JP6090989B2 - Dyeable fiber composition - Google Patents

Description

  The present invention relates to a dyeable fiber composition. More specifically, the present invention relates to a novel dyeable fiber composition capable of obtaining good dyeability by adding specific hydrotalcites to fibers that have been difficult to dye. Furthermore, the present invention relates to a method for improving dyeing fastness that suppresses the detachment of dyes by washing or the like after dyeing the dyeable fiber.

Polyolefin fibers such as polypropylene and polyethylene are nonpolar polymers and can therefore be bound by dyes. Since it does not have a polar group, it cannot be dyed with a dye. It has been a challenge since these polymers were developed to enable dyeing with dyes.
Therefore, a method of adding a pigment to a resin and dyeing it before spinning is performed. For this reason, there is an inconvenience that there is no flexibility that can be dyed in response to changes in the market needs, and because there are fewer types of colors compared to dyeing methods with dyes, polyolefin fibers such as polypropylene fibers are compared to dyeable fibers. The applications used have been limited.
Moreover, although there is dyeability, the dyeing power is relatively weak. For example, polyurethane fibers have another problem. It is rarely used alone, and in most cases it is used by blending with nylon or polyester, so there is a problem of uneven dyeing between the blended nylon or polyester and polyurethane, reducing the commercial value. There is.

  In order to solve the problem of dyeability of the fiber, the present inventors made use of the anion exchange property of hydrotalcite to melt and mix the hydrotalcite in the resin before spinning, and after spinning, the anion We proposed the following three technologies that can be dyed with dyes (acid dyes).

Japanese Unexamined Patent Publication No. 2000-119510, Japanese Patent No. 3671191 In the technique of Patent Document 1, at least one monovalent anion selected from the group consisting of NO ₃ ⁻ , Cl ⁻ , Br ⁻ , ClO ₄ ⁻ , HCOO ⁻ , and CH ₃ COO ⁻ is used as the interlayer anion of hydrotalcites. This is a polyurethane composition containing 0.1 to 20% by weight of hydrotalcite as a seed in polyurethane.
JP2007-303025, Japanese Patent No. 4728874 The technology of Patent Document 2 is based on the fact that an interlayer anion of hydrotalcite is an ion of a carboxylic acid having an aromatic group in which 1 to 3 alkyl groups having 1 to 5 carbon atoms are bonded, or an aromatic amine sulfone. This is a polyurethane elastic fiber composition in which hydrotalcites which are acid ions are blended in an amount of 0.1 to 20% by weight based on the polyurethane polymer.
Japanese Patent Application Laid-Open No. 2006-351894, Japanese Patent No. 4828398 The technique of Patent Document 3 is a fiber composition containing 0.1 to 20% by weight of hydrotalcite whose interlayer anion is a higher fatty acid ion having 10 to 25 carbon atoms with respect to the fiber.

From the first technique to the second technique, and further to the third technique, the diameter of the anion entering the interlayer of the hydrotalcite is increased, and the dyeability is improved correspondingly, Despite the third technique, it has become possible to dye with a blue dye, which has been the most difficult to dye until now, and it has become possible to dye all colors.
However, as a result of examining the entire dyeing process in detail, in order to ensure economical productivity in a dry spinning process such as polypropylene, it is necessary to set the spinning temperature to about 280 to 300 ° C. It was found that the higher fatty acid ions between the layers of hydrotalcite, which is the third technique, are partially pyrolyzed.
Accordingly, a first problem is to provide a dyeable fiber that can be dyed in all colors including blue having a heat resistance of about 300 ° C. or higher.

  The second problem is that the third technique still solves the problem that a part of the dye is released into water or an organic solvent (such as tetrachloroethylene used for dry cleaning) after washing, That is to improve dyeing fastness.

  The present invention provides the following formula (1)

[Chemical 1]
(M ²⁺ ) _1-x (M ³⁺ ) _x (OH) ₂ (A ⁻ ) _x · mH ₂ O (1)
(Wherein, M ²⁺ is at least one divalent metal such as Mg or Zn, M ³⁺ is at least one trivalent metal such as Al or Ga, and A ⁻ is an alkyl group having 8 carbon atoms. Or more, preferably 10 to 14 alkylbenzene sulfonate ions, preferably at least one kind of linear alkyl benzene sulfonate ions, and x and m are each 0 <x <0.5, preferably 0.2 ≦ x ≦ 0.45, particularly preferably 0.25 ≦ x ≦ 0.4, 0 ≦ m <5, preferably 0 ≦ m <2. , acrylic, acetate, nylon, polyvinylidene, vinylon, polyacetal, polyurethane, polyester, polyethylene, polyvinyl chloride, polychlal, polypropylene and polyurethane To fibers made from a material selected from the down provides a dyeable fiber composition characterized in that it contains 0.1 to 30 wt%.

  Further, after dyeing the dyeable fiber, an acid of a polymer type anion such as alginic acid, polycarboxylic acid, polycarboxylic acid partial alkyl ester, naphthalenesulfonic acid formalin condensate, carboxymethylcellulose (CMC), polyphosphoric acid and / or Add alkali metal salt, and then add and react with polyvalent metal ions such as Ca, Mg, Al, Ti, Zr, etc. to coat the surface of hydrotalcite with polyvalent metal salt of polymer type anion Provides a method of enhancing dyeing fastness.

  According to the present invention, the heat resistance of the dyeable fiber, which has been a problem, is about 300 ° C. or more, and there is no problem of spinning workability, and the dye is removed from the fiber into water or an organic solvent during washing. Almost no recognition was observed, and the dyeing fastness was improved.

In formula (1), the interlayer anion A ⁻ of the hydrotalcite used in the present invention is changed to an alkylbenzene sulfonate ion to ensure an interlayer distance equal to or greater than the size of the dye necessary for ensuring good dyeability. The heat resistance temperature, which is a drawback of higher fatty acids, can be improved by about 50 ° C. Alkyl benzene sulfonate ions include straight-chain (soft) and branched types, but the straight-chain ion can increase the interlaminar distance with a smaller number of carbons, and the hydrophilicity is improved with the same number of carbons. (The dye is easily accessible). The alkyl group moiety has 8 or more carbon atoms, preferably 10 to 14 carbon atoms. The reason is that the greater the number of carbons, the greater the distance between the layers, making it easier for anionic dyes to enter the layers and improving the dyeability. However, the greater the number of carbons, the worse the hydrophilicity and hinder access to the dye. Due to these conflicting actions, there is an optimum range of carbon numbers.
Preferred anions, such as linear dodecylbenzene sulfonic acid ions _{(n-C 10 H 21 C} 6 H 4 SO 3 -), a straight-chain undecyl benzene sulfonate ion _{(n-C 11 H 23 C} 6 H 4 SO 3 ^-), linear dodecyl benzene sulfonate ion _{(n-C 12 H 25 C} 6 H 4 SO 3 -), linear tridecyl benzene sulfonate ion _{(n-C 13 H 2 7C} 6 H 4 SO 3 -), linear tetradecyl benzene sulfonate ion _{(n-C 14 H 29 C} 6 H 4 SO 3 -) , and the like.

The most difficult blue dye to dye has an ionic diameter of about 20 mm, so that the strongest peak angle of the X-ray diffraction of hydrotalcites is the unit layer thickness (basic layer thickness is About 4.7 mm, the thickness of the intermediate layer containing anions is about 20 mm. Here, the basic layer corresponds to an octahedral layer made of M ²⁺ and M ³⁺ hydroxides), and it is preferably about 25 mm or more. . The hydrotalcite having an aromatic amine sulfonate ion proposed in Patent Document 2 as an interlayer ion has a unit layer thickness much shorter than 25 mm, and thus has particularly poor blue dyeability.

A ^{− in the} formula (1) can contain a small amount of anions such as SO ₄ ²⁻ , NO ₃ ⁻ , Cl ⁻ , and CO ₃ ²⁻ as impurities derived from raw materials, the atmosphere, and the like. However, it is preferable that the amount of these impurities is small. For example, it is 20 mol% or less, preferably 10 mol% or less, particularly preferably 5 mol% or less of all interlayer ions.

As M ^{2+ in the} formula (1), divalent ions such as Mg, Ni, Zn, Cu, and Co can be used. However, for reasons such as whiteness, low toxicity, and cost, the divalent ions of Mg and / or Zn Is preferably used. As M ³⁺ , trivalent ions such as Al, Fe, Ga, In, and Co can be used, but Al is most preferable for the same reason as M ²⁺ .

The range of x in formula (1) can be as broad as 0 <x <0.5, but the amount of interlayer anions increases corresponding to the increase in x. Since the amount which can be combined also increases, it is preferable that x is large. However, the maximum value of x is about 0.4 corresponding to the maximum amount of M ^{3+ that} can be dissolved in M ²⁺ (OH) ₂ . Therefore, a particularly preferable range of x is 0.25 ≦ x ≦ 0.4.

The hydrotalcite of the formula (1) needs to be well dispersed in the fiber. For this purpose, the secondary particles are 2 μm or less, particularly 1.0 μm or less, and the BET specific surface area is 30 m. ² / g or less, and particularly preferably 20 m ² / g or less.

  The compounding quantity with respect to the fiber of the hydrotalcite of Formula (1) is 0.1-30 weight%, Preferably it is 1-20 weight%, Most preferably, it is 5-15 weight%. In order to improve the workability such as spinning, it is preferable to use a hydrotalcite, for example, by preparing a masterbatch having a concentration of 20 to 50% by weight with respect to the resin and then mixing it with a virgin resin. .

The present invention further provides a method for preventing a part of the dye from being released into water or an organic solvent after washing after dyeing the dyeable fiber of the present invention with an anionic dye (acidic dye). This prevention method is the next A process or the B process following A.
(A) Polyphosphoric acid such as tetrapolyphosphoric acid, hexametaphosphoric acid, acidic hexametaphosphoric acid or alkali metal or ammonium salt thereof, carboxymethylcellulose, alginic acid or alkali metal or ammonium salt thereof, olefin / maleic acid copolymer, β-naphthalene sulfone Acid formalin condensate, polycarboxylic acid, polycarboxylic acid, polycarboxylic acid partial polyester anion (polycarboxylic acid, polysulfonic acid) acid or alkali metal or ammonium salt thereof selected from at least one or more Is added to the dyed fiber and surface-treated. Preferably, after treatment A, (B) a polyvalent metal ion solution such as Ca, Mg, Zn, Al or the like is further added and reacted with the polymer-type polyanion to form a hardly soluble film.

  The addition amount of the polymer polyanion is 0.01 to 20%, preferably 0.1 to 10%, based on the weight of the hydrotalcite. The addition amount of the polyvalent metal ion to be reacted with the polymer type polyanion may be 1 to 100% in terms of metal with respect to the addition amount of the polymer type polyanion.

The polymer polyanion needs to be larger than the interlayer distance of the hydrotalcite in which the dye is bonded between the layers, and the size is about 30 mm or more, preferably about 50 mm or more. If it is such a polymer type polyanion of such a size, it is hardly substituted by ion exchange with a dye. Various solvents can be used for the polymer polyanion solution, but water is most preferable. The reaction temperature is not particularly limited but is preferably 40 to 90 ° C.
The polymer surface of the hydrate talcite that is positively charged is coated with the polymer polyanion. This alone is effective in preventing the release of interlayer anions, but the polyvalent metal ion to be added next reacts with some anions of the polyanion to form a sparingly soluble film, and is a dye located between the layers of hydrotalcites. Is more strongly prevented from being released into the solvent.

The production of hydrotalcites of formula (1) is conventionally known. For example, an aqueous solution of a water-soluble salt of M ²⁺ and M ³⁺ , an alkali metal hydroxide such as sodium hydroxide and / or an alkali aqueous solution of an alkali metal carbonate such as sodium carbonate, and the pH is adjusted in an aqueous medium with stirring. CO ₃ ^2- type (interlayer anion is CO ₃ ²⁻ ) hydrotal, co-precipitated with 8 or more, preferably 9 to 11 and then washed with an aqueous alkali metal carbonate solution and then with water. Synthesize sites. This is hydrothermally treated in an autoclave at 100 ° C. or higher, preferably 120 to 200 ° C., preferably 10 hours or longer to reduce crystal growth and aggregation. Thereafter, CO ₃ ²⁻ is ion-exchanged with NO ₃ ⁻ or Cl ⁻ with a monovalent acid such as nitric acid or hydrochloric acid, followed by ion exchange with an alkali metal salt aqueous solution of alkylbenzene sulfonic acid, and the target formula ( 1) Hydrotalcite can be produced.

  The ion exchange reaction is preferably carried out with a supply amount of the target anion amount of 0.8 to 1.5 equivalents, particularly 0.9 to 1.2 equivalents of the amount of interlayer anions. After the ion exchange reaction, conventional processes such as washing with water, drying, pulverization, and classification can be appropriately selected and used.

As the fiber used in the present invention, for example, almost all fibers such as acrylic, acetate, nylon, vinylidene, vinylon, polyacetal, polyurethane, polyester, polyethylene, polyvinyl chloride, polyclar, and polypropylene can be used. , Elastic polyurethane fiber.
The dyeable fiber composition of the present invention includes not only fibers but also a dyeable resin composition before spinning.

  The dyeable fiber of the present invention can be produced by mixing the polymer with the hydrotalcite represented by the formula (1) and then spinning it. As the spinning method, any of conventionally known dry, wet and melt can be appropriately selected and processed into fibers. In the case of dry type and melt spinning, it is preferable to use a master batch in which hydrotalcite is previously melt-kneaded in a resin and the concentration thereof is about 10 to 50% with respect to the resin.

As the fiber dyeing method, the same dyeing method as that for conventional synthetic fibers and natural fibers can be used. For example, a dyeing method such as a pad steam method, a pad thermofix method, dip dyeing, a printing method, and a spray method can be applied.
As the dyeing machine, a normal dyeing machine such as a liquid dyeing machine, a wins dyeing machine, and an airflow dyeing machine can be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited only to these Examples.

Various measurements were performed by the following methods.
(1) Measurement of unit thickness of hydrotalcites X-ray diffraction pattern was measured by a powder X-ray diffraction method, and determined from the strongest peak position on the lowest angle side by the Bragg equation.
(2) BET specific surface area It measured by the liquid nitrogen adsorption method.
(3) Measurement of particle size distribution The sample powder was put in ethanol and treated with ultrasonic waves for 5 minutes, and then the particle size distribution in an ethanol solvent was measured by a laser diffraction method.
(4) Dyeability evaluation test Polypropylene having a melt flow index of 110 g / 10 min, hydrotalcite and an antioxidant (IRGANOX 1010) were mixed at a weight ratio of 80: 20: 0. 2 and this mixture was melt-kneaded at about 240 ° C. using a twin-screw extruder to produce pellets having a diameter of about 3 mm and a length of about 4 mm. 20 g of this pellet was added to 300 ml of an aqueous solution in which 6 g of a blue dye: Nirosan Blue N-GFL was dissolved, heated at about 90 ° C. for 1 hour, dyed, and washed with water. The washed pellets were dispersed in water, added with the polymer polyanion and the polyvalent metal ion in this order under stirring, washed with water and dried. The dyeing level of the pellets after drying was determined according to the following criteria.
Grade 5 dark blue
4th grade Blue
Grade 3 light blue
Level 2 Slight blue
Grade 1 White (5) Fastness of dyeing 2 g of the same sample used for the dyeing test is placed in a test tube, 10 ml of water or tetrachloroethylene is added, and the mixture is allowed to stand at about 30 ° C. for 20 hours, and then dyed into the solvent. The degree of elution was determined visually according to the following criteria. Class 0 represents the best.
<Dye elution level>
Grade 0 Colorless: Zero elution
First grade Slight blue: Elution is slight
Second grade Light blue: There is a little elution
Class 3 Dark blue: Many elutions (6) Heat resistance test DTA-TGA of hydrotalcite powder was measured and evaluated by weight loss rate from 200 ° C to 300 ° C.

<Dye: Synthesis of hydrotalcites whose interlayer anion is mainly composed of dodecyl (lauryl) benzenesulfonate ion>
CO ₃ type hydrotalcite (BET specific surface area = 12 m ² / g, average secondary particle size = 0.46 μm, chemical composition: Mg _0.68 Al _0.32 (OH) ₂ (CO ₃ ) _0.16 · _0.5 H ₂ O)) is added to about 2 liters of warm water (about 70 ° C.), and with stirring, 1.9 liters of a 0.5 mol / liter nitric acid aqueous solution is added with a pH between about 3-4. And added. In this reaction, CO ₃ ²⁻ was ion-exchanged into NO ₃ ⁻ . Next, after neutralizing 256 g of linear alkylbenzene sulfonic acid (Nippon Yushi Co., Ltd., Soft Oarai 5S), which is mainly composed of linear dodecylbenzene sulfonic acid equivalent to NO ₃ , with caustic soda, the pH was adjusted to about 7 and dissolved. About 2 liters of the aqueous solution was added to NO ₃ type hydrotalcite with stirring, and an ion exchange reaction was performed at about 80 ° C. for about 30 minutes. Thereafter, filtration under reduced pressure, washing with water, drying (about 120 ° C.), and pulverization were performed.

As a result of measuring X-ray diffraction of the obtained powder, it was only diffraction of hydrotalcites. Since the strongest diffraction peak is at about 30.4 mm, this corresponds to the unit layer thickness of hydrotalcites. In this X-ray diffraction pattern, there were almost no strongest diffraction peaks of NO ₃ type (d = about 8.9Å) and CO ₃ type (d = about 7.6Å) hydrotalcites. The chemical composition obtained by chemical analysis, total organic carbon analysis and thermal analysis (DTA, TGA) measurement (quantification of the amount of interlayer water) was almost as follows. Mg _0.68 Al _0.32 (OH) ₂ (C ₁₂ H ₂₅ C ₆ H ₄ SO ₃ ) _0.32 · 0.5H ₂ O
In addition, Table 1 shows heat resistance data obtained from thermal analysis measurement.

This material had a BET specific surface area of 17 m ² / g, an average secondary particle size of 0.66 μm, and a maximum secondary particle size of 1.1 μm. This material was dried in a dryer at 120 ° C. for 2 hours, then kneaded with polypropylene according to the above formulation, pellets were prepared and dyed.

  50 g of dyed polypropylene pellets are put into 500 ml of water, and with stirring, 0.6 g of polymer type polyoxyalkylene carboxylic acid (manufactured by NOF Corporation, Marialim AKM0531) is dissolved in 50 ml of water, and further with NaOH. After neutralization, it was added and reacted at about 90 ° C. for 20 minutes. Thereafter, 20 ml of 0.5 mol / liter calcium acetate was added and allowed to react for about 5 minutes. Thereafter, filtration, washing with water and drying were carried out, and a dyeability and dyeing fastness test were conducted. The results are shown in Table 1.

[Comparative Example 1]
In Example 1, it carried out similarly to Example 1 except using a reagent primary lauric acid (dodecanoic acid) instead of a linear alkylbenzenesulfonic acid.
As a result of X-ray diffraction measurement of the obtained product, it was a diffraction pattern of only hydrotalcites, and the strongest diffraction peaks of NO ₃ type and CO ₃ type hydrotalcites were not recognized. From the position of the strongest diffraction peak, the unit layer thickness was about 24.1 mm, and the chemical composition was as follows.
Mg _0.68 Al _0.32 (OH) ₂ (C ₁₁ H ₂₃ COO) _0.32 · 0.4H ₂ O
This product had a BET specific surface area of 15 m ² / g, an average secondary particle size of 0.50 μm, and a maximum secondary particle size of 0.96 μm. Table 1 shows the heat resistance test results of this product, and the test results of the dyeability and fastness of dyeing performed on pellets prepared by blending and kneading 30% by weight of this product with polypropylene.

[Comparative Example 2]
In Example 1, it carried out like Example 1 except having used 149g of m-aminobenzenesulfonic acid instead of the linear alkylbenzenesulfonic acid. X-ray diffraction of the obtained product is a diffraction pattern of only hydrotalcites, except that there is a slight diffraction peak of about 8.9８ corresponding to NO ₃ type hydrotalcites. It was a diffraction pattern of hydrotalcite having a unit layer thickness of about 13.5 mm with ions as interlayer ions. The chemical composition of this product was almost as follows.
Mg _0.68 Al _0.32 (OH) ₂ (NH ₂ C ₆ H ₄ SO ₃ ) _0.31 (NO ₃ ) _0.1 · _0.4 H ₂ O
Table 1 shows the test results of heat resistance, dyeability and dyeing fastness.

[Comparative Example 3]
Table 1 shows the results of the dyeing test of the polypropylene pellets.

Claims (7)

Following formula (1)
[Chemical 1]
(M ²⁺ ) _1-x (M ³⁺ ) _x (OH) ₂ (A ⁻ ) _x · mH ₂ O (1)
(Wherein, M ²⁺ is at least one kind of divalent metal, M ³⁺ is at least one kind of trivalent metal, and A ⁻ is at least one kind of alkylbenzene sulfonate ion whose alkyl group has 8 or more carbon atoms. And x and m are in the range of 0 <x <0.5 and 0 ≦ m <5), respectively, and the dyes are acrylic, acetate, nylon, vinylidene. , vinylon, polyacetal, polyurethane, polyester, polyethylene, polyvinyl chloride, polychlal, dyeable fibers composition to fibers of a material selected from polypropylene and polyurethane, characterized in that it contains 0.1 to 30 wt%. The dyeable fiber composition according to claim 1, wherein in the formula (1), M ²⁺ and M ³⁺ are each Mg and / or Zn, Al. In the formula (1), A ^- is, according to claim 1 or 2 dyeable fiber composition according carbon atoms in the alkyl group is 10 or more linear alkyl benzene sulfonic acid ions. The dyeable fiber composition according to any one of claims 1 to 3 , wherein the hydrotalcite of formula (1) has a surface spacing of 25 mm or more. Dyeable fiber composition according to any one of claims 1-4 which fiber made of polypropylene or polyethylene. Dyeable fiber composition according to any one of claims 1-4 in which fibers are made of polyurethane. After dyeing the dyeable fiber according to any one of claims 1 to 6 with an anionic dye, (A) polyphosphoric acid, carboxymethylcellulose, alginic acid, polycarboxylic acid, polycarboxylic acid partial alkyl ester, naphthalenesulfonic acid Surface treatment with at least one polymer polyanion selected from alkali metal salts of formalin condensates, or (A) after treatment, and (B) polyvalent metal such as Ca, Mg, Zn, Al, etc. A method for enhancing dyeing fastness, characterized by adding and reacting ions.