KR20080020457A - Blue dope dyed-polyurethane fiber containing ultramarine blue pigment - Google Patents

Abstract

A blue-dyed polyurethane fiber is provided to generate a uniform and deep blue color, by reforming a surface of blue pigments, which are contained in the blue-dyed polyurethane fiber, through solution treatment or electrochemical treatment. A blue-dyed polyurethane fiber contains 0.03-10 wt% of ultramarine blue pigments based on the final polymer solid. The ultramarine blue pigment has a particle size of 0.01-100 um, wherein a surface of the ultramarine blue pigment is treated. The surface treatment of the ultramarine blue pigment is performed by using an acid solution or a base solution. The surface treatment of the ultramarine blue pigment is electrochemically performed by using a plasma apparatus or a corona apparatus.

Description

Blue dope dyed-polyurethane fiber containing ultramarine blue pigment}

The present invention relates to a blue polyurethane primary yarn to which an ultramarine blue (UMB, ultramarine blue) pigment is added, characterized in that it is prepared by adding an ultramarine blue pigment to the pre-spun polyurethane polymer. More specifically, ultramarine blue which is surface treated with an acidic solution or a basic solution or electrochemically surface treated with a plasma or corona device is used. The blue polyurethane primary yarn of the present invention prepared using the present pigment exhibits a b * value of -2.0 or less, and their basic physical properties such as strength and elongation are similar to those of conventional polyurethane yarns, and wash fastness is 4-5 grade. great.

In order to color a polyurethane elastic yarn, a liquid coloring agent or a solid coloring substance is mixed with polyurethane resin. However, a major problem in coloring the polyurethane elastic yarn is that not only can not color the polyurethane in the desired color, but also there is a limitation by the method of manufacturing the polyurethane elastic yarn.

 Korean Patent Laid-Open Publication No. 2002-0092588 refers to a polyurethane black yarn of black color using carbon black, and Korean Patent Laid-Open No. 2001-0025956 discloses a color to be colored in manufacturing a polyurethane black yarn. It is described that it is difficult to obtain brightness and saturation and to obtain a uniform color.

On the contrary, the Republic of Korea Patent Publication No. 2003-0095101 deals with a blue polyurethane elastic yarn using a blue phthalocyanine pigment, but in this case, since the phthalocyanine pigment itself is not only expensive but also an organic pigment, it is used when preparing a polyurethane for dry spinning. Part of the organic material used as a coating material in the solvent is dissolved, there is a big disadvantage that the contamination of the polymerization equipment during the purification and recovery of the solvent.

In order to solve the problems of the prior art, the present invention is characterized in that the addition of an ultramarine blue pigment capable of imparting a blue color to the polyurethane polymer, wherein the added ultramarine blue is acidic or basic Surface modification by an aqueous solution treatment such as a solution or an electrochemical treatment such as a plasma or corona device to provide a uniform and deep blue polyurethane primary yarn.

In another aspect, the present invention is to provide a blue polyurethane primary yarn that can express the color of the deep color with acid dyes or disperse dyes when working with nylon yarns and polyester yarns and also excellent washing fastness.

In order to achieve the above object, the present invention is a polyurethane containing 0.03 to 10% by weight of ultramarine blue surface-treated with an acidic solution or a basic solution, or surface-treated by a plasma or corona device electrochemical method It's an arrival story.

The segmented polyurethane used in the polyurethane production of the present invention is prepared by reacting an organic diisocyanate with a polymer diol to prepare a polyurethane precursor, as known in the art, and then dissolving it in an organic solvent and then reacting with a diamine and a monoamine. do.

The organic diisocyanate used in the present invention is 4.4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylenedi isocyanate, hexamethylene diisocyanate,, 1,4'-cyclohexane It can be illustrated by 1 type of diisocyanate, 4,4'- dicyclohexyl methane diisocyanate, 1 type of organic diisocyanate, such as isopron diisocyanate, or mixture of 2 or more types thereof.

The polymer diol may be polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, or the like. The diamines are used as chain extenders, and examples thereof include ethylenediamine, 1,2'-propylenediamine, hexamethylenediamine, xylenediamine, 4,4'-diphenylmethanediamine, hydrazine and the like, or two of them. Mixtures of species or more can be exemplified.

Other fillers may include UV stabilizers, antioxidants, NOx gas anti-yellowing agents, anti-sticking agents, dyeing enhancers, chlorine-proofing agents, matting agents, etc., which are uniformly dispersed by dispersing with an attrition bowl mill and sand grinder. It is used as a primary particle diameter.

Examples of the solvent for the polyurethane include N, N'-dimethylformamide, N, N'-dimethylacetamide, tetramethylurea and hexamethylphosphonoamide.

The present invention is characterized by producing a blue polyurethane primary yarn by spinning after adding the ultramarine blue pigment to the polyurethane polymer prepared by the above method.

In the present invention, the spinning method is not particularly limited, and dry spinning, wet spinning, and melt spinning methods other than chemical spinning may be used, and dry spinning is particularly preferable.

In the case of the surface treatment or the electrochemical surface treatment by the aqueous solution as described above, the affinity with the polyurethane can be increased by developing the functional groups introduced on the surface of the ultramarine blue, and the specific surface area of the ultramarine blue can be increased. Or surface activation or characterization, it may be advantageous to express higher concentrations of color at the same content than when using conventional ultramarine blue.

In general, ultramarine blue is a kind of silicate having a composition such as 3NaAlSiO ₄ Na ₂ S _2, and is a pigment in powder form that can exhibit a dark blue color unlike other inorganic pigments.

In the present invention, the amount of the ultramarine blue pigment used varies depending on the kind, particle diameter, specific gravity, etc., but is preferably 0.03 wt% to 10 wt% relative to the final polymer solids. If it is less than 0.03wt%, the color of the color becomes poor, causing color unevenness in the yarn, and if it exceeds 10wt%, performance loss as an elastic fiber, wear of the gear pump by inorganic materials, stagnation and spinning in piping, etc. It can cause defects in gender.

In the present invention, the particle size of the pigment is preferably 0.01 to 100 μm, and when the particle size of the pigment is less than 0.01 μm, the dispersion state is good in the solvent or polymer, but N, It may possibly be recovered together with N'-dimethylacetamide, and if the particle size of the pigment exceeds 100 µm, aggregation of the pigments may occur and a uniform color may not be obtained, and workability may be reduced. There is a problem.

In particular, the ultramarine blue pigment is excellent in solvent resistance to the solvent because it is composed of inorganic substances, unlike dyes or organic pigments. This is a very important factor in the polyurethane elastic yarn produced through dry spinning. In general, in the process of recovering a solvent such as N, N'-dimethylacetamide, in the case of an organic pigment coated with an organic material on the outermost layer, the organic material is easily dissolved in the solvent, which is recovered together with the solvent in the spinning barrel. After being mixed with freshly replenished solvents, it can be reused causing significant contamination of the entire elastic yarn production facility.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, which are intended to illustrate the present invention and should not be construed as limiting the scope of the present invention to only Examples.

< Example  1>

In order to prepare a polyurethane primary yarn having a blue color, a pre-treated ultramarine blue pigment was used, and the particle size of the pigment was about 10 μm. The ultramarine blue pigment used is washed with distilled water to remove impurities that may be present on the surface, and the distilled water and pigment are separated by centrifuge. Repeat this 3-4 times, put in a drying oven to dry completely. Thereafter, the dried ultramarine blue was treated with 10% CH ₂ CHCOOH for 24 hours in order to increase affinity with the polyurethane polymer, which was washed several times with distilled water again and dried completely at 90 ° C., and then used.

0.3 wt% Ultramarine Blue Pigment (C.I. Pigment Blue 29) to the final polymer solids weight is mixed with the polyurethane polymer prepared by the above-mentioned method and stirred to obtain a polymer having a viscosity of 4000 poise. The 40 denier polyurethane primary yarn is produced by spinning this polymerized product using a conventional dry spinning method. Prepared polyurethane yarn is knitted with a polyamide yarn pre-dyed in blue color and then measured the fastness to washing.

< Example  2>

The raw yarn prepared in the same manner as in Example 1 was knitted with a polyester yarn pre-dyed in blue color and then measured the color fastness to washing.

< Example  3>

It is the same as that of Example 1 except the original complex yarn was prepared by adding the amount of the ultramarine marine blue pigment to 2.0 wt% based on the final polymer solid content. Prepared polyurethane yarn is knitted with a polyamide yarn pre-dyed in blue color and then measured the fastness to washing.

< Example  4>

The raw yarn prepared in the same manner as in Example 3 was knitted with a blue yarn-dyed polyester yarn and a teaching fabric, and then measured washing fastness.

< Example  5>

The surface was treated with 1M KOH of ultramarine blue, and the same as in Example 1 except that the original yarn was prepared by 2.0 wt% of the final polymer solids. Prepared polyurethane yarn is knitted with a polyamide yarn pre-dyed in blue color and then measured the fastness to washing.

< Example  6>

The raw yarn prepared in the same manner as in Example 5 was knitted with a polyester yarn pre-dyed in blue color and then measured the color fastness to washing.

< Example  7>

Ultramarine blue was surface modified using a plasma apparatus in the following manner. Plasma was used in a nitrogen atmosphere using a radiofrequency plasma (Tegal Plasmod), and the distance between the electrodes was fixed to 50 mm in a petri dish containing about 200 mg of ultramarine blue for 5 minutes at a frequency of 13.56MHz. Treated ultramarine blue was grafted by immersion in 1N KOH solution to stabilize activated radicals. The ultramarine blue treated as above was added in an amount of 2.0 wt% based on the final polymer solids, and the same procedure as in Example 1 was performed except that a polyurethane elastic yarn was prepared. Prepared polyurethane yarn is knitted with a polyamide yarn pre-dyed in blue color and then measured the fastness to washing.

< Example  8>

The raw yarn prepared in the same manner as in Example 7 was knitted with a blue yarn-dyed polyester yarn and a teaching fabric, and then measured washing fastness.

< Comparative example  1>

It is the same as Example 1 except not adding an ultramarine blue pigment compared with Example 1. The prepared polyurethane fiber is dyed with an acid dye (blue) after knitting with a polyamide-based yarn.

< Comparative example  2>

It is the same as Example 1 except not adding an ultramarine blue pigment compared with Example 1. The prepared polyurethane fiber is dyed with a dispersion dye (blue) after knitting with a polyester yarn.

< Comparative example  3>

It is the same as Example 3 except adding the ultramarine blue which was not surface-treated at the time of polyurethane elastic yarn manufacture. The prepared polyurethane fiber is dyed with an acid dye (blue) after knitting with a polyamide-based yarn.

< Comparative example  4>

Compared with Example 1, except that phthalocyanine-based pigments are added instead of the ultramarine blue pigments are the same as in Example 1. The prepared polyurethane fiber is dyed with a dispersion dye (blue) after knitting with a polyester yarn.

The physical property evaluation method of the product manufactured according to the said Example and the comparative example was performed as follows, and the result is shown in Table 1.

o Elongation: Measure with 50mm of sample length and 500mm / min of tensile speed by using universal testing machine (UTM).

o Color evaluation: The reflectance of polyurethane elastic yarn was measured using a spectrophotometer and calculated using the CIE 76 CIE Lab formula. If b * is (+) in the color coordinate, it is yellow, and if it is (-), it is blue.

o Wash fastness: measured by KS K 0430 AI method.

Purified Dimethyl Acetamide (DMAc) Chromaticity

         In general, in the case of dry spinning, as mentioned above, the solvent is recovered and reused. At this time, the recovered solvent is mixed with fresh solvent by condensation and purification. At this time, the solvent used was sampled in the condenser, and the color of the solvent according to each condition was compared and evaluated. The color of the solvent recovered means that if it is white and transparent like new material, it can be regenerated; if it becomes opaque or otherwise opaque, that is, if it is not purified, it will contaminate the color of the final elastic yarn by contaminating the whole spinning system. .

TABLE 1

 Strength [g / d]  Elongation [%]  Yarn Color  Color fastness DMA _C color after purification b *  Example 1  1.52  741  -10.4  4-5 class  Transparency  Example 2  Grade 5  Example 3  1.55  731  -49.1  Grade 5  Transparency  Example 4  Grade 5  Example 5  1.50  729  -52.4  Grade 5  Transparency  Example 6  Grade 5  Example 7  1.52  733  -53.6  Grade 5  Transparency  Example 8  Grade 5  Comparative Example 1  1.52  745  -  2nd class  Transparency  Comparative Example 2  2-3 grade  Comparative Example 3  1.50  734  -41.2  Grade 5  Transparency  Comparative Example 4  1.47  722  -44.5  4-5 class  Slightly blue

The functional group of the surface of the ultramarine blue is developed by the surface modification of the ultramarine blue by acid or alkali treatment or plasma or corona device of the present invention, and the affinity with the polyurethane which is the resin is increased due to the surface activation of the ultramarine blue. This makes it possible to produce a blue polyurethane primary yarn with excellent color and high quality and depth. In addition, the polyurethane yarn thus prepared can not only be deeply dyed even when dyed blue with nylon yarn or polyester yarn, but can also provide excellent washing fastness.

Claims (5)

Blue polyurethane raw yarn comprising an ultramarine blue pigment, characterized in that the particle size of 0.01 ~ 100㎛ and contains a surface treated ultramarine blue pigment 0.03 ~ 10wt% compared to the final polymer solids. The blue polyurethane primary yarn containing an ultramarine blue pigment according to claim 1, wherein the ultramarine blue pigment is surface treated with an acidic or basic solution. The yarn of claim 1, wherein the ultramarine blue pigment is surface-treated by an electrochemical method using a plasma or corona device. The blue polyurethane primary yarn comprising an ultramarine blue pigment according to claim 1, wherein the blue polyurethane primary yarn has a b * value of −2.0 or less in chromaticity coordinates. A fabric comprising a blue polyurethane primary yarn comprising the ultramarine blue pigment according to any one of claims 1 to 4.