JP7301696B2 - Leveling agent for dyeing cationized cellulose fibers - Google Patents

Description

The present invention relates to a leveling agent for dyeing cationized cellulose fibers and a method for producing cationized cellulose fiber dyed products 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 inherently have an anionic charge on the surface and are likely to cause poor dyeing due to electrical repulsion with anionic dyes _. A method of adding a neutral salt such as SO ₄ ) to the cellulose fiber has been used. A 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, this method requires the use of a large amount of neutral salt, which poses a problem of environmental load due to the waste liquid.

For the purpose of improving the dyeability of cellulose fibers (specifically, shortening the dyeing time and reducing dye loss), cationization of cellulose fibers has been conventionally proposed. For example, US Pat. No. 6,200,009 describes a method of treating cellulose fibers comprising contacting the cellulose fibers with a solution comprising a wetting agent, an alkaline composition and an ammonium salt. According to such a method, the cationic site (e.g., quaternary ammonium structure) introduced into the cellulose fiber forms an ionic bond with the anionic dye, thereby strongly dyeing the cellulose fiber with the dye. It is possible to shorten the time and reduce the loss of the dye, and reduce the burden on the environment.

On the other hand, various leveling agents have been proposed in order to improve levelness in dyeing cellulose fibers. For example, Patent Document 2 describes a compound obtained by addition polymerization of ethylene oxide to an alkylamine as a leveling agent for exhaust dyeing cellulosic fiber products or blended knitted and woven fiber products containing cellulosic fibers with direct dyes or reactive dyes, A compound obtained by esterifying an aliphatic polycarboxylic acid or an aromatic polycarboxylic acid is described. Further, Patent Document 3 describes a sulfate ester salt or a sulfonate obtained by sulfating a fatty acid ester having a specific structure as a leveling agent for absorbing and dyeing a cellulose fiber alone or a textile product containing a cellulose fiber with a reactive dye. be described. However, these leveling agents do not provide sufficient levelness for cationized cellulose fibers.

Japanese Patent Publication No. 2016-511331 JP-A-61-89383 JP-A-63-92787

Cationization of cellulose fibers as described in Patent Document 1 is advantageous in that anionic dyes can easily migrate from the dyeing solution to the cellulose fibers. However, cationized cellulose fibers have the problem that the dyeing speed is difficult to control and uneven dyeing tends to occur, compared to non-cationized cellulose fibers. That is, if the affinity between the cellulose fiber and the dye is too high, the dye will adhere to the cellulose fiber rapidly, resulting in localized dyeing. Even staining is difficult because it is also difficult to move to the inside.

One aspect of the present invention solves the above problems and provides a leveling agent that exhibits excellent levelness in dyeing cationized cellulose fibers, and a method for producing a product dyed with cationized cellulose fibers using the leveling agent. for the purpose.

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

According to one aspect of the present invention, a leveling agent that exhibits excellent levelness in dyeing cationized cellulose fibers, and a method for producing a product dyed with cationized cellulose fibers using the leveling agent can be provided.

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

<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 alkylbenzenesulfonic acids and salts thereof. Although not bound by theory, alkylbenzenesulfonic acids and their salts (also referred to as “alkylbenzenesulfonic acids (salts)” in the present disclosure) have strong anionic properties due to their sulfonic acid system. When added to a dyeing solution containing cationized cellulose fibers, the cationic property of the cationized cellulose fibers can be weakened and excessive adhesion of the anionic dye to the fiber surface can be suppressed. In cationized cellulose fibers, the anionic dye forms ionic bonds with many cationic sites present on the surface of the fiber, and is difficult to permeate into the interior of the fiber. Alkyl benzene sulfonic acids (salts) moderately block such cationic sites on the cationized cellulose fibers. It is believed that this allows the anionic dye to move not only to the surface of the fiber but also to the interior of the fiber, thereby improving levelness and color fastness (especially wet color fastness).

The weakening of the cationic character of the cationized cellulose fibers also results in increased dye mobility (and hence diffusion over a wider area) due to the relaxation of the affinity between the anionic dyes and the cationic sites on the fibers, which also contributes to level dyeing. contribute to the improvement of sexuality. For example, when a reactive dye (that is, a dye having a reactive site capable of forming a covalent bond with a hydroxyl group in cellulose) is used as the dye, the increased mobility of the dye causes the reaction sites of the dye and the cationized cellulose fibers to be separated. The increased opportunity for access to hydroxyl groups facilitates the formation of covalent bonds between the dye and the cationized cellulose fibers. A 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 color fastness. Therefore, when the leveling agent of the present disclosure is applied to a dyeing system with reactive dyes, the advantage of improving color fastness (especially wet color fastness) is remarkable. A high wet color fastness is advantageous in that the dye is less likely to come off from the textile product due to perspiration during wearing or during washing. The wet color fastness can be evaluated by the JIS L 0848 perspiration color fastness test method and the JIS L 0844 color fastness test method for washing.

As described above, the leveling agent of the present disclosure has unique advantages that can solve the problems inherent in dyeing cationized cellulose fibers with 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。 [Alkylbenzenesulfonic acids and salts thereof]
Alkylbenzenesulfonic acids and salts thereof (alkylbenzenesulfonic acids (salts)) are represented by the following general formula (1):

(Wherein, R represents an alkyl group having 1 to 22 carbon atoms, M ⁿ⁺ represents an n-valent cation, and n is 1 or 2.)
The compound represented by is mentioned.

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

In 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. As the alkanolammonium cation, the following general formula (2):
N ₍ ^R1p )H4 _-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. Alkanolammonium cations include ammonium cations having 1 to 3 hydroxyalkyl groups of 1 to 3 carbon atoms (preferably monoethanolammonium cation, diethanolammonium cation, triethanolammonium cation, etc.). M is preferably H ⁺ or Na ⁺ from the viewpoint of good levelness and availability.

Alkylbenzenesulfonates are compounds (hydroxides ^, amines, etc.). For example, sodium alkylbenzenesulfonate obtained by neutralizing alkylbenzenesulfonic acid having 10 to 18 carbon atoms with sodium hydroxide, alkylbenzenesulfonic acid diethanolamine salt obtained by neutralizing alkylbenzenesulfonic acid having 10 to 18 carbon atoms with diethanolamine. and alkylbenzenesulfonic acid triethanolamine salt obtained by neutralizing alkylbenzenesulfonic acid having 10 to 18 carbon atoms with triethanolamine.

[Additional ingredients]
The leveling agent may further contain additional components in addition to the alkylbenzene sulfonic acid (salt). Examples of additional components include surfactants (other than the alkylbenzenesulfonic acid (salt) of the present disclosure), solubilizers, antifoaming agents, inorganic salts, solvents, and the like, and those known to those skilled in the art can be appropriately selected. you can Preferred surfactants are nonionic surfactants and anionic surfactants that are not alkylbenzene sulfonic acids (salts) of the present disclosure.

Examples of nonionic surfactants include aliphatic alcohols or phenols having 1 to 22 carbon atoms, alkyl (alkyl group having 1 to 10 carbon atoms) phenols, mono- or polystyrenated phenols, and mono- or polystyrenated alkyl (alkyl The group has 1 to 10 carbon atoms and alkylene oxide (alkylene oxide with 2 or 3 carbon atoms) adducts of alcohols such as phenol can be mentioned.

Examples of anionic surfactants include alkanesulfonates, α-olefinsulfonates, α-sulfo fatty acid methyl esters, alkyl sulfates, alkyl phosphates, and sulfates of polyoxyalkylene alkyl monoethers. or phosphate salts, and the like. 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 also contain, for example, diethylene glycol.

A preferred composition of the leveling agent is alkylbenzenesulfonic 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, Defoamer: A composition containing 0.01% to 5% by mass and the remainder being a solvent can be exemplified.

<Method for producing cationized cellulose fiber dyed product>
One aspect of the present invention provides a method of making a dyed product of cationic cellulose fibers comprising dyeing cationized cellulose fibers in the presence of a 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). Cellulose fibers that are cationized can be unmodified or modified, and include natural cellulose fibers such as cotton, regenerated cellulose fibers such as rayon and cupra, and semi-synthetic fibers such as acetate (i.e., cellulose that has been esterified and modified). Cellulose fibers are mentioned. Cationic groups are usually associated with a counterion (eg chloride ion). Examples of cationized cellulose fibers include fibers obtained by subjecting cellulose fibers to quaternary ammonium etherification (for example, ammonium chloride etherification). Glycidyltrimethylammonium chloride or the like can be used as the cationizing agent. The cationic group introduction rate per anhydroglucose unit is not limited to this, but may be, for example, 0.1% to 10%.

The cationized cellulose fiber may be used in a composite state by blending, blending, twisting, weaving, knitting, entangling, fusing, bonding, or the like with other fibers. Other fibers include natural fibers, regenerated fibers, semi-synthetic fibers, synthetic fibers, and blended or composite fibers thereof, and non-cationized cellulose fibers can also be used. Examples of natural fibers include hemp, wool and cotton, examples of regenerated 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 includes cotton, sliver, thread, fabric (knitted fabric, woven fabric, non-woven fabric, etc.) and the like. The ratio of cationized cellulose fibers in the fibers to be dyed is preferably 3% by mass to 100% by mass, and more It is preferably 5% by mass to 100% by mass, 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 impart no significant disadvantages to dyeing other fibers.

(dye)
An anionic dye is typically used as the dye. Examples of anionic dyes include reactive dyes, direct dyes, acid dyes, and metallized dyes. As the reactive dye, a dye having reactivity with hydroxyl groups of cellulose fibers can be used. As direct dyes, dyes capable of forming hydrogen bonds with cellulose fibers are suitable.

Suitable examples of reactive dyes are vinyl sulfone dyes, dichlorotriazine dyes, dichloroquinoxaline dyes, fluoromethylchloropyrimidine dyes, monofluorotriazine dyes, trichloro Examples include pyrimidine dyes and monochlorotriazine dyes.

The dye is preferably used in an amount of 0.001 to 15 parts by weight, more preferably 0.01 to 10 parts by weight, per 100 parts by weight of the cationized cellulose fiber.

(Amount of alkylbenzenesulfonic acid (salt) used)
The amount of alkylbenzenesulfonic acid (salt) used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of cationized cellulose fibers. The amount used is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more from the viewpoint of obtaining good levelness, and preferably 15 parts by mass from the viewpoint of obtaining good build-up properties. parts or less, more preferably 10 parts by mass or less, and even more preferably 3 parts by mass or less.

There are no particular restrictions on the equipment used for dyeing, and conventionally known dyeing machines can be used. For example, jet dyeing machine, wince dyeing machine, Jigger dyeing machine, beam dyeing machine, cheese dyeing machine, Obermeyer dyeing machine, high-pressure jet dyeing machine and the like can be used.

The leveling agent may be brought into contact with the cationized cellulose fiber before the dye, at the same time as the dye, or after the dye. preferably prior to contacting the cationized cellulose fibers. For example, cationized cellulose fibers are preferably brought into contact with the leveling agent 3 to 30 minutes before contact with the dye. 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. Even if the time from the contact of the leveling agent to the contact of the dye exceeds 30 minutes, the effect of improving the leveling property does not significantly change, so from the viewpoint of economy, it is preferably 30 minutes or less. In a typical embodiment, the cationized cellulose fibers are contacted with a liquid medium (eg, including water and optionally surfactants, etc.) followed by a leveling agent and then a dye. For example, after forming an immersion bath comprising the above liquid medium and immersing the cationized cellulose fibers in the immersion bath, a leveling agent and then a dye can be added to the immersion bath.

The temperature of the immersion bath during the leveling treatment may be in the temperature range conventionally employed when using a leveling agent, but is usually 10°C to 60°C, preferably 15°C to 55°C, more preferably 15°C to 55°C. 20°C to 50°C. Within the above range, there is no need for special cooling or the like, which is excellent in terms of economy, and the effect of level dyeing is also good.

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

As the dyeing treatment conditions, conventionally known conditions may be applied, and examples thereof include a heating condition of an immersion bath temperature of 40° C. to 135° C. and a condition of a dyeing treatment time of 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.

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

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

<Production of cationized cellulose fiber dyed products>
The cationized fabric 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 Dye Machine Co., Ltd.) was used for the dyeing treatment. The cationized fabric was wrapped around a holder attached to the dyeing machine, and the upper and lower sides were fixed with rubber bands to fix the cationized fabric to the holder. The cationized fabric was set in the dyeing machine, water (as a dipping bath) was introduced and the dipping bath was adjusted to 40°C. At 40° C., the leveling agent was added to the dipping bath, then 10 minutes after the addition of the leveling agent, the dye was added and held for 5 minutes. Next, the temperature of the immersion bath is raised from 40°C at a rate of 2°C/min, and when the temperature reaches 60°C, a dyeing assistant is added, and the immersion bath is held at 60°C for 60 minutes to allow dyeing to proceed. The fabric was taken out (dyeing finished). After neutralizing with a 1 g/L acetic acid aqueous solution, the product was washed with 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. I. Reactive Red 21 (Remazol Brilliant Red BB 150%, manufactured by Deister) is 0.6 parts by mass (for Examples 1 to 3 and Comparative Examples 1 to 9) or 1.8 parts per 100 parts by mass of the cationized fabric. It was used in an amount corresponding to 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 per 1 L of water in the immersion bath).

[Examples 6-7, Comparative Examples 12-14]
As a 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) is used in an amount of 0.5 parts by mass with respect to 100 parts by mass of the cationized fabric, and the dyeing aid is added at a time when the immersion bath is 50%. A cationized cellulose fiber dyed product was obtained in the same manner as in Example 1, except that the temperature at which the dipping bath was held for 60 minutes was 50°C.

<Level dyeing evaluation>
The degree of dyeing unevenness of the cationized cellulose fiber dyed products obtained in the above Examples and Comparative Examples was visually evaluated in the following five grades from grade 5 (no unevenness) to grade 1 (extremely unevenness). bottom.
Grade 5 (no unevenness)
Grade 4 (a little unevenness is recognized)
Grade 3 (slightly uneven)
Grade 2 (many unevenness)
Grade 1 (Very uneven)
The results are shown in Tables 2-4.

From the results shown in Tables 2-4, it can be seen that the alkylbenzene sulfonate compounds 1 or 2 give significantly better levelness than the comparative compounds 3-9.

The leveling agent of the present disclosure is useful in the production of cationized cellulose fiber dyed products because it can impart good leveling properties when dyeing cationized cellulose fibers with anionic dyes.

Claims (4)

A leveling agent for dyeing cationized cellulose fibers with an anionic dye , comprising at least one sulfonic acid compound selected from the group consisting of alkylbenzenesulfonic acids and salts thereof. The leveling agent according to claim 1, wherein the alkyl group of the alkylbenzenesulfonic acid has 10 to 18 carbon atoms. A method for producing a cationized cellulose fiber dyed product, comprising:
A method comprising dyeing a cationized cellulose fiber with an anionic dye in the presence of a leveling agent containing at least one sulfonic acid compound selected from the group consisting of alkylbenzenesulfonic acids and salts thereof. 4. The method of claim 3, wherein the alkyl group of the alkylbenzenesulfonic acid has 10-18 carbon atoms.