JP4828398B2 - Fiber composition and dyeing assistant - Google Patents

Description

  The present invention relates to a fiber dyeing assistant, a fiber excellent in dyeability and fastness, and a fiber product thereof.

  The fiber can be dyed using an anionic or cationic dye having a chemical bond or strong affinity with the polar group of the fiber, in other words, cationic or anionic property.

  On the other hand, with polyurethane or polyester having a weak polar group or almost no polarity, there is a method in which empty marks are generated between fibers in high-temperature and high-pressure water, and a disperse dye is introduced into the empty marks to confine them.

  However, this method has a problem that costs are high and disperse dyes are discharged during high-temperature washing, so that the color shifts to other laundry, so-called firmness is poor. In many cases, UV resistance, heat resistance, etc. are insufficient.

  In the background as described above, the inventor of the present invention, based on a completely new concept, dyes polyurethane by adding hydrotalcite having a strong positive charge on the crystal surface represented by the following formula (2) to the polyurethane. It was proposed that the sex could be improved. (See Patent Document 1)

（但し、式中、Ｍ^２＋はＭｇおよびＺｎの２価金属の少なくとも１種を、Ｍ^３＋はＡｌおよびＦｅの３価金属の少なくとも１種を、Ａ⁻はＮＯ_３ ⁻，Ｃｌ⁻，Ｂｒ⁻，ＣｌＯ_４ ⁻，ＨＣＯＯ⁻およびＣＨ_３ＣＯＯ⁻からなる群から選ばれた１価アニオンの少なくとも１種を示し、ｘおよびｍはそれぞれ次の範囲を満足する数を表す。０＜ｘ＜０．５，０≦ｍ＜２）

(Wherein, M ²⁺ is at least one of Mg and Zn divalent metals, M ³⁺ is at least one of Al and Fe trivalent metals, and A ⁻ is NO ₃ ⁻ , Cl ⁻ , Br ^−. , ClO ₄ ⁻ , HCOO ⁻ and CH ₃ COO ⁻ are at least one monovalent anion selected from the group consisting of x and m, each representing a number satisfying the following range: 0 <x <0. 5, 0 ≦ m <2)

  Hydrotalcites composed of a specific monovalent anion represented by the above formula (2) have a considerable effect on improving the dyeability of fibers having poor dyeability such as polyurethane. However, the dyeing property is still insufficient, particularly the effect on blue is weak, and the fastness in high temperature water is insufficient, fading easily by washing, etc., and stains other fibers. I understood that.

JP 2000-229510 A

  The object of the present invention has not been solved even by the prior art using the above formula (2). (A) Further improvement of dyeability, especially good dyeing even in the most difficult blue, (b) Furthermore, also for high temperature water (about 70-80 ° C.) frequently used in Europe and the like It is to develop a dyeing assistant that can show good fastness properties.

  As a result of further intensive studies to solve the above problems, the present inventor has discovered the causes of the above two problems. According to the results, acid dyes are only chemically adsorbed on the crystal surface of the positively charged hydrotalcite of formula (2). It is not chemically bonded. It was also found that the blue acid dye has a larger ion size than red or yellow, and is less likely to enter the interlayer than the red or yellow dye. Therefore, if the acid dye enters between the hydrotalcite layers through an ion exchange reaction and chemically bonds, it is considered that the two problems can be solved at the same time because the bonding force is stronger than the surface adsorption.

Based on the above idea, since the blue color having the largest anion diameter among acid dyes is about 20 mm, all acid dyes can easily enter the interlayer by ion exchange reaction by hydrotalcites. A unit layer thickness of about 24 to 25 mm or more (basic layer is about 4.7 mm, an anion-containing intermediate layer is about 20 mm, and the basic layer is an octahedral layer made of M ²⁺ and M ³⁺ hydroxide).

  As a result of diligent search for hydrotalcites satisfying such conditions and their synthesis methods, the following formula (1)

（但し、式中、Ｍ^２＋は２価金属の少なくとも１種以上、好ましくはＭｇおよび／またはＺｎを示し、Ｍ^３＋は３価金属の少なくとも１種以上、好ましくはＡｌおよび／またはＧａ、特に好ましくはＡｌを示し、Ａ⁻は炭素数が１０以上、好ましくは１２〜２２、特に好ましくは１２〜１８の高級脂肪酸の少なくとも１種以上、例えば、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、エルカ酸、リノール酸、リノレイン酸等を示し、ｘおよびｍは、それぞれ、０＜ｘ＜０．５、好ましくは０．２≦ｘ≦０．４、特に好ましくは０．２５≦ｘ≦０．４，０≦ｍ＜５、好ましくは０≦ｍ＜２の範囲にある）で表されるハイドロタルサイト類を有効成分として用いることにより、染色性と堅ろう性の優れた繊維を得られることを発明した。

(In the formula, M ²⁺ represents at least one divalent metal, preferably Mg and / or Zn, and M ³⁺ represents at least one trivalent metal, preferably Al and / or Ga, particularly preferably. Represents Al, and A ⁻ represents at least one of higher fatty acids having 10 or more, preferably 12 to 22 and particularly preferably 12 to 18 carbon atoms, such as capric acid, lauric acid, myristic acid, palmitic acid, stearin. Acid, oleic acid, erucic acid, linoleic acid, linolenic acid and the like, and x and m are each 0 <x <0.5, preferably 0.2 ≦ x ≦ 0.4, particularly preferably 0.25. ≦ x ≦ 0.4, 0 ≦ m <5, preferably in the range of 0 ≦ m <2)). By using hydrotalcites represented as an active ingredient, excellent dyeability and fastness It invented that obtained by Wei.

  The dyeing aid of the present invention can exhibit the intended effect by containing 0.1 to 20% by weight of the fiber.

  As the dye used in the present invention, reactive dyes and metal-containing dyes which are the same anionic type can be used in addition to the acid dye. Furthermore, disperse dyes can also be used.

  According to the present invention, the dyeability of the fibers is remarkably improved, the fastness is also improved, the uneven dyeing at the time of fiber blending is substantially eliminated, and the same color can be enhanced.

  The hydrotalcite represented by the formula (1) of the present invention has a higher fatty acid having 10 or more carbon atoms, preferably 12 to 20, and particularly preferably 12 to 18 as an interlayer anion having ion exchange properties. Features. The ion exchange of the interlayer anion with the anion dye is more easily performed as the interlayer anion diameter is larger than the ion diameter of the dye. Therefore, it should be preferable that the higher fatty acid has a larger number of carbon atoms. On the other hand, in terms of hydrophilicity, the affinity of the dye ion between the hydrotalcite layers is better as the carbon number of the higher fatty acid is smaller. Further, the higher the number of carbons in higher fatty acids, the lower the water solubility of these alkali metal salts. At least about 25 or more, the water becomes insoluble, and the synthesis of hydrotalcites having such anions as interlayer anions is possible. It becomes practically difficult.

  Therefore, there is a preferred range for the number of carbons to simultaneously satisfy the conflicting requirements of large ionic radius and hydrophilicity. The particularly preferred carbon number is 12-18, and examples of such higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, erucic acid and the like. Among these, at least one of lauric acid, myristic acid, palmitic acid, and oleic acid is particularly preferable.

  The thickness of the unit layer is the most important factor that determines the ion exchange property, and it can be determined from the diffraction peak at the lowest angle side in the XRD measurement. The thickness of the unit layer is 21 mm or more, preferably 24 mm or more, particularly preferably 26 mm or more.

As M ^{2+ in the} formula (1), Mg, Ni, Cu, Zn, Co, Mn and the like can be used, but Mg and / or Zn are preferable for reasons such as whiteness, non-toxicity and cost. Al, Fe, Co, Ga, In, or the like can be used as M ³⁺ , but Al is most preferable for the same reason as M ²⁺ .

The range of x in the formula (1) can take a wide range of 0 <x <0.5, but the amount of interlayer anion increases corresponding to the increase in the value of x. Since the amount that can be bonded to increases, the larger x, the better. However, when x becomes too large, the solid solution limit of M ³⁺ to M ²⁺ (OH) ₂ is exceeded, and the amount of interlayer anions reaches a peak. The peak value is about 0.4.

  For the above reason, a particularly preferable range of x is 0.25 ≦ x ≦ 0.4.

  The hydrotalcite of the formula (1) of the present invention is blended in an amount of 0.1 to 20% by weight, preferably 1 to 6% by weight with respect to the fiber, without adversely affecting the fiber such as mechanical strength. Exhibits excellent dyeability.

In order for the hydrotalcite of the formula (1) of the present invention to be an excellent dyeing aid for fibers, it is also necessary that the spinnability in fiber production is good. In order to show good spinnability, the BET specific surface area of the hydrotalcites of formula (1) is preferably 1 to 30 m ² / g, particularly 5 to ²⁰ m ² / g, and the particle size distribution measurement The required average secondary particle diameter is preferably 1.5 μm or less, particularly preferably 1.0 μm or less.

The hydrotalcite of formula (1) of the present invention is prepared by using an aqueous solution of M ²⁺ and M ³⁺ , an alkali metal hydroxide such as sodium hydroxide and / or an alkali metal carbonate such as sodium carbonate. The aqueous solution is coprecipitated in an aqueous medium with stirring while maintaining the pH at 8 or more, preferably in the range of 9 to 11, and then washed with an aqueous alkali metal carbonate solution and then with water to obtain a CO ₃ ^2- type. Synthesize hydrotalcites (interlayer anion is CO ₃ ²⁻ ). This is heat-treated with water in an autoclave at 100 ° C. or higher, preferably 120 ° C. 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 anionic acid such as nitric acid and hydrochloric acid, and then a higher fatty acid having 10 or more carbon atoms corresponding to the formula (1). In addition to the aqueous alkali metal salt solution, it can be produced preferably by heating and hydrating at 100 to 200 ° C.

A of the present invention ^- the ion exchange reaction with preferably carried out by adding equimolar or more anions. It is preferable to wash with water after the ion exchange reaction.

  Examples of the fiber used in the present invention include acrylic, acetate, nylon, vinylidene, vinylon, polyacetal, polyurethane, polyester, polyethylene, polyvinyl chloride, polyclar, polypropylene, etc., preferably nylon, polyurethane, polyester, Polyethylene and polypropylene fibers.

  The fiber having good dyeability of the present invention can be produced by spinning the above polymer containing the hydrotalcite of formula (1). As the spinning method, any of conventionally known dry, wet and melt can be appropriately selected and formed into a fiber shape.

  The fiber of the present invention may be dyed using the same method as that for ordinary synthetic fibers and natural fibers. That is, dyeing methods such as a dip dyeing method, a pad steam method, a pad thermofix method, 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.

[Example]
Various evaluations were performed by the following methods.
(1) Measurement of unit layer thickness of hydrotalcite X-ray diffraction pattern is measured by powder X-ray diffraction method, and Bragg's formula is calculated from the position of the peak at the lowest angle (most intense peak in most cases). Determined by
(2) The BET specific surface area was measured by a liquid nitrogen adsorption method.
(3) Measurement of particle size distribution The 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) Evaluation of dyeability of fiber 400 g of polytetramethylene ether glycol having a number average molecular weight of 1800 and 91.7 g of 4,4′-diphenylmethane diisocyanate are obtained at 80 ° C. for 3 hours in a dry nitrogen atmosphere. Then, the reaction was carried out with stirring to obtain a polyurethane prepolymer whose ends were capped with an isocyanate. After cooling to room temperature, 720 g of dimethylacetamide was added and dissolved to prepare a polyurethane prepolymer solution. On the other hand, 8.111 g of ethylenediamine and 1.37 g of diethylamine were dissolved in 390 g of dimethylacetamide, and this was added to the prepolymer solution at room temperature to obtain a polyurethane solution having a viscosity of 4500 poise (30 ° C.).
To this polyurethane solution, 1% by weight of 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol), 2- (2′-hydroxy-3′-t- 0.5% by weight of butyl-5′-methylphenyl) -5-chloro-benzotriazole and 2% by weight of hydrotalcites described in Table 1 were added to obtain a polyurethane urea stock solution. 1110 g of dimethylacetamide was added to the polyurethane urea stock solution thus obtained, and a film dope was formed under the following conditions to obtain a film.
[Film forming conditions]
Dope slit length; 0.035 mm
Solvent removal conditions: Hot air 100 ° C. × 15 minutes each film obtained was dyed in each separate bath under the following conditions.
Dye; Nairosan Blue N-GFL
pH: 4 (adjusted with acetic acid)
Temperature, time; 90 ° C., 60 minutes bath ratio; 1:20
Rinsing after dyeing; rinsing with running water 10 minutes after dyeing, the level of dyeing was determined according to the following criteria.
5th grade Dark blue, 4th grade blue, 3rd grade light blue, 2nd grade pale light blue, 1st grade white or colorless and transparent (5) Dye fastness of fabric was evaluated by JIS L0844 discoloration. The detergent used at that time was manufactured by Kao Corporation, the detergent product name “ATTACK” 2 g / liter, washed for 30 minutes each under two conditions of washing liquid temperature 50 ° C. and 80 ° C., rinsed with running water for 30 minutes, and then dehydrated. The change in hue after drying for 24 hours at room temperature (25 ° C., 70% RH) was measured.
[Hue change (△ grade) = grade before washing fabric-grade after washing fabric]
It can be said that as the series before washing is larger and the numerical value of Δ is smaller, the color change is smaller and the dyeability and fastness are better.

[Dyeing aid: Synthesis of lauric acid hydrotalcites]
Commercially available CO ₃ type hydrotalcite (trade name: DHT-4) 200 g: BET specific surface area = 12 m ² / g, average secondary particle size = 0.46 μm, maximum secondary particle size = 0.81 μm, chemical composition Mg _0.68 Al _0.32 (OH) ₂ (CO ₃ ) _0.16 · 0.50H ₂ O is added to about 2 liters of warm water (about 70 ° C.), and 0.5 mol / liter of HNO under stirring. 1.9 liters of ₃ aqueous solutions were added, mainly keeping the pH between about 3-4. In this reaction, CO ₃ ²⁻ was ion-exchanged into NO ₃ ⁻ . 188 g of lauric acid (NAA-122 manufactured by NOF Corporation) was added to about 1.5 liters of warm water (about 90 ° C.) together with approximately equivalent NaOH, and after dissolution, added to NO ₃ type hydrotalcite slurry, about 90 Stir at 30 ° C. for 30 minutes. Then, after vacuum filtration and washing with warm water (about 80 ° C.), the mixture was put in a hot air dryer, dried at about 120 ° C. for 10 hours, and then pulverized with an atomizer. As a result of X-ray diffraction measurement of this product, the thickness d of the unit layer was 24.1 mm. In this X-ray diffraction pattern, NO ₃ type (d = about 8.9%) and CO ₃ type (d = about 7.6%) hydrotalcites did not remain. The chemical composition obtained by chemical analysis, total organic carbon, and thermal analysis is as follows. Mg _0.68 Al _0.32 (OH) ₂ (C ₁₁ H ₂₃ COO) _0.32 · 0.40H ₂ O. This product had a BET specific surface area of 14 m ² / g, an average secondary particle size of 0.40 μm, and a maximum secondary particle size of 0.85 μm.

[Dyeing aid: Synthesis of myristic acid hydrotalcites]
In Example 1, it carried out similarly to Example 1 except using 220 g of myristic acid (NAA-142 made from NOF Corporation) instead of lauric acid, and NaOH equivalent to it. As a result of X-ray diffraction measurement of the obtained powder, the thickness d of the unit layer was 27.1 mm. Neither NO ₃ nor CO ₃ type hydrotalcites remained in this X-ray diffraction pattern. The chemical composition of this product is as follows. Mg _0.68 Al _0.32 (OH) ₂ (C ₁₃ H ₂₇ COO) _0.32 · 0.42H ₂ O. This product had a BET specific surface area of 15 m ² / g, an average secondary particle size of 0.47 μm, and a maximum secondary particle size of 1.2 μm.

[Dyeing aid: Synthesis of palmitic acid type hydrotalcites]
In Example 1, it carried out similarly to Example 1 except using 242 g of palmitic acid (A-1600 made from NOF Corporation) instead of lauric acid, and NaOH equivalent to it. As a result of X-ray diffraction measurement of the obtained powder, the thickness d of the unit layer was 29.5 mm. Neither NO ₃ nor CO ₃ type hydrotalcites remained in this X-ray diffraction pattern. The chemical composition of this product is as follows. Mg _0.68 Al _0.32 (OH) ₂ (C ₁₅ H ₃₁ COO) _0.32 · 0.44H ₂ O. This product had a BET specific surface area of 12 m ² / g, an average secondary particle size of 0.45 μm, and a maximum secondary particle size of 0.92 μm.

[Dyeing aid: Synthesis of oleic acid type hydrotalcite]
In Example 1, it carried out like Example 1 except using 290 g of oleic acid (extra olein A-1981 made from Japanese fats and oils) instead of lauric acid, and NaOH equivalent to it. As a result of X-ray diffraction measurement of the obtained powder, the thickness d of the unit layer was 36.7 mm. Neither NO ₃ nor CO ₃ type hydrotalcites remained in this X-ray diffraction pattern. The chemical composition of this product is as follows. Mg _0.68 Al _0.32 (OH) ₂ (C ₁₇ H ₃₃ COO) _0.32 · 0.48H ₂ O. This product had a BET specific surface area of 12 m ² / g, an average secondary particle size of 0.47 μm, and a maximum secondary particle size of 0.98 μm.

[Dyeing aid: Synthesis of lauric acid-oleic acid mixed hydrotalcite]
In Example 1, the amount of lauric acid was reduced to 110 g. Instead, 145 g of oleic acid was added thereto, and this was performed in the same manner as in Example 1 except that they were mixed with an equivalent amount of NaOH. As a result of X-ray diffraction measurement of the obtained powder, the thickness d of the unit layer was 29.5 mm. Neither NO ₃ nor CO ₃ type hydrotalcites remained in this X-ray diffraction pattern. The chemical composition of this product is as follows. Mg _0.68 Al _0.32 (OH) ₂ (C ₁₁ H ₂₃ COO) _0.16 (C ₁₇ H ₃₃ COO) _0.16 · 0.48H ₂ O. This product had a BET specific surface area of 16 m ² / g, an average secondary particle size of 0.52 μm, and a maximum secondary particle size of 0.98 μm.

[Comparative Example 1]
Table 1 shows the results of evaluation conducted in the same manner as in the Examples except that the dyeing assistant hydrotalcite was not added.

[Comparative Example 2]
As a dyeing assistant, 4 g of stearic acid (NAA-180 manufactured by NOF Corporation) and an equivalent amount of NaOH in about 100 ml of warm water (about 80 ° C.) were added to the slurry of NO ₃ type hydrotalcite synthesized in Example 1. The dissolved solution was added under stirring, stirred for 5 minutes at about 80 ° C., filtered, washed with water, dried and pulverized, added to polyurethane and evaluated in the same manner as in the examples. As a result of X-ray diffraction measurement of this powder, the thickness d of the unit layer was 8.9 mm. The chemical composition of this product is as follows. Mg _0.68 Al _0.32 (OH) ₂ (NO ₃ ) _0.32 · 0.36H ₂ O. This product had a BET specific surface area of 15 m ² / g, an average secondary particle size of 0.56 μm, and a maximum secondary particle size of 0.86 μm.

Claims (9)

Following formula (1)

(Wherein, M ²⁺ represents at least one or more divalent metals, M ³⁺ represents at least one or more trivalent metals, and A ⁻ represents at least one or more higher fatty acids having 10 to 25 carbon atoms. , X and m are in the range of 0 <x <0.5 and 0 ≦ m <5), respectively, and 0.1 to 20% by weight of hydrotalcite represented by fiber is contained. A fiber composition having excellent dyeability. The fiber composition according to claim 1, wherein, in the formula (1), M ²⁺ and M ³⁺ are Mg and / or Zn, Al, respectively. A of formula (1) ^- is, fiber composition of claim 1 wherein the higher fatty acid in the range of 12 to 18 carbon atoms. A of formula (1) ^- is, lauric acid, myristic acid, palmitic acid, at least one of claims 1 fiber composition according chosen from among stearic acid and oleic acid. The fiber composition according to claim 1, wherein the range of x in the formula (1) is in the range of 0.2 ≦ x ≦ 0.4. The fiber composition according to claim 1, wherein the hydrotalcite of formula (1) has a BET specific surface area and an average secondary particle diameter in the range of 1 to 30 m ^{2 /} g and 0.1 to 1.0 µm, respectively. Following formula (1)

(Wherein, M ²⁺ represents at least one or more divalent metals, M ³⁺ represents at least one or more trivalent metals, and A ⁻ represents at least one or more higher fatty acids having 10 to 25 carbon atoms. , X and m are each in the range of 0 <x <0.5 and 0 ≦ m <5). In formula (1), M ²⁺ is Mg and / or Zn, M ³⁺ is Al, A ⁻ is at least one of higher fatty acids in the range of 12 to 20 carbon atoms, and x is 0.2 The dyeing assistant according to claim 7, which is in the range of ≤x≤0.4. The dyeing assistant according to claim 7, wherein the hydrotalcite of formula (1) has a BET specific surface area of 1 to 30 m ² / g and an average secondary particle diameter of 0.1 to 1.0 µm.