JP2021046634A - Leveling agent for dyeing cationized cellulose fiber - Google Patents

Abstract

To provide a leveling agent having excellent leveling properties in dyeing of a cationized cellulose fiber, and a method for producing a cationized cellulose fiber dyed product using the leveling agent.SOLUTION: A leveling agent for dyeing a cationized cellulose fiber contains at least one sulfonic acid compound selected from the group consisting of alkyl benzene sulfonic acid and a salt thereof. A method for producing a cationized cellulose fiber dyed product includes dyeing a cationized cellulose fiber in the presence of the leveling agent.SELECTED DRAWING: None

Description

The present invention relates to a leveling agent for dyeing cationized cellulose fibers and a method for producing a cationized cellulose fiber dyeing product using the leveling agent.

Conventionally, anionic dyes such as direct dyes and reactive dyes are usually used for dyeing cellulose fibers such as cotton. Cellulose fibers originally have an anionic charge on the surface and tend to cause dyeing defects due to electrical repulsion with anionic dyes. Therefore, as a method for improving the dyeability of cellulose fibers, bladder glass (Na ₂₎ A method of adding a neutral salt such as SO _{4) to cellulose fibers has been used.} The neutral salt has the effect of reducing the electrical repulsion between the dye and the fiber by neutralizing the fiber surface and forming dye micelles by salting out. However, in this method, since it is necessary to use a large amount of neutral salt, the environmental load due to the waste liquid has become a problem.

Conventionally, cationization of cellulose fibers has been proposed for the purpose of improving the dyeability of cellulose fibers (specifically, shortening the dyeing time and reducing dye loss). For example, Patent Document 1 describes a method for treating cellulose fibers, which comprises a step of contacting the cellulose fibers with a solution containing a wetting agent, an alkaline composition and an ammonium salt. According to such a method, the cation site (for example, a quaternary ammonium structure) introduced into the cellulose fiber is ionically bonded to the anionic dye, so that the dye can be strongly dyed on the cellulose fiber, so that the dyeing can be performed. It is possible to shorten the time and reduce the loss of dyes, and it is possible to reduce the burden on the environment.

On the other hand, various leveling agents have been proposed in order to improve the leveling property when dyeing cellulose fibers. For example, Patent Document 2 describes a compound obtained by adding ethylene oxide to an alkylamine as a leveling agent for directly absorbing and dyeing a cellulosic fiber product or a blended braided fiber product containing a cellulosic fiber with a dye or a reactive dye. A compound obtained by esterifying an aliphatic polyvalent carboxylic acid or an aromatic polyvalent carboxylic acid is described. Further, Patent Document 3 describes a sulfate ester salt or a sulfonate obtained by sulfated a fatty acid ester having a specific structure as a leveling agent for absorbing and dyeing a cellulosic fiber alone or a fiber product containing a cellulosic fiber with a reactive dye. Is described. However, with these leveling agents, sufficient leveling property of the cationized cellulose fiber has not been obtained.

Special Table 2016-511331 Japanese Unexamined Patent Publication No. 61-89383 Japanese Unexamined Patent Publication No. 63-92787

Catification of cellulose fibers as described in Patent Document 1 is advantageous in that anionic dyes can be easily transferred from the dyeing solution to cellulose fibers. However, the cationized cellulose fiber has a problem that the dyeing rate is difficult to control and uneven dyeing is likely to occur as compared with the non-cationized cellulose fiber. That is, if the affinity between the cellulose fiber and the dye is too large, the dye rapidly adheres to the cellulose fiber and the dyeing becomes local, and the dye once adhered to the fiber is separated from the fiber and differs. Uniform dyeing is difficult because it is also difficult to move to.

One aspect of the present invention solves the above-mentioned problems and provides a leveling agent having excellent leveling property in dyeing cationized cellulose fibers, and a method for producing a cationized cellulose fiber dyed product using the leveling agent. The purpose is.

The present invention includes the following aspects.
[1] A leveling agent for dyeing cationized cellulose fibers, which comprises at least one sulfonic acid compound selected from the group consisting of alkylbenzene sulfonic acid and salts thereof.
[2] The leveling agent according to the above aspect 1, wherein the alkyl group of the alkylbenzene sulfonic acid has 10 to 18 carbon atoms.
[3] A method for producing a cationized cellulose fiber dyed product.
A method comprising dyeing a cationized cellulose fiber in the presence of the leveling agent according to aspect 1 or 2 above.

According to one aspect of the present invention, there can be provided a leveling agent having excellent leveling property in dyeing cationized cellulose fibers, and a method for producing a cationized cellulose fiber dyed product using the leveling agent.

Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited to these aspects.

<Leveling agent>
One aspect of the present invention provides a leveling agent containing at least one sulfonic acid compound selected from the group consisting of alkylbenzene sulfonic acids and salts thereof. Although not bound by theory, alkylbenzene sulfonic acid and salts thereof (also referred to as "alkylbenzene sulfonic acid (salt)" in the present disclosure) have strong anionic properties due to being sulfonic acid-based. When added to a dyeing solution containing cationized cellulose fibers, the cationism of the cationized cellulose fibers can be weakened and excessive adhesion of the anionic dye to the fiber surface can be suppressed. In the cationized cellulose fiber, it is considered that the anionic dye forms an ionic bond with a large number of cation sites existing on the fiber surface, and it is difficult for the anionic dye to penetrate into the fiber. Alkylbenzene sulfonic acid (salt) moderately blocks such cation sites on the cationized cellulose fibers. As a result, the anionic dye can move not only on the fiber surface but also inside the fiber, and it is considered that the leveling property and the dyeing fastness (particularly the wet dyeing fastness) are improved.

When the cationicity of the cationized cellulose fiber is weakened, the affinity between the anionic dye and the cation site on the fiber is relaxed, resulting in increased mobility of the dye (and thus widespread diffusion), which is also uniform dyeing. Contributes to improving sex. For example, when a reactive dye (that is, a dye having a reaction site capable of forming a covalent bond with a hydroxyl group in cellulose) is used as the dye, the reaction site of the dye and the cationized cellulose fiber are affected by the increased mobility of the dye. The increased chance of access to the hydroxyl groups facilitates the formation of covalent bonds between the dye and the cationized cellulose fibers. The covalent bond is a stronger bond than, for example, an ionic bond, and an increase in the number of covalent bonds contributes to an improvement in dyeing fastness. Therefore, when the leveling agent of the present disclosure is applied to a dyeing system using a reactive dye, the advantage of improving the dyeing fastness (particularly the wet dyeing fastness) is remarkable. High wet dyeing fastness is advantageous in that the dye does not easily come off from the textile product during sweating during wearing, washing, etc. The wet dyeing fastness can be evaluated by the dyeing fastness test method for sweat of JIS L 0848 and the dyeing fastness test method for washing of JIS L 0844.

As described above, the leveling agent of the present disclosure has a unique advantage of being able to solve the problems peculiar to dyeing cationized cellulose fibers using anionic dyes.

（式中、Ｒは、炭素数１〜２２のアルキル基を表し、Ｍ^ｎ+は、ｎ価カチオンを表し、そしてｎは１又は２である。）
で表される化合物が挙げられる。 [Alkylbenzene sulfonic acid and salts thereof]
As the alkylbenzene sulfonic acid and its salt (alkylbenzene sulfonic acid (salt)), the following general formula (1):

(In the formula, R represents an alkyl group having 1 to 22 carbon atoms, M ^{n +} represents an n-valent cation, and n is 1 or 2.)
Examples thereof include compounds represented by.

In the general formula (1), R is an alkyl group having 1 to 22 carbon atoms. The alkyl group may be a straight chain or a branched chain, but a straight chain is preferable in terms of good biodegradability. The number of carbon atoms of the alkyl chain is preferably 10 to 18 from the viewpoint of soaking property, and is 10 to 16 in one embodiment.

In the general formula (1), M is an n-valent cation. For example, when n = 1, M ⁺ includes H ⁺ , alkali metal cations (sodium cation (Na ⁺ ), potassium cation (K ⁺ ), etc.), ammonio group-containing cations (ammonium cation (NH ₄ ⁺ ), alkanol). (Ammonium cation, etc.) can be exemplified. The alkanolammonium cation has the following general formula (2):
N (R ¹ _p ) H _4-p ⁺ (2)
(In the formula, R ¹ is a hydroxyalkyl group having 1 to 3 carbon atoms, and p is an integer of 1 to 3).
Can be exemplified. When n = 2, M ²⁺ includes alkaline earth metal cations (calcium cation (Ca ²⁺ ), magnesium cation (Mg ²⁺ ), zinc cation (Zn ²⁺ ), barium cation (Ba ²⁺ )). Etc.) can be exemplified. Examples of the alkanolammonium cation include an ammonium cation having 1 to 3 hydroxyalkyl groups having 1 to 3 carbon atoms (preferably a monoethanolammonary cation, a diethanolammonium cation, a triethanolammonium cation, etc.). ^{M is preferably H +} or Na ⁺ from the viewpoint of good leveling property and availability.

The alkylbenzene sulfonic acid salt is a compound (hydroxide, which gives an alkylbenzene sulfonic acid having an alkyl group corresponding to R in the general formula (1) ^{and a cation component corresponding to M n + in the general formula (1).} It may be prepared by reacting with amine etc.). For example, sodium alkylbenzene sulfonic acid obtained by neutralizing alkylbenzene sulfonic acid having 10 to 18 carbon atoms with sodium hydroxide, and diethanolamine alkylbenzene sulfonic acid salt obtained by neutralizing alkylbenzene sulfonic acid having 10 to 18 carbon atoms with diethanolamine. , Alkylbenzenesulfonic acid triethanolamine salt obtained by neutralizing alkylbenzenesulfonic acid having 10 to 18 carbon atoms with triethanolamine and the like are preferable.

[Additional ingredients]
The leveling agent may further contain additional components in addition to the alkylbenzene sulfonic acid (salt). Examples of the additional component include surfactants (those not the alkylbenzene sulfonic acid (salt) of the present disclosure), solubilizers, defoamers, inorganic salts, solvents, etc., and those known to those skilled in the art can be appropriately selected. It's okay. As the surfactant, a nonionic surfactant and an anionic surfactant other than the alkylbenzene sulfonic acid (salt) of the present disclosure are preferable.

Nonionic surfactants include, for example, aliphatic alcohols or phenols having 1 to 22 carbon atoms, alkyl (alkyl groups having 1 to 10 carbon atoms) phenols, mono or polystyreney phenols, and mono or polystyreneated alkyls (alkyls). Examples thereof include alkylene oxides (2 or 3 carbon atoms of alkylene oxides) of alcohols such as phenols having 1 to 10 carbon atoms in the group.

Examples of the anionic surfactant include alkane sulfonate, α-olefin sulfonate, α-sulfo fatty acid methyl ester, alkyl sulfate ester salt, alkyl phosphate ester salt, and polyoxyalkylene alkyl monoether sulfate ester salt. Alternatively, a phosphate ester salt, etc. may be mentioned. These anionic surfactants can be used in the form of alkali metal salts, alkaline earth metal salts, ammonium salts, alkanolamine salts and the like.

The solvent is typically water, but may include, for example, diethylene glycol or the like.

Suitable compositions of the leveling agent include alkylbenzene sulfonic acid (salt): 10% by mass to 50% by mass, surfactant: 0.5% by mass to 10% by mass, solubilizer: 0% by mass to 30% by mass, Defoaming agent: A composition containing 0.01% by mass to 5% by mass and the balance being a solvent can be exemplified.

<Manufacturing method of cationized cellulose fiber dyed product>
One aspect of the present invention provides a method for producing a cationized cellulose fiber dyed product, which comprises dyeing the cationized cellulose fiber in the presence of the leveling agent of the present disclosure.

(Cationized cellulose fiber)
The cationized cellulose fiber may be one in which the functional group of the cellulose fiber is cationized by a conventionally known method to introduce a cationic group (for example, a quaternary ammonium group). The cationized cellulose fibers may be unmodified or modified, and are semi-synthetic such as natural cellulose fibers such as cotton, regenerated cellulose fibers such as rayon and cupra, and acetate (that is, esterified-modified cellulose). Cellulose fibers can be mentioned. Cationic groups are usually associated with counterions (eg, chloride ions). Examples of the cationized cellulose fiber include fibers in which the cellulose fiber is quaternary ammonium etherified (for example, ammonium chloride etherified). As the cationizing agent, glycidyltrimethylammonium chloride or the like can be used. The rate of introduction of cationic groups per anhydrous glucose unit is not limited to this, and may be, for example, 0.1% to 10%.

The cationized cellulose fiber may be used in a state of being compounded with other fibers by blending, blending, twisting, cross-weaving, cross-knitting, entanglement, fusion, adhesion and the like. Examples of other fibers include natural fibers, regenerated fibers, semi-synthetic fibers, synthetic fibers, and blended fibers or composite fibers thereof, and non-cationized cellulose fibers can also be used. Examples of natural fibers include hemp, wool, cotton and the like, examples of recycled fibers include rayon and cupra, examples of semi-synthetic fibers include acetate and the like, and examples of synthetic fibers include polyester, polyamide, acrylic and spandex. The form of the fiber is not particularly limited, and examples thereof include cotton, sliver, yarn, and cloth (knitted fabric, woven fabric, non-woven fabric, etc.). The ratio of the cationized cellulose fibers in the fibers to be dyed is preferably 3% by mass to 100% by mass, more preferably, in that the build-up property is good (that is, the amount of dyeing increases satisfactorily as the dye concentration increases). It is preferably 5% by mass to 100% by mass, and more preferably 10% by mass to 100% by mass. In addition to being useful for dyeing cationized cellulose fibers, the leveling agent of the present disclosure can not give significant inconvenience to dyeing other fibers.

(dye)
As the dye, an anionic dye is typically used. Examples of anionic dyes include reactive dyes, direct dyes, acid dyes, and metal-containing dyes. As the reactive dye, a dye having reactivity with the hydroxyl group of the cellulose fiber can be used. As the direct dye, a dye capable of forming a hydrogen bond with the cellulose fiber is suitable.

Preferable examples of reactive dyes are vinyl sulfone dyes, dichlorotriazine dyes, dichloroquinoxalin dyes, fluoromethylchloropyrimidine dyes, monofluorotriazine dyes, trichloro dyes in terms of good reactivity with cationized cellulose fibers. Pyrimidine dyes, monochlorotriazine dyes, etc.

The amount of the dye used with respect to 100 parts by mass of the cationized cellulose fiber is preferably 0.001 part by mass to 15 parts by mass, and more preferably 0.01 part by mass to 10 parts by mass.

(Amount of alkylbenzene sulfonic acid (salt) used)
The amount of the alkylbenzene sulfonic acid (salt) used is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the cationized cellulose fiber. The amount used is preferably 0.1 part by mass or more, more preferably 0.3 parts by mass or more from the viewpoint of obtaining good leveling property, and preferably 15 parts by mass from the viewpoint of obtaining good build-up property. Parts or less, more preferably 10 parts by mass or less, still more preferably 3 parts by mass or less.

The apparatus used for dyeing is not particularly limited, and a conventionally known dyeing machine can be used. For example, a liquid flow dyeing machine, a Wins dyeing machine, a jigger dyeing machine, a beam dyeing machine, a cheese dyeing machine, an Overmeier dyeing machine, a high pressure jet dyeing machine and the like can be used.

The leveling agent may be brought into contact with the cationized cellulose fibers at any time before the dye, at the same time as the dye, or after the dye, but from the viewpoint of obtaining a good leveling property improving effect, the leveling agent is more than the dye. Also preferably contacted with cationized cellulose fibers before. For example, it is preferable to contact the cationized cellulose fiber with a leveling agent 3 to 30 minutes before the dye is brought into contact with the fiber. When the time from the contact of the leveling agent to the contact of the dye is 3 minutes or more, the effect of improving the leveling property is good. The time from the contact of the leveling agent to the contacting of the dye is preferably 30 minutes or less from the viewpoint of economy because the effect of improving the leveling property does not change remarkably even if the time is longer than 30 minutes. In a typical embodiment, the cationized cellulose fibers are contacted with a liquid medium (including, for example, water and optionally a surfactant, etc.) and then with a leveling agent and then with a dye. For example, a dipping bath made of the above liquid medium can be formed, the cationized cellulose fibers can be dipped in the dipping bath, and then a leveling agent and then a dye can be added to the dipping bath.

The temperature of the immersion bath during the leveling treatment may be in the temperature range conventionally used when using the leveling agent, but is usually 10 ° C. to 60 ° C., preferably 15 ° C. to 55 ° C., more preferably. It may be 20 ° C to 50 ° C. Within the above range, no special cooling or the like is required, the economy is excellent, and the leveling effect is also good.

The bath ratio during the leveling treatment and the dyeing treatment (that is, the mass ratio of the fiber to be dyed: the immersion bath) is preferably 1: 3 to 1:50, more preferably 1: 4 to 1:20. Good.

Conventionally known conditions may be applied as the dyeing treatment conditions, and examples thereof include a heating condition in which the immersion bath temperature is 40 ° C. to 135 ° C. and a condition in which the dyeing treatment time is 30 minutes to 90 minutes.

After the dyeing treatment, a cationized cellulose fiber dyed product can be obtained through conventionally known steps such as soaping and washing.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

<Manufacturing of cationized cellulose fiber>
A 100% cotton twill fabric (as a cellulose fiber) was cationized under the following conditions to obtain a cationized fabric as a cationized cellulose fiber.
(Cationization treatment conditions)
Used equipment:
Mini color dyeing machine (manufactured by Texam Giken Co., Ltd.)
Cationic solution:
In water, GTA-80 (manufactured by Yokkaichi Chemical Co., Ltd., glycidyltrimethylammonium chloride 80%) is 60 g / L (60 g per 1 L of water), and NaOH is 9 g / L (9 g per 1 L of water). To obtain a cationized solution.
Processing conditions:
In the above dyeing machine, after performing cationization treatment at 80 ° C. for 60 minutes at a bath ratio of 1:10 (cellulose fiber: cationized solution, mass standard), the dough was taken out, neutralized with acetic acid, washed with water, dehydrated, and so on. Drying was performed to obtain a cationized dough.

<Manufacturing of cationized cellulose fiber dyed products>
The cationized dough obtained above was dyed under the following conditions to obtain a cationized cellulose fiber dyed product.

[Examples 1 to 5, Comparative Examples 1 to 11]
A color pet dyeing machine (manufactured by Nippon Dyeing Machinery Co., Ltd.) was used for the dyeing treatment. The cationized fabric was wrapped around the holder attached to the dyeing machine, and the top and bottom were fixed with rubber bands to fix the cationized fabric to the holder. The cationized dough was set in the dyeing machine, water (as an immersion bath) was introduced, and the temperature of the immersion bath was adjusted to 40 ° C. At 40 ° C., a leveling agent was added to the immersion bath, and then the dye was added 10 minutes after the addition of the leveling agent and held for 5 minutes. Next, the temperature of the immersion bath was raised from 40 ° C. to 2 ° C./min, a dyeing aid was added when the temperature reached 60 ° C., and the immersion bath was held at 60 ° C. for 60 minutes to proceed with dyeing. The dough was taken out (dyeing finished). After neutralizing with a 1 g / L acetic acid aqueous solution, the product was washed with water in running water, dehydrated and dried (60 ° C. × 30 minutes) to obtain a cationized cellulose fiber dyed product.
The details of the above components used in the immersion bath are as follows.

(1) Leveling agent The compounds shown in Table 1 were used in the amounts shown in Tables 2 and 3.

(2) Dye C. I. Reactive Red 21 (Remazol Brilliant Red BB 150%, manufactured by Dyster) was added to 100 parts by mass of the cationized dough by 0.6 parts by mass (for Examples 1 to 3 and Comparative Examples 1 to 9) or 1.8. It was used in an amount of parts by mass (for Examples 4 and 5 and Comparative Examples 10 and 11).

(3) Dyeing aid Soda ash was used in an amount of 10 g / L (10 g with respect to 1 L of water in the immersion bath).

[Examples 6 to 7, Comparative Examples 12 to 14]
As the leveling agent, the compounds of the types and amounts shown in Tables 1 and 4 were used, and as the dye, C.I. I. Reactive Black 5 (Sumifix Black B 150%, manufactured by Sumika Chemtech) was used in an amount of 0.5 parts by mass with respect to 100 parts by mass of the cationized dough. A cationized cellulose fiber dyed product was obtained in the same manner as in Example 1 except that the temperature reached 50 ° C. and the temperature at which the immersion bath was held for 60 minutes was set to 50 ° C.

<Evaluation of uniform dyeing>
The degree of dyeing unevenness of the cationized cellulose fiber dyed products obtained in the above Examples and Comparative Examples is visually evaluated in the following 5 grades from 5th grade (no unevenness) to 1st grade (very unevenness). did.
Grade 5 (no unevenness)
4th grade (a little unevenness is admitted)
Level 3 (slightly uneven)
Level 2 (many unevenness)
Level 1 (very uneven)
The results are shown in Tables 2-4.

From the results shown in Tables 2 to 4, it can be seen that the alkylbenzene sulfonate compound 1 or 2 gives significantly better leveling property as compared with the comparative compounds 3 to 9.

The leveling agent of the present disclosure is useful in the production of a cationized cellulose fiber dyeing product because it can impart good leveling property particularly when dyeing a cationized cellulose fiber with an anionic dye.

Claims (3)

A leveling agent for dyeing cationized cellulose fibers, which comprises at least one sulfonic acid compound selected from the group consisting of alkylbenzene sulfonic acids and salts thereof. The leveling agent according to claim 1, wherein the alkyl group of the alkylbenzene sulfonic acid has 10 to 18 carbon atoms. A method for producing a cationized cellulose fiber dyed product.
A method comprising dyeing a cationized cellulose fiber in the presence of the leveling agent according to claim 1 or 2.