JP2014237905A - Flame-retardant fabric having high visibility - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant fabric having excellent high visibility.SOLUTION: The flame-retardant fabric is made by applying a specific amount of an ultraviolet ray absorbent to a polyetherimide-based fiber and subjecting the resultant to dyeing and has a color satisfying a need criterion of European Standards EN471 regarding high visibility.

Description

  The present invention provides a flame retardant fabric having a color satisfying the requirements of the European High Visibility Standard EN471, obtained by applying a specific amount of an ultraviolet absorber to a flame retardant polyetherimide fiber and dyeing it. About.

  Polyetherimide fiber is excellent in heat resistance and flame retardancy, and has many applications including industrial materials, electrical and electronic fields, agricultural materials, apparel, optical materials, aircraft, automobiles, ships, etc. It is used extremely effectively.

  Many high-performance synthetic fibers, not limited to polyetherimide fibers, are used in a colored state in many applications, mainly in the apparel field. Especially in outdoor construction sites, outdoor work such as car accidents, work clothes when conducting traffic guidance, traffic control, etc., the visibility is colored with fluorescent colors to ensure the safety of the work. There is a growing demand for textile products such as flame retardant clothes that are high and have excellent light resistance.

  European high visibility standard EN471 has been established for materials used for such highly visible textiles. In this standard, requirements for the color properties of materials are defined by conditions such as CIE chromaticity coordinates and luminance coefficients known in the art.

  As a material that can be applied to the above-mentioned applications, Patent Document 1 discloses a flame retardant fiber made of aramid, viscose, and polyimide that has high visibility by printing, but only the printed portion is colored. Thus, the entire fabric cannot be colored.

JP 2013-32612 A

  It is an object of the present invention to provide a flame retardant fabric having a color that satisfies the requirements of the European High Visibility Standard EN471 using fibers that can be adapted to the above-mentioned applications.

  As a result of intensive studies on the above problems, the inventors of the present invention imparted a specific amount of an ultraviolet absorber to a polyetherimide fiber having excellent flame retardancy and dyeing it, thereby achieving excellent flame retardancy and high European visibility. The inventors have found that a fabric having a color that satisfies the requirements of the standard EN471 can be obtained, and reached the present invention.

  That is, the present invention is made of a polyetherimide fiber, and has a color satisfying the requirements of the European high visibility standard EN471 by dyeing and dyeing 3 to 10% owf UV absorber inside the fiber. It is a flame retardant fabric.

  The flame retardant fabric has a CIE chromaticity coordinate (x, y) of a color after dyeing of (0.624, 0.374), (0.589, 0.366), (0.609, 0.343). ) And (0.655, 0.345), and the luminance coefficient β is preferably 0.40 or more.

  Alternatively, the flame retardant fabric has a CIE chromaticity coordinate (x, y) of a color after dyeing of (0.450, 0.549), (0.420, 0.483), (0.375, 0). .528) and (0.395, 0.602), and the luminance coefficient β is preferably 0.70 or more.

  In the present invention, at least one of the ultraviolet absorbers is preferably a hydroxyphenyltriazine-based ultraviolet absorber.

  Alternatively, in the present invention, it is preferable that at least one of the ultraviolet absorbers is an inorganic ultraviolet absorber.

  According to the configuration of the present invention, the polyetherimide fiber is dyed with a specific amount of an ultraviolet absorber, so that it has a color that satisfies the requirements of the European high visibility standard EN471 and has high visibility. A flame retardant fabric can be obtained.

  In the present invention, a flame retardant fabric obtained by applying a specific amount of an ultraviolet absorber to a flame retardant polyetherimide fiber and dyeing it satisfies the requirements of the European high visibility standard EN471. It is characterized by having a color.

(Polyetherimide resin)
Examples of the polyetherimide resin used in the present invention include polymers composed of combinations of repeating structural units represented by the following formula. Wherein R1 is a divalent aromatic residue having 6 to 30 carbon atoms; R2 is a divalent aromatic residue having 6 to 30 carbon atoms, 2 to 20 2 selected from the group consisting of an alkylene group having 2 carbon atoms, a cycloalkylene group having 2 to 20 carbon atoms, and a polydiorganosiloxane group chain-terminated with an alkylene group having 2 to 8 carbon atoms Valent organic group.

前記Ｒ１、Ｒ２としては、例えば、下記式群に示される芳香族残基やアルキレン基（例えば、ｍ＝２〜１０）を有するものが好ましく使用される。

As said R1, R2, what has an aromatic residue and alkylene group (for example, m = 2-10) shown by the following formula group, for example is used preferably.

  In the present invention, 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride mainly having a structural unit represented by the following formula from the viewpoint of amorphousness, melt moldability, and cost. A condensate of the product with m-phenylenediamine is preferably used. Such polyetherimides are commercially available from Servic Innovative Plastics under the trademark “Ultem”.

  The polyetherimide resin used in the present invention preferably has a molecular weight distribution (Mw / Mn) of less than 2.5. When the molecular weight distribution is 2.5 or more, the spinnability is unfavorable.

(UV absorber)
The present inventors have found that a flame retardant fabric having a color satisfying the requirements of the European High Visibility Standard EN471 can be obtained from a polyetherimide fiber when dyeing by adding 3 to 10% owf of an ultraviolet absorber. It was. Preferably it is 4-8% owf, More preferably, it is 5-7% owf. If the ultraviolet absorber is less than 3% owf, discoloration occurs, and if it exceeds 10% owf, the fiber strength decreases, which is not preferable.

  As the ultraviolet absorber used in the present invention, an organic ultraviolet absorber such as hydroxyphenyltriazine, benzophenone, or benzotriazole compound, or an inorganic ultraviolet absorber such as zinc oxide or cerium oxide is used. Most preferred is a cerium-based ultraviolet absorber because it is difficult to deactivate the effect. The ultraviolet absorber is preferably mixed with the resin in a state of being dissolved or dispersed in water or an organic solvent in order to be used in a state of being uniformly dispersed in the above-described resin emulsion or solution. The hydroxyphenyltriazine-based ultraviolet absorber can be obtained as “Tinuvin 1600” (manufactured by BASF).

(dye)
As the dye used in the present invention, any dye can be used as long as it is a disperse dye used for dyeing ordinary polyester fibers, and is not particularly limited. Disperse dyes particularly suitable for polyetherimide fibers are dyes with good diffusibility and high inorganicity in the inorganic / organic ratio, and are generally dyes containing hydroxyl groups and halogens. Examples of suitable dyes for the polyetherimide fiber include, for example, yellow “Dianix Yellow AM-42”, “Dianix Luminous Yellow GN”, “Dianix Luminous Yellow 10G”, orange “Kayalon Brilliant Orange 200”. “Reform Brilliant Orange CV-N”, “Dianix Orange AM-SLR”, red “Dianix Br. Scarlet SF” and the like. Among the above-mentioned dyes, there are those that can satisfactorily dye fibers without using a carrier. However, when a carrier is used, deep dyeing and fastness to washing can be achieved. In addition, since a dye that cannot be dyed satisfactorily without using a carrier can be dyed well by using a carrier, the dye that can be used in the present invention is not particularly limited to the above.

(Career)
In the present invention, it is preferable to use a benzyl alcohol compound, a phthalimide compound, a chlorobenzene compound, a methylnaphthalene compound, or the like as a carrier. These carriers can be used alone, but when used in combination, they can still be dyed darkly. The benzyl alcohol carrier is “benzyl alcohol” (manufactured by Tokyo Chemical Industry Co., Ltd.), the phthalimide imide carrier is “Die Carrier TN-55” (manufactured by Daiwa Chemical Industry Co., Ltd.), and the chlorobenzene carrier is “IPC- Methylnaphthalene series such as “71P Carrier C-71” (manufactured by Yushi Kogyo Co., Ltd.) can be obtained as “Tetrocin AT-M” (Yamakawa Pharmaceutical Co., Ltd.). In addition, “Brian FOK-3” (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), which is a carrier containing an ultraviolet absorber, may be used.

(color)
The flame-retardant fabric of the present invention is characterized by having a color that satisfies the requirements of the European high visibility standard EN471.
In EN471, a required standard is determined from conditions such as CIE chromaticity coordinates and CIE tristimulus values for each type of color used in the material. That is, for red materials, the CIE chromaticity coordinates (x, y) are (0.655, 0.345), (0.570, 0.340), (0.595, 0.315). And (0.690, 0.310), and the luminance coefficient β is specified to be 0.25 or more. Similarly, orange-red materials have chromaticities of (0.610, 0.390), (0.535, 0.375), (0.570, 0.340), and (0.655, 0.345) and the luminance coefficient β must be 0.40 or more, and the yellow material has chromaticity of (0.387, 0.610), ( 0.356, 0.494), (0.398, 0.452), and (0.460, 0.540), and the luminance coefficient β must be 0.70 or more. I must.

For use in applications requiring high visibility, it is indispensable for textile products to meet the requirements of EN471 immediately after dyeing, but various environmental factors, such as the material being difficult to discolor due to light, Alternatively, it is preferable to maintain a state satisfying the requirements of EN471 even when the color changes.
Therefore, the flame retardant fabric of the present invention is orange-red, and the CIE chromaticity coordinates (x, y) of the color after dyeing are (0.624, 0.374), (0.589, 0.366). ), (0.609, 0.343) and (0.655, 0.345), and the luminance coefficient β is preferably 0.40 or more. The flame-retardant fabric of the present invention dyed to a color within this color space falls within the color space defined for the orange-red system of EN471 even when exposed to light. be able to.

  Further, the flame retardant fabric of the present invention is yellow, and the CIE chromaticity coordinates (x, y) of the dyed color are (0.450, 0.549), (0.420, 0.483), Preferably, it is within the range of the color space delimited by (0.375, 0.528) and (0.395, 0.602), and the luminance coefficient β is 0.70 or more. Even when the flame retardant fabric of the present invention dyed in a color within the color space range is exposed to light, the chromaticity of the fabric may fall within the color space range defined for the yellow system of EN471. it can.

(Fiber forming method)
Next, a fiber forming method will be described. The fiber-forming resin is melt-extruded using a single-screw or twin-screw extruder and extruded into a fiber shape from a nozzle having a diameter of 0.1 to 10.0 mm. The fiber of 0.1 to 1000 dtx can be obtained by winding this fiber at 300 to 3000 m / min.

(Method of adding UV absorber)
The ultraviolet absorber is kneaded into the resin in advance and melt-spun the kneaded resin to form a fiber, or after the fiber is formed, the fiber is impregnated with an ultraviolet absorber by post-processing. A flame-retardant fiber having a color that satisfies the requirements of the visibility standard EN471 can be formed.

  In the method of kneading the UV absorber in the resin in advance, a specific amount of UV absorber is given by melt spinning while blending the UV absorber with the fiber forming resin, or by melt spinning using a pre-blended resin composition. Fibers can be obtained. When using an organic ultraviolet absorber, kneading at the time of spinning is preferable because the thermal history is small and thermal decomposition is suppressed. On the other hand, when an inorganic ultraviolet absorber is used, a masterbatch is prepared by melting and mixing the resin and the ultraviolet absorber, and the masterbatch and the remaining fiber-forming resin are melted and kneaded. It is preferable for improving the dispersibility.

  In addition, when the fiber is impregnated with UV absorber by post-processing after fiber formation, the UV absorber is dispersed in water and the fiber is treated in a dispersion to impregnate the fiber with the UV absorber. be able to. When dispersing the ultraviolet absorber in water, a carrier may be added.

(Fabric)
In the present invention, a flame-retardant fabric having high visibility is obtained using the polyetherimide fiber, but any fabric such as a woven fabric, a knitted fabric, and a nonwoven fabric can be obtained.

(Use)
Since the flame retardant fabric having high visibility of the present invention has a color that satisfies the requirements of the European high visibility standard EN471, it is widely used as protective clothing and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited at all by these Examples. In the following Examples, flame retardancy evaluation, chromaticity / luminance evaluation, and light resistance evaluation were performed by the following methods.

[Flame retardance evaluation]
In accordance with the JIS K7201 test method, a sample with a test length of 18 cm made of braided fiber is made, and when the upper end of the sample is ignited, the sample burns continuously for 3 minutes or longer, or after ignition The minimum oxygen concentration (limit oxygen index value (LOI)) necessary for the combustion length of the gas to continue to burn for 5 cm or more was measured, and an average value of n = 3 was adopted.

[Chromaticity / luminance evaluation]
For each cylindrical knitted fabric after dyeing and irradiation with a xenon lamp, the CIE chromaticity coordinates (x, y) and the luminance coefficient β of the reflected light are measured by using a spectrophotometer 3700d manufactured by Minolta, and the chromaticity and luminance are evaluated. did.

[Light resistance evaluation]
A xenon lamp irradiation test was performed according to the third exposure method in ISO 105-B02: 1994. In the orange-red system, irradiation was performed until the level changed from the fifth grade blue scale control standard to 3 levels of gray scale, and in the yellow series, the level was changed from the fourth grade blue scale control standard to 4 levels of gray scale.

<Example 1>
“Ultem 9011” manufactured by Servic Innovative Plastics as a polyetherimide resin (amorphous PEI resin having a weight average molecular weight (Mw) of 32,000, a number average molecular weight (Mn) of 14500, and a molecular weight distribution of 2.2) Was used. Hereinafter, this resin is abbreviated as “U-PEI resin”. While kneading the 3% owf hydroxyphenyltriazine UV absorber “Tinuvin 1600” with U-PEI resin, melt extrusion at 400 ° C., weigh with a gear pump, and discharge from a nozzle of Φ0.2 mm. Winding was performed at a speed of 1500 m / min to obtain 84 dtex / 24 f of fiber, and a tubular knitted fabric was prepared.
The obtained tubular knitted fabric was put into a hermetic pressure-resistant stainless steel container together with a dyeing solution containing a dye, a dye dispersant, a carrier and the like shown below, and dyed at 135 ° C. for 40 minutes. The dyed tubular knitted fabric was subjected to reduction cleaning at 80 ° C. for 20 minutes in the following reduction cleaning bath to remove impurities adhering to the fiber surface.

(Staining solution composition and volume)
7g tubular knitted fabric made of polyetherimide fiber
Ultra MT level [pH adjuster] (manufactured by Mitsima Chemical Co., Ltd.) 1 g / L
Disper TL [dye dispersant] (manufactured by Nikka Chemical Co., Ltd.) 1 g / L
Reform Brilliant Orange CV-N [Dye] (Nikka Fine Techno Co., Ltd.) 3.0% owf
Brian FOK-3 [Carrier] (Matsumoto Yushi Seiyaku Co., Ltd.) 5% owf
Benzyl alcohol [Carrier] 2.1ml (28% owf)
Total liquid volume 210cc

(Reduced cleaning solution composition)
Sodium carbonate 1g / L
Hydrosulfite 1g / L
Amiradine D (Daiichi Kogyo Seiyaku Co., Ltd.) 1g / L
Liquid volume 200cc

<Example 2>
90 parts by weight of U-PEI resin and 10 parts by weight of U-PEI masterbatch resin containing 10% owf of zinc oxide as an inorganic ultraviolet absorber in advance were melt extruded at 400 ° C., weighed with a gear pump, and Φ0 It was discharged from a 2 mm nozzle, and wound at a speed of 1500 m / min to obtain 84 dtex / 24 f fiber. A tubular knitted fabric was created from the yarn. Using the obtained tubular knitted fabric, dyeing and reduction washing were performed in the same manner as in Example 1.

<Example 3>
A tubular knitted fabric was prepared in the same manner as in Example 1, and dyeing was performed under the same conditions as in Example 1 except that the dye was changed to Dianix Luminous Yellow GN (1.5% owf).

<Comparative Example 1>
U-PEI resin is melt-extruded alone at 400 ° C., weighed with a gear pump, discharged from a Φ0.2 mm nozzle, wound up at a speed of 1500 m / min, to obtain 84 dtex / 24 f fibers, and a tubular knitted fabric Created. Using the obtained tubular knitted fabric, dyeing and reduction cleaning were performed under the same conditions as in Example 1.

  Table 1 shows the evaluation results of the tubular knitted fabrics obtained in Examples 1 to 3 and Comparative Example 1.

  Since the flame retardant fabric made of the polyetherimide fiber obtained by the present invention has a color that satisfies the requirements of the European high visibility standard EN471, high visibility protective clothing that requires flame retardancy, etc. Therefore, there is industrial applicability in the field of manufacturing and processing of this fiber.

  As described above, the preferred embodiments of the present invention have been described. However, those skilled in the art will readily consider various changes and modifications within the obvious scope by looking at the present specification. Accordingly, such changes and modifications are to be construed as within the scope of the invention as defined by the appended claims.

Claims (5)

  A flame retardant fabric comprising a polyetherimide fiber and having a color satisfying the requirements of the European High Visibility Standard EN471 by dyeing the fiber with a 3 to 10% owf UV absorber.   The CIE chromaticity coordinates (x, y) of the dyed color are (0.624, 0.374), (0.589, 0.366), (0.609, 0.343) and (0.655). , 0.345), and the brightness coefficient β is 0,40 or more, and the flame-retardant fabric according to claim 1.   The CIE chromaticity coordinates (x, y) of the color after dyeing are (0.450, 0.549), (0.420, 0.483), (0.375, 0.528) and (0.395). , 0.602), and the luminance coefficient β is not less than 0.70.   The flame retardant fabric according to any one of claims 1 to 3, wherein at least one of the ultraviolet absorbers is a hydroxyphenyltriazine ultraviolet absorber.   The flame-retardant fabric according to any one of claims 1 to 4, wherein at least one of the ultraviolet absorbers is an inorganic ultraviolet absorber.