JPH059879A - Colored ultrahigh-molecular polyethylene fiber assembly - Google Patents

Abstract

PURPOSE:To obtain a colored fiber assembly having hue capable of sufficiently enduring to practical use and having excellent fastness without impairing characteristics of the fiber by coloring an ultrahigh molecular polyethylene fiber assembly with a solvent color and cleaning the assembly with acetone. CONSTITUTION:An ultrahigh molecular polyurethane fiber assembly (e.g. yarn, wool, woven fabric, knitted fabric, etc.) is colored using a solvent color of an azo based compound, anthraquinone based compound or metal complex dissolved in an organic solvent such as hydrocarbons, alcohols or ethers and cleaned with acetone to provide an ultrahigh molecular polyethylene fiber assembly colored so that lightness index L value in Hunter color difference type may indicate >=50. The colored assembly has fastness to lightness capable of sufficiently and practically enduring without impairing characteristics of ultrahigh strength, high modulus, etc., which the fiber has and is suitable for rope for yacht, sail cloth, fishing net, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigmented fiber assembly, and more particularly to a pigmented high strength ultra high molecular weight polyethylene fiber assembly.

[0002]

2. Description of the Related Art Conventionally, as a method for coloring a fiber, there are a deposition method in which a colorant such as a dye or a pigment is added and mixed into a raw material polymer, and a so-called dyeing processing in which a fiber is formed and then various treatments are performed for coloring. The law is known.

However, the first-dip method is a change in manufacturing brand,
For example, in the case of changing the color or changing to a non-colored fiber, there is a drawback that it takes a lot of time and material loss.
With regard to the ultra high molecular weight polyethylene fiber which is the object of the present invention, the additive for depositing acts as a defect in the crystal formation process for expressing high strength and adversely affects the strength. This is not preferable because it may affect On the other hand, when applying the method of forming fibers and then dyeing them to high-strength ultrahigh molecular weight polyethylene fibers, the polyethylene has a simple chemical structure and the degree of crystallinity is very high. Was difficult to dye. For the above reasons, the pigment padding method, the pigment printing method and the like are currently used. However, this method requires the use of a binder for fixing the pigment onto the fiber, and therefore has the disadvantages that the texture is hard due to the effect of the binder and that the color is easily faded by washing or the like. In addition, it is also known that a clear hue is difficult to obtain and that spots are likely to occur, and that dark colors have poor rubbing fastness and are limited to medium to light colors.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention did not use a dyeing method or a conventional dyeing processing method, or a pigment padding method or a pigment printing method, and colored with a color fastness that can be practically used. The present invention has been accomplished as a result of intensive research to provide a high-strength ultrahigh molecular weight polyethylene fiber assembly.

[0005]

That is, the present invention provides a monoazo compound dissolved in at least one organic solvent selected from hydrocarbons, alcohols, ethers, ketones, esters and / or glycol derivatives. -Based, disazo-based, anthraquinone-based, metal complex salt-based solvent colors, or a mixture thereof, and most of the coloring is substantially removed by washing with acetone. It is intended to provide a polyethylene fiber assembly. Furthermore, by performing acetone cleaning, the lightness index L value in the Hunter color difference formula is 50 or more.

The high-strength ultrahigh molecular weight polyethylene in the present invention does not have to be a homopolymer, and includes, for example, a copolymer of ethylene and an α-olefin or a compound having another functional group. . It may also be a blend of a homopolymer and a copolymer thereof.

The viscosity average molecular weight is 500,000 or more, preferably 1,000,000 or more, more preferably 1,500,000 or more. The tensile strength required for the high-strength fiber is not limited, but it is preferably at least 20 g / denier or more, and when the viscosity average molecular weight is less than 500,000, the tensile strength of 20 g / denier is not expressed. difficult.

The fiber assembly referred to in the present invention is an assembly of formed high-strength ultrahigh molecular weight polyethylene fibers, and its form is not particularly limited. For example, thread, cotton,
Examples include woven and knitted fabrics, nets, strings, ropes, laminated sheet-like products and three-dimensional structures.

Further, the organic solvent in the present invention includes hydrocarbons such as toluene, xylene and styrene, alcohols such as methanol, isopropyl alcohol and 2-butanol, ethyl ether, tetrahydrofuran, 1,
Ethers such as 4-dioxane, ketones such as acetone, methyl ethyl ketone and methyl butyl ketone, esters such as methyl acetate, ethyl acetate and propyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc. It is selected from glycol derivatives or a mixture thereof.

The solvent color referred to in the present invention is
There is no particular limitation as long as the target amount (about 0.001 to 30% by weight) can be dissolved in the organic solvent, but a solvent color such as a monoazo-based, disazo-based, anthraquinone-based, metal complex salt-based solvent color is used. preferable. Specific examples of the color index numbers are Solvent Yellow 21, Solvent Yellow 151, Solvent Orange 40, Solvent Red 83, Solvent Red 11
8, Solvent Red 122, Solvent Red 13
2, Solvent Red 218, Solvent Blue 70,
Solvent Black 22, Solvent Black 27 and the like can be mentioned. Further, in order to obtain a desired hue, these two or more kinds can be freely combined and used as a mixture.

Acetone washing, which is an important requirement of the present invention, means that the colored high-strength ultrahigh molecular weight polyethylene fiber aggregate is repeatedly washed with acetone of the 4th class petroleum and 1st class under normal temperature and normal pressure. Is replaced with fresh acetone and washed repeatedly until the acetone solution does not become cloudy due to the removed colorant.

The lightness index L value in the Hunter's color difference formula refers to JIS Z-87, which is indicated as a color difference display method.
30 (1980) According to 6.3.2.

A feature of the present invention is a fiber assembly colored by a so-called solvent dyeing method using a solvent color dissolved in an organic solvent. Generally speaking, water dyeing method using water as a solvent is common sense for dyeing formed fiber, but when trying to apply to the above problem, that is, high strength ultra high molecular weight polyethylene fiber, polyethylene has a chemical structure However, there is a problem that dyeing with sufficient fastness is difficult because it is simple and its crystallinity is very high. The present inventors have noticed that the above-mentioned solvent has a high affinity for polyethylene fibers, and that solvent dyeing has characteristics such as a high dyeing speed and a good dye transfer property and level dyeing property.

Further, most of the coloring of the colored fiber assembly obtained in the present invention is removed by washing with acetone. Therefore, the reflectance of the fiber assembly after washing is significantly improved, and the lightness index L value in the Hunter color difference formula becomes 50 or more. From this fact, it is presumed that the fiber aggregate obtained in the present invention is colored only in the fiber surface in the intended hue. However, except for use in an organic solvent such as acetone, the hue does not fall off under normal use conditions and can be sufficiently put to practical use.

The colored high-strength ultra-high-molecular-weight polyethylene fiber aggregates obtained by the present invention are various ropes for ships, yachts, cords, sail cloths, various nets such as fishing nets, explosion-proof sheets, work and sports. It can be used in various fields such as protective clothing. It is suitable for applications that require particularly excellent lightfastness.

The present invention will be specifically described below with reference to Examples and Comparative Examples. However, the present invention is not limited as long as the gist thereof is not exceeded.
It is not limited to the embodiment.

[0017]

EXAMPLES The measuring methods and measuring conditions used in the present invention are explained below. The viscosity average molecular weight was conveniently calculated using the following formula from the intrinsic viscosity measured by a capillary viscometer method with decalin at 135 ° C. Mv = 5.37 × 10 ⁴ [η] ^1.37

Strength / elongation measurement According to JIS L-1013 (1981). That is, using Tensilon manufactured by Orientec, the test length is 200m.
The S-S curve of the woven fabric constituent yarn was measured under the conditions of m and a pulling speed of 100 mm / min, and the tensile breaking strength and the tensile elastic modulus were calculated. The tensile elastic modulus was calculated from the maximum gradient near the origin of the SS curve.

Friction fastness According to JIS L-0849 (1971). That is, the Daiei Kagaku Seiki Seisakusho's academic vibration type friction tester (friction tester I
(Type I) was used to measure the fastness to rubbing in a dry state and a wet state.

Light fastness was measured according to JIS L-0842 (1988). That is, using a carbon arc lamp type light resistance tester manufactured by Suga Seisakusho, the temperature of the black panel was adjusted to 63 ° C. ± 3 ° C. and the light fastness was determined by exposure according to the second exposure method.

Lightness index L value JIS Z-8722 (1982) and JIS Z-8
730 (1980) 6.3.2. That is, the measurement was performed using a color difference meter (double beam system automatic color computer) manufactured by Tokyo Denshoku Co., Ltd.

Example 1 Using a high-strength ultrahigh molecular weight polyethylene fiber having a viscosity average molecular weight of 1.7 million and 800 denier 780 filament raw yarn (L value 93), a warp density of 33 yarns / inch and a weft density of 33 yarns / Inch plain weave was woven. This woven fabric was mixed with 95 parts by weight of methyl ethyl ketone (MEK) as a solvent color (color index number = solvent black 27: Oleosol manufactured by Taoka Chemical Industry Co., Ltd.).
After immersing in a solution in which 5 parts by weight of FastBlack RL) was dissolved for 30 seconds, the solution was squeezed with a mangle. The pickup rate was 60%. Continue to 100 in the warm air dryer
It heat-processed at 2 degreeC for 2 minutes. The tensile strength of the obtained colored woven fabric was 31 g / d and the tensile elastic modulus was 1140 g / d, which showed high strength, and no decrease in strength due to coloring was observed. In addition, the fastness to rubbing was excellent at 4th grade in both the dry and wet states, and the fastness to light was very good at 7th grade. The lightness index L value of this colored woven fabric was 20, but the L value was 76 after washing with acetone.

Example 2 Using a raw yarn (L value 93) of 800 denier 780 filaments made of high-strength ultrahigh molecular weight polyethylene fibers having a viscosity average molecular weight of 2.9 million, vertical density of 33 fibers / inch, weft density of 33 fibers / Inch plain weave was woven. This woven fabric was immersed in a solution prepared by dissolving 10 parts by weight of solvent color (color index number = solvent black 27) in 90 parts by weight of MEK in the same manner as in Example 1 for 30 seconds,
Squeezed with mangle. The pickup rate was 60%. Subsequently, heat treatment was performed in a warm air dryer at 100 ° C. for 2 minutes. The tensile rupture strength of the obtained colored woven fabric is 40 g /
d, the tensile elastic modulus was 1480 g / d, which showed high strength, and no decrease in strength due to coloring was observed. In addition, the fastness to rubbing was excellent at 4th grade in both the dry state and the wet state, and the fastness to light was very good at 6-7th grade. The lightness index L value of this colored woven fabric was 18, but the L value was 62 after washing with acetone.

Comparative Example 1 The same plain weave woven as in Example 1 was colored by the pigment padding method. Pigment as a color base (Color index number = Pigment Black 7: Sandy Super Black manufactured by Sanyo Dye Co., Ltd.)
C) 5 parts by weight, padding binder (acrylic ester resin) 7 parts by weight, binder catalyst 1 part by weight,
In order to prevent migration, 5 parts by weight of the main paste containing sodium alginate as a main component was mixed with 82 parts by weight of water and stirred to impregnate the padding solution with a pickup rate of 80%, and dried in a warm air dryer at 5 ° C at 120 ° C. Heat treated for minutes. The tensile rupture strength of the obtained colored woven fabric was 30 g / d, and the tensile elastic modulus was 1080 g / d, which showed high strength. Further, the light fastness was 4-5, which was a barely fastness for practical use. However, the texture was very hard and the application was limited. The lightness index L value of this colored fabric is 1
8, the L value was 19 even after washing with acetone, which was almost unchanged.

Comparative Example 2 The same plain weave woven as in Example 2 was colored by the pigment padding method as in Comparative Example 1. 10 parts by weight of pigment (color index number = Pigment Black 7) as a color base, binder 12 for padding
1 part by weight, 5 parts by weight of a binder catalyst, and 5 parts by weight of a main paste containing sodium alginate as a main component for preventing migration are mixed with 71 parts by weight of water and impregnated with a padding solution at a pick-up rate of 80% to obtain a warm air flow. After drying in a dryer, it was heat-treated at 120 ° C. for 5 minutes. The tensile rupture strength of the obtained colored woven fabric is 36 g / d, and the tensile elastic modulus is 1400 g / d.
Although it showed a high strength of d, the light fastness was slightly low as 4-5 grade, and the friction fastness was 1-2 grade in the dry state and 1 in the wet state.
It was a practical problem in the class. The lightness index L value of this colored woven fabric was 17, and even after washing with acetone, the L value was 18, showing almost no change.

From these results, it is clear that the colored high-strength ultrahigh molecular weight polyethylene fiber aggregate obtained in the present invention is very practical and can be identified by washing with acetone.

[0027]

The present invention is configured as described above,
The colored high-strength ultra-high-molecular-weight polyethylene fiber aggregate obtained in the present invention has its excellent properties, that is, light and ultra-high strength / high elastic modulus, excellent abrasion resistance, impact resistance, light resistance, etc. Without impairing the characteristics, various ropes for ships and yachts, cords, sail cloths, various nets such as fishing nets, explosion-proof sheets, and the intended hues required for work and sports protective clothing, etc. It has a robustness that can stand out.

Claims (2)

[Claims] 1. A monoazo type, a disazo type, an anthraquinone type, which is dissolved in at least one organic solvent selected from hydrocarbons, alcohols, ethers, ketones, esters and / or glycol derivatives. A colored ultra-high molecular weight polyethylene fiber assembly characterized in that it is colored with a solvent color such as a metal complex salt type or a mixture thereof, and most of the coloring is removed by washing with acetone. 2. The colored ultra-high molecular weight polyethylene fiber assembly according to claim 1, wherein the lightness index L value in the Hunter color difference formula is 50 or more by washing with acetone.