JP2015168908A - Flame-retardant fabric having high visibility - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant fabric excellent in high visibility.SOLUTION: The flame-retardant fabric is obtained by using and dyeing a flame-retardant fiber comprising a resin in which a polyetherimide-based resin and a specific thermoplastic resin are blended and has a color satisfying need criteria of Europe high visibility standard EN471.

Description

  The present invention relates to the requirements of European high visibility standard EN471 obtained by dyeing using a flame retardant fiber made of a resin blended with a flame retardant polyetherimide resin and a specific thermoplastic resin. It relates to a flame retardant fabric having a color satisfying the above.

  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 determined 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 earnestly examining the above problems, the present inventors made flame retardancy by dyeing using a fiber made of a resin blended with a polyetherimide resin having excellent flame retardancy and a specific thermoplastic resin. The inventors have found that a fabric having excellent color and satisfying the requirements of the European high visibility standard EN471 can be obtained, and the present invention has been achieved.

  That is, the present invention is a resin obtained by blending a polyetherimide resin (A) and a thermoplastic resin (B) having a glass transition temperature lower than that of the resin (A) and being completely compatible. And dyeing with a flame-retardant fiber comprising a resin having a mass ratio of the resin (A) to the resin (B) of (A) / (B) = 50/50 to 95/5 A flame retardant fabric having a color that satisfies the requirements of the European high visibility standard EN471.

  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.

  It is preferable that the flame retardant fabric is dyed at a temperature of 95 to 120 ° C.

  The flame retardant fabric is preferably characterized in that the flame retardant fiber contains 1 to 10% owf of an ultraviolet absorber.

  In the flame retardant fabric, it is preferable that at least one of the ultraviolet absorbers is a hydroxyphenyltriazine-based ultraviolet absorber.

  In the flame retardant fabric, at least one of the ultraviolet absorbers is preferably an inorganic ultraviolet absorber.

  According to the present invention, a color satisfying the requirements of the European High Visibility Standard EN471 is obtained by dyeing with a flame retardant fiber made of a resin obtained by blending a polyetherimide resin and a specific thermoplastic resin. The flame retardant fabric having both high visibility and sufficient fiber strength can be obtained. Moreover, it can dye | stain by comparatively low temperature by using the said blend fiber, and can suppress the strength fall by a dyeing process.

  In the present invention, a flame retardant fabric obtained by dyeing with a flame retardant fiber composed of a resin obtained by blending a flame retardant polyetherimide resin and a specific thermoplastic resin is highly visible in Europe. One of the characteristics is that it has a color that satisfies the requirements of the sex standard EN471.

(Polyetherimide resin)
Examples of the polyetherimide resin (A) 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 (A) 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.

(Thermoplastic resin)
In the present invention, it is important to use a flame-retardant fiber made of a resin obtained by blending the polyetherimide resin (A) and a specific thermoplastic resin (B). By using fibers made of such a blended resin, it is possible to dye at a lower temperature than in the case of the polyetherimide fiber (A) alone, and it is difficult to combine high visibility and sufficient fiber strength. A fuel fabric is obtained. The thermoplastic resin (B) is a resin having a glass transition temperature lower than that of the polyetherimide resin (A), and the blend resin with the polyetherimide resin (A) needs to have fiber forming ability. It is.

  Since the thermoplastic resin (B) has a glass transition point lower than that of the polyetherimide resin (A) as described above, it has conventionally been necessary to perform spinning and dyeing at a high temperature. Even when an etherimide resin is used, not only the spinning temperature and dyeing temperature can be lowered, but also the functionality of the polyetherimide resin (A) having a rigid and strong molecular structure. It is possible to favorably provide the functionality by the additive.

  The glass transition point (Tg) of the thermoplastic resin (B) is preferably 160 ° C. or lower (eg, about 50 to 160 ° C.), more preferably 130 ° C. or lower, and even more preferably 100 ° C. or lower. The glass transition point is measured by measuring the temperature dependence of the loss tangent (tan δ) at a frequency of 10 Hz and a heating rate of 10 ° C./min using, for example, a solid dynamic viscoelastic device Leospectra DVE-V4 manufactured by Rheology. The peak temperature can be obtained. .

  Examples of the thermoplastic resin (B) include polyester resins (preferably polyethylene terephthalate resins and polyethylene naphthalate resins), polycarbonate resins, and polyether ether ketone resins. Among these, more preferable thermoplastic resins are polyester resins and polycarbonate resins from the viewpoint of a low glass transition point, and among them, crystalline polyester resins (excellent thermal stability between polyetherimide resins) For example, crystalline polyethylene terephthalate resin, crystalline polyethylene naphthalate resin, particularly crystalline polyethylene terephthalate resin) are preferable.

  Crystalline polyethylene terephthalate refers to polyethylene terephthalate having a crystal melting peak around 255 ° C. in differential scanning calorimetry (DSC), and the intrinsic viscosity [η] is 0.5 to 0.8 from the viewpoint of spinnability. preferable.

  From the viewpoint of improving the blendability, it is important that the thermoplastic resin (B) is a resin that is completely compatible with the polyetherimide resin (A). In this case, the thermoplastic resin may be partially modified in the molecular chain as long as it is completely compatible.

  Here, the complete compatibility with the polyetherimide resin (A) means complete compatibility in a temperature range in which spinning is possible (for example, room temperature to 450 ° C.), and such complete compatibility is It can be determined by confirming that it has a single glass transition point in the dynamic viscoelasticity measurement.

  The mass ratio of the polyetherimide resin (A) and the thermoplastic resin (B) is preferably 50/50 to 95/5, more preferably about 55/45 to 90/10, and still more preferably 60/50. It may be about 40 to 85/15.

(UV absorber)
In the present invention, it is preferable to add 1 to 10% owf of an ultraviolet absorber for dyeing. More 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, 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. 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). In addition, a dyeing assistant containing an ultraviolet absorber may be used, and for example, “Brian FOK-3” (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) may be used.

(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.) and the like.

(Dyeing method)
In the present invention, as a method for dyeing a flame-retardant fiber made of a resin obtained by blending a polyetherimide resin (A) and a thermoplastic resin (B), it can be dyed with a disperse dye similar to a normal polyester. . The presetting and final setting temperatures are preferably 160 ° C. or lower. The dyeing temperature can be appropriately set in accordance with the desired dyeing concentration, the kind of dye, the presence or absence of a carrier (phthalimide, etc.), etc. It is 95-120 degreeC, More preferably, it is 100-115 degreeC. When the dyeing temperature is less than 95 ° C., it cannot be dyed darkly, and when it exceeds 120 ° C., the fiber becomes hard, which is not preferable.

(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 dyed color 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. A blend resin of a polyetherimide resin (A) and a thermoplastic resin (B), which is a fiber-forming resin, is melt-extruded using a single screw or twin screw extruder, and has a diameter of 0.1 to 10.0 mm. Extruded from the nozzle to form a fiber. 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)
When the flame retardant fiber according to the present invention contains an ultraviolet absorber, the ultraviolet absorber is kneaded in advance in the resin and melt-spun the kneaded resin to form a fiber, or after fiber formation, By impregnating the fiber with an ultraviolet absorber by post-processing, it is possible to form a flame-retardant fiber having a color that satisfies the requirements of the European high visibility standard EN471.

  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 can be obtained using a flame retardant fiber made of a resin obtained by blending the polyetherimide resin and a specific thermoplastic resin. This fabric can also 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, strength evaluation, and chromaticity / luminance 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 fibers is made, and when the upper end of the sample is ignited, the sample burns continuously for 3 minutes or more, 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.

[Strength evaluation]
A filament knitted fabric was prepared, the fiber was unwound, the filament fiber strength was subjected to a tensile test using an autograph manufactured by Shimadzu Corporation, and the strength was evaluated before and after dyeing.

[Chromaticity / luminance evaluation]
The CIE chromaticity coordinates (x, y) and the luminance coefficient β of the reflected light were measured for each of the tubular knitted fabrics after dyeing and after irradiation with the xenon lamp using a spectrophotometer 3700d manufactured by Minolta Co., Ltd. Evaluated.
The 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>
Polyethylene terephthalate resin (manufactured by Tainan Boseki Co., Ltd.) ([η] = 0.6, Tg = 69 ° C. crystalline polyethylene terephthalate resin) (hereinafter abbreviated as C-PET resin) 25 parts by mass, polyetherimide resin ( “Ultem 9011” manufactured by Servic Innovative Plastics) (amorphous polyetherimide resin having a weight average molecular weight (Mw) of 32000, a number average molecular weight (Mn) of 14500, and a molecular weight distribution of 2.2) (We abbreviate as U-PEI resin) Kneading 25 parts by mass with a twin screw extruder, measuring with a gear pump as it is, discharging from a nozzle of Φ0.2 mm at 340 ° C, winding at a speed of 1500 m / min The fiber which consists of 84 dtex / 24f blend resin was obtained, and the cylinder knitted fabric was created.

  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 115 ° 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 blend fiber of U-PEI and C-PET
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] (manufactured by Nikka Fine Techno Co., Ltd.) 4.0% owf
Brian FOK-3 [Dyeing assistant containing UV absorber] (Matsumoto Yushi Seiyaku Co., Ltd.) 5% owf
Die Carrier TN-55 [Carrier] (Daiwa Chemical Industry Co., Ltd.) 4% 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>
Similar to Example 1, except that a tubular knitted fabric made of a blended fiber of U-PEI and C-PET was prepared and the dye was changed to Dianix Luminous Yellow GN (1.5% owf). Dyeing and reduction cleaning were performed under the conditions.

<Comparative Example 1>
U-PEI resin is melt-extruded alone at 400 ° C., weighed with a gear pump, discharged from a nozzle with a diameter of 0.2 mm, wound at a speed of 1500 m / min to obtain a fiber of 84 dtex / 24 f, 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. Since the dyeing temperature is low and not suitable for the U-PEI single resin, it was not possible to dye in a color that satisfies the requirements of the European high visibility standard EN471.

<Comparative Example 2>
A cylindrical knitted fabric made of U-PEI single fiber was prepared in the same manner as in Comparative Example 1, and dyeing and reduction washing were performed in the same manner as in Example 1 except that the dyeing temperature was changed to 135 ° C. Although it was possible to dye to a color satisfying EN471, the strength was significantly reduced due to the high dyeing temperature.

Table 1 shows the evaluation results of the tubular knitted fabrics obtained in Examples 1-2 and Comparative Examples 1-2.

  A flame retardant fabric made of a flame retardant fiber made of a resin obtained by blending a polyetherimide resin and a specific thermoplastic resin obtained by the present invention has a color that satisfies the requirements of the European High Visibility Standard EN471. In addition, since the decrease in fiber strength due to the dyeing process can be suppressed, it can be used as a highly visible protective clothing that requires flame retardancy. May be available.

  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 (7)

  A resin obtained by blending a polyetherimide-based resin (A) with a thermoplastic resin (B) having a glass transition temperature lower than that of the resin (A) and being completely compatible, and the resin (A) And a resin having a mass ratio of (A) / (B) = 50/50 to 95/5, and dyeing with a flame retardant fiber, European high visibility standard EN471 A flame retardant fabric having a color that satisfies the required standards.   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 luminance coefficient β is 0.40 or more.   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 0.70 or more, and the flame-retardant fabric according to claim 1.   The flame retardant fabric according to any one of claims 1 to 3, wherein the flame retardant fabric is dyed at a temperature of 95 to 120 ° C.   The flame retardant fabric according to any one of claims 1 to 4, wherein the flame retardant fiber contains 1 to 10% owf of an ultraviolet absorber.   The flame-retardant fabric according to claim 5, wherein at least one of the ultraviolet absorbers is a hydroxyphenyltriazine ultraviolet absorber.   The flame retardant fabric according to claim 5 or 6, wherein at least one of the ultraviolet absorbers is an inorganic ultraviolet absorber.