monomer may be added to the monomer mixture in an amount of 0 to 10%.
It can be used in the range of 10% by weight. Examples of these vinyl monomers include carboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, diolefins such as butadiene and isoprene, and maleimide compounds such as N-ethylmaleimide and N-cyclohexylmaleimide. These can be used in combination of two or more.

The polymer fine particles of the present invention can be produced mainly by an emulsion polymerization method in an aqueous medium. Examples of the aqueous medium include ion-exchanged water and a small amount of an organic solvent such as methanol. A mixture is used, and the amount thereof is 100 to 500 parts by weight, based on 100 parts by weight of the monomer mixture.
More preferably, it is 150 to 450 parts by weight.

The emulsifier used to obtain the disperse dye improver of the present invention includes anionic emulsifiers such as sodium salts and ammonium salts of lauryl sulfate, lauryl sarcosine acid, dioctyl sulfosuccinic acid, dodecylbenzene sulfonic acid and the like; Nonionic emulsifiers such as amino ethers, nonionic emulsifiers such as polyoxyethylene sorbitan monostearate and sorbitan stearate, sodium salts such as polyoxyethylene nonyl phenyl ether sulfate and polyoxyethylene alkyl ether sulfate, and nonionics such as ammonium salts. A known emulsifier such as an anionic emulsifier can be used, and more preferably, a nonionic anionic emulsifier or an anionic emulsifier is used. In particular, the number of moles of ethylene oxide added to the nonionic anionic emulsifier is preferably 4 to 20 moles, because if it is too large, the foamability increases and the fiber spinning process is adversely affected. It is also possible to use two or more of these.

These emulsifiers can be added to the aqueous system and then added to the monomer mixture, or can be further added during polymerization. However, it is possible to disperse the monomer mixture in the emulsifier in advance. By continuously supplying the liquid to the polymerization tank, the target polymer can be obtained stably and in good yield. Examples of emulsifiers suitable for such polymerization include dodecylbenzenesulfonate, dioctylsulfosuccinate, polyoxyethylene alkyl ether sulfate and polyoxyethylene nonylphenyl ether sulfate, among which polyoxyethylene nonylphenyl A sodium salt or an ammonium salt of ether sulfate is preferred, and the number of moles of ethylene oxide added is preferably 30 mol or less, preferably 20 mol or less, more preferably 10 mol or less.

As the polymerization initiator, any of a persulfate initiator such as potassium persulfate and ammonium persulfate and a redox initiator such as persulfoxylate / organic peroxide can be used. Good. Further, the temperature at the time of polymerization is usually 30 to 150 ° C, more preferably 50 to 1 ° C.
00 ° C. If necessary, a chain transfer agent such as octyl mercaptan or lauryl mercaptan can be added to the monomer mixture.

The particle size of the crosslinked polymer fine particles is as follows:
0.1 μm to 2.0 μm, more preferably 0.15 μm
To 1.0 μm, more preferably 0.2 μm to 0.6 μm
It is. When it is less than 0.2 μm, it is not preferable because when it is mixed with the stock solution of the fiber to be spun, it tends to cause agglomeration and the spinnability is deteriorated, and when it exceeds 2.0 μm, the dispersion stability of the emulsion when used in the form of an emulsion is unfavorable. It is not preferable because it decreases.

In the present invention, the pH of the emulsion of the crosslinked polymer fine particles may be adjusted to 6-1 after completion of the polymerization operation.
It is preferable that the adjustment be made to be zero. In this case, p
Examples of H adjusters include ammonia, sodium hydroxide, and sodium carbonate as basic adjusters, and sulfuric acid, acetic acid, and the like as acidic adjusters. These are usually used as an aqueous solution, and the concentration is 10 to 30.
% By weight is appropriate.

Further, a surfactant having at least one sulfonic acid group or a sulfuric acid group in the molecule may be added to the disperse dye improver of the present invention for the purpose of improving the spinnability of the fiber. . Examples of this surfactant include alkyl naphthalene sulfonate, naphthalene sulfonate formalin polycondensate, polyoxyethylene alkyl ether sulfate and polyoxyethylene nonyl phenyl ether sulfate, and the like. 0.05 to 10 parts, preferably 0.08 to 5 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts of the combined emulsion.
~ 2 parts by weight.

The disperse dye improver of the present invention may be used by adhering it to the fiber surface, but is preferably used by dispersing it in the fiber. The method of dispersing in the fiber is not particularly limited, but it is desirable to uniformly disperse the inside of the fiber. For this reason, for example, a method of wet-spinning by mixing a dispersion dyeing improver in the form of an emulsion into a spinning stock solution, kneading the dispersion dyeing improver taken out as a solid powder by salting out coagulation, spray drying, etc., into a raw material of a fiber or a spinning stock solution. The method is raised with. More specifically, as an example of wet spinning, the disperse dyeing improver of the present invention is added in an emulsion state to an aqueous alkali solution of viscose, which is a stock solution for spinning rayon fibers, and the mixture is uniformly mixed and spun. Can be obtained. The amount of the disperse dye improver is suitably about 5 to 30% by weight based on the viscose.

The mechanism by which the disperse dyeability improving agent of the present invention is used to improve the disperse dyeability has not been sufficiently elucidated, but the above-mentioned specific monomer composition, crosslinked structure and particle size are considered. This is considered to be because the disperse dye is taken into the inside of the crosslinked fine particles, which are the disperse dye improver of the present invention, dispersed in the fibers in the dyeing step, and becomes dyed fine particles. It is considered that the disperse dye incorporated in the crosslinked polymer fine particles is hardly re-dispersed outside the fine particles due to the crosslinked structure, so that the dyeing fastness is also improved.

The disperse dye improver of the present invention can be applied to known fibers. For example, viscose rayon, cuprammonium rayon (cupra),
Examples include regenerated celluloses such as organic solvent rayon, celluloses such as acetate, polyvinyl alcohols, polyamides, polyesters, polyurethanes, and polyacrylonitrile.

It is to be noted that a preservative, an antifoaming agent, an ultraviolet absorber, an antioxidant, and the like can be added to the disperse dyeing improver of the present invention as long as the object of the present invention is not impaired.

[0022]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Further, “%” and “parts” used in Examples and Comparative Examples indicate “% by weight” and “parts by weight”, respectively. Abbreviations of compounds used in Examples, Comparative Examples and Tables are as follows.

MMA: methyl methacrylate NPGDM: neopentyl glycol dimethacrylate 9G: polyethylene glycol dimethacrylate
EO addition: 9 mol ALMA: allyl methacrylate St: styrene αMS: α-methylstyrene CHMI: N-cyclohexylmaleimide

Evaluation of Examples and Comparative Examples Evaluations of Examples and Comparative Examples were made according to the following methods. (1) Measurement of particle diameter The particle diameter of the polymer was about 10%
Dilute 000-fold. The particles are settled by centrifugation, the supernatant liquid is removed, and washing is performed three times by adding and dispersing pure water and further centrifuging. The particles are dispersed on an aluminum foil and dried. Next, this gold-palladium alloy is vapor-deposited by ion sputtering for 3 minutes (the thickness of the vapor-deposited film is 150 Å). The average value of 100 particles was randomly taken as a particle size from a secondary electron image photograph observed at about 20,000 times with an electron microscope JSM-6300F manufactured by JEOL Ltd. to determine the particle size.

(2) Evaluation of Dyeability Evaluation of the dyeability of the dispersion dye improver of the present invention shown in Examples and the polymer shown in Comparative Examples was performed by the following methods. A viscose (cellulose concentration 8.0%, alkali concentration 6.0%) adjusted by a conventional method was mixed with a concentrated alkali solution of 350 g / L and mixed with the polymer emulsions obtained in Examples and Comparative Examples. -1 (Dainichi Seika Co., Ltd.
) Was slowly added, and the mixture was stirred and mixed using a high-speed stirrer at 1000 rpm to add 20% of the fine particles to cellulose and an alkali concentration of 7.0%. Then, the mixture was allowed to stand and deaerated for one day and night to obtain a spinning stock solution. Then, the undiluted solution was coagulated from a spinneret of 0.07 mm × 40 holes into a coagulation regeneration bath (sulfuric acid: 155 g / L, zinc sulfate: 22 g / L, sodium sulfate: 250 g / L,
(A bath temperature of 60 ° C.) at a discharge rate of 11.9 cc / min, and at a spinning speed of 90 m / min, using a conventionally known centrifugal spinning apparatus, drawing at a draw ratio of 20%, and winding into a pot.
It was refined and dried to obtain rayon yarn.

The obtained dispersible dyeable rayon yarn is formed into a knitted fabric by a small tube knitting machine, and Sumicaron Brilliant Red SE-2BF (manufactured by Sumitomo Chemical) is used as a disperse dye at 3% ow.
f, Disper TL at 1 g / L, Ultra MT level at 1 g / L, bath ratio 1:50, 120 ° C. × 40 minutes (4
It rises from 0 ° C to 120 ° C in 30 minutes.
1 minute sodium hydroxide 1g
/ L, 1 g / L of sodium sulfate and 1 g / L of amylazine (manufactured by Daiichi Kogyo Seiyaku) at 80 ° C for 20 minutes, and then washed with water (30 minutes) and dried (60 ° C for 10 minutes) and knitted. I got the land. The resulting knitted fabric was evaluated for dyeability by the following dispersion dyeing ratio and light fastness (discoloration).

(Dispersion Dyeing Rate) The dispersion first-arrival rate was evaluated numerically by the following equation. Dyeing rate (%) = [(S0-S1) / S0] .times.100 Here, S0 and S1 are determined by an aqueous acetone solution (acetone / water = 1/1) for the dye solution and the dyeing residue before and after dyeing, respectively. Is the absorbance at the maximum absorption wavelength measured with a spectrophotometer for the dye solution diluted and adjusted with the dilution degree.

(Light Fastness) The light fastness was evaluated according to JI
This was performed according to SL0842-1988, and the exposure method was the third exposure method.

Example 1 850 g of ion-exchanged water was charged into a 2 L separable flask equipped with a reflux condenser under a nitrogen atmosphere, and the temperature was raised to 75 ° C. with stirring. Separately, add 30 liters of ion-exchanged water to a 1L beaker.
To 0 g of emal NC-35 (manufactured by Kao Corporation: sodium polyoxyethylene nonylphenyl ether sulfate: 35)
After dissolving 6.5 g, a monomer mixture obtained by mixing 499 g of methyl methacrylate, 88 g of styrene, and 59 g of neopentyl glycol dimethacrylate was added, and the mixture was stirred at 400 rpm for 30 minutes to obtain an emulsion of the monomer mixture. And When the temperature of the ion-exchanged water in the separable flask reaches a predetermined temperature, potassium persulfate is used as a polymerization initiator.
After charging 32 g, the monomer mixture emulsion was first fed at a rate of 1.73 ml / min for 10 minutes, and then the feed rate was increased to 6.4 ml / min and 0.3
Polymerization was performed by supplying an aqueous solution of a polymerization initiator in which 23 g of potassium persulfate was dissolved in 50 g of ion-exchanged water at a rate of 0.35 ml / min. When the supply of the monomer mixture emulsion was completed, the mixture was maintained at 75 ° C. for 60 minutes with stirring to drive in unreacted monomers to complete the polymerization (see Table 1 for the monomer composition). After completion of the polymerization, the mixture was cooled to 40 ° C., pH was adjusted with 10% aqueous ammonia to obtain a polymer emulsion, and a disperse dye improver was prepared. Using the obtained disperse dye improver, the disperse dye dyeing rate and light fastness were evaluated. Table 2 summarizes the evaluation results.

[0030]

[Table 1]

[0031]

[Table 2]

Examples 2-3 Using 646 g of the monomer mixture having the composition shown in Table 1 and using Neoperex F-25 (25% sodium dodecylbenzenesulfonate) as an emulsifier for polymerization, the ED was used for evaluation of dyeability. -1 instead of Emar NC-35 (Kao
Co., Ltd .: sodium polyoxyethylene nonylphenyl ether sulfate: 35% aqueous solution) A polymer emulsion obtained by the same operation as in Example 1 except that 1% was used was used as a disperse dye improver. Similarly, the disperse dye dyeing rate and the light fastness were evaluated. Second evaluation result
Summarize in a table.

Examples 4 to 7 The same procedure as in Example 1 was repeated except that 646 g of the monomer mixture having the composition shown in Table 1 was used. Evaluation of the disperse dye dyeing rate and light fastness was performed in the same manner as in the above. Table 2 summarizes the evaluation results.

Example 8 Under a nitrogen atmosphere, 850 g of ion-exchanged water and 2 g of Emal NC-35 were charged in a 2 L separable flask equipped with a reflux condenser, and the temperature was raised to 75 ° C. with stirring. 1L separately
Emar NC-35 in 300 g of ion exchange water in a beaker
After dissolving 6.5 g (manufactured by Kao Corporation: sodium polyoxyethylene nonylphenyl ether sulfate: 35% aqueous solution), 499 g of methyl methacrylate and 88 of styrene were dissolved.
g, 59 g of neopentyl glycol dimethacrylate, and 30 minutes at 400 rpm.
Stir for a minute to obtain a monomer mixture emulsion. When the temperature of the ion-exchanged water in the separable flask reached a predetermined temperature, 0.32 g of potassium persulfate was added as a polymerization initiator, and then the emulsion of the monomer mixture was first fed at a rate of 1.73 ml / min for 10 minutes. After that, the feed rate was increased to 6.4 ml /
The polymerization was carried out by feeding a polymerization initiator aqueous solution in which 0.323 g of potassium persulfate was dissolved in 50 g of ion-exchanged water at a rate of 0.35 ml / min. When the supply of the monomer mixture emulsion is completed, the mixture is stirred for 75 minutes.
The mixture was kept at 60 ° C. for 60 minutes to drive in unreacted monomers to complete the polymerization. After completion of the polymerization, the mixture was cooled to 40 ° C., pH was adjusted with 10% aqueous ammonia to obtain a polymer emulsion, and a disperse dye improver was prepared. Using the obtained disperse dye improver, the disperse dye dyeing rate and light fastness were evaluated. Table 2 summarizes the evaluation results.

Comparative Examples 1 to 6 The same procedure as in Example 1 was repeated except that 646 g of the monomer mixture having the composition shown in Table 1 was used, and the polymer emulsion obtained in Example 1 was used as a disperse dye improver. Evaluation of the disperse dye dyeing rate and light fastness was performed in the same manner as in the above. Table 2 summarizes the evaluation results.

[0036]

Industrial Applicability The disperse dyeing improver of the present invention enables dispersion dyeing of natural fiber such as regenerated cellulose fiber, which has been difficult so far, and disperse dyeing without reducing spinnability. This is extremely useful because it can facilitate the dyeing of a mixed product with a chemical fiber having a property.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Junji Ohkita 7471 Otajima Oshima, Kurashiki City, Okayama Prefecture Kuraray Co., Ltd.

Claims (6)

[Claims] 1. At least one alkyl methacrylate monomer having an alkyl group having 1 to 12 carbon atoms (a), 45 to 95% by weight, an aromatic vinyl monomer (b) 1
-50% by weight and 1-20% by weight of polyfunctional monomer (c)
And a disperse dye improver comprising crosslinked polymer fine particles obtained by polymerizing the polymer. 2. A crosslinked polymer fine particle comprising a monomer (a),
The disperse dye improver according to claim 1, which is a fine particle obtained by polymerizing a monomer mixture containing (b) and (c) by an emulsion polymerization method. 3. The method according to claim 1, wherein the monomer (a), (b) and (c) further contains 10% by weight or less of a copolymerizable vinyl monomer (d). Disperse dyeing improver. 4. A crosslinked polymer particle having a particle size of 0.1 to 2 μm.
The disperse dyeing improver according to any one of claims 1 to 3, wherein m is m. 5. The dispersion according to claim 1, wherein the ratio (a) / (b) of the monomer (a) to the monomer (b) is from 1.5 to 20. Dyeing improver. 6. The disperse dye improver according to claim 2, wherein the crosslinked polymer fine particles are present as a polymer emulsion adjusted to pH 6 to 10.