JP2018003192A - Molded product of nonwoven fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded product of nonwoven fabric excellent in combustion and heat generation properties, capable of achieving both of fire retardancy and shading.SOLUTION: The molded product of nonwoven fabric of the present invention contains a polyetherimide fiber, with a phosphorus fire retardant and a disperse dye added thereto.SELECTED DRAWING: None

Description

  The present invention relates to a nonwoven fabric molded article containing a polyetherimide fiber.

  Polyetherimide fiber is excellent in heat resistance and flame retardancy, and is used in many applications such as industrial materials, electrical and electronic fields, agricultural materials, apparel, optical materials, aircraft, automobiles, and ships. It is used.

  Moreover, although the fabric which consists of a polyetherimide type fiber excellent in a flame retardance can consider the application to an aircraft use etc., the light-shielding property may be calculated | required by the polyetherimide fabric in that case. In this case, in order to impart light shielding properties to the fiber, it is necessary to dye the polyetherimide fiber to a black color.

  Here, the polyetherimide fiber is a fiber excellent in dyeability, but the fabric composed of the polyetherimide fiber alone has a problem that the strength is substantially lowered.

  Therefore, the strength of the nonwoven fabric can be increased by dyeing a fabric obtained by blending a polyetherimide fiber with a heat-resistant fiber (for example, a meta-aramid fiber) that can withstand high-temperature exposure using a disperse dye. Secured fabrics have been proposed. And it is described that the fabric excellent in the flame retardance and dyeability can be obtained by such a structure (for example, refer patent document 1).

JP 2012-36511 A

  Here, in general, since organic dyes cannot withstand the spinning temperature, as described in Patent Document 1, dyeing is performed using a disperse dye after spinning, but since this dye is an organic substance, a polyether is used. When the imide fiber is exposed to a high temperature, the dye adhering to the surface of the polyetherimide fiber is decomposed by heat, resulting in a problem that flame retardancy and light shielding properties are lowered.

  That is, in a composite material combining a polyetherimide fiber and a heat-resistant fiber, it is difficult to impart light-shielding properties by coloring while maintaining the flame retardancy of the polyetherimide fiber. There was a problem.

  In addition, when an inorganic dye is added after spinning instead of an organic dye, there is a problem that the combustion exotherm of the polyetherimide resin deteriorates and the combustion exotherm of the polyetherimide fiber decreases. It was.

  Then, this invention is made | formed in view of the above-mentioned problem, and it aims at providing the nonwoven fabric molded object which can be compatible with a flame retardance and light-shielding property while being excellent in combustion exothermic property.

  In order to achieve the above object, the nonwoven fabric molded article of the present invention is characterized in that it contains polyetherimide fibers and is provided with a phosphorus flame retardant and a disperse dye.

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in combustion exothermic property, the nonwoven fabric molded object which can make a flame retardance and light-shielding property compatible can be provided.

  Hereinafter, the present invention will be described in detail. The nonwoven fabric molded body of the present invention is a nonwoven fabric molded body containing polyetherimide fibers and provided with a phosphorus-based flame retardant and a disperse dye.

<Polyetherimide fiber>
The polyetherimide fiber in the present invention is composed of a polyetherimide polymer containing an aliphatic, alicyclic or aromatic ether unit and a cyclic imide as repeating units. The polyetherimide polymer is not particularly limited as long as it has amorphous and melt moldability.

  Moreover, as long as the effect of the present invention is not impaired, the main chain of the etherimide-based polymer has a cyclic imide, a structural unit other than an ether bond, such as an aliphatic, alicyclic or aromatic ester unit, an oxycarbonyl unit, or the like. It may be contained. More specifically, for example, 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride mainly having a structural unit represented by the following general formula (1) and m- A polyetherimide polymer obtained by a polycondensate with phenylenediamine can be used. This polyetherimide polymer can be obtained by fiberizing an amorphous polyetherimide polymer commercially available from Sabic Innovative Plastics under the trade name “Ultem”.

  The molecular weight of the polyetherimide-based polymer is not particularly limited, but the weight average molecular weight (Mw) is 1000 to 80000 from the viewpoint of mechanical properties, dimensional stability, and process passability of the obtained fiber. Is preferred.

  In addition, it is preferable to use a polymer having a high molecular weight because it is excellent in terms of fiber strength, heat resistance, and the like, but from the viewpoint of reducing manufacturing cost and fiberization cost, the range of Mw is preferably 2000 to 50000, and 3000 ˜40000 is more preferred.

  In addition, the polyetherimide fiber of the present invention may contain an antioxidant, a radical inhibitor, a matting agent, an ultraviolet absorber, an inorganic substance, and other polymers as long as the effects of the present invention are not impaired.

  For example, specific examples of inorganic materials include carbon nanotubes, fullerene, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, alumina silicate and other silicates, silicon oxide, magnesium oxide , Metal oxides such as alumina, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, calcium hydroxide, magnesium hydroxide and aluminum hydroxide Such hydroxides, glass beads, glass flakes, glass powders, ceramic beads, boron nitride, silicon carbide, and silica are used. Specific examples of the polymer include polyamide, polybutylene terephthalate, polyethylene terephthalate, modified polyphenylene ether, polysulfone, polyether sulfone, polyallyl sulfone, polyketone, polyarylate, liquid crystal polymer, polyether ketone, polythioether ketone, poly Ether ether ketone, polyimide, polyamideimide, polyethylene tetrafluoride, polycarbonate and the like are used.

<Disperse dye>
The disperse dye is not particularly limited as long as it is a disperse dye that can be used for dyeing polyetherimide fibers.

  Disperse dyes 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. Specific examples of suitable dyes for polyetherimide fibers include, for example, “Dianix Yellow E-3G”, “Dianix Red E-FB”, “Dianix Orange 2G-FS”, and “Dianix Blue 3RSF” manufactured by Dystar. ”,“ Dianix Blue S-2G ”,“ Dianix Navy S-2G ”,“ Kayalon Micro Yellow AQ-LE ”,“ Kayalon Micro Red AQ-LE ”,“ Kayalon P Black ”manufactured by Nippon Kayaku Co., Ltd. Etc.

  The amount of the disperse dye contained in the polyetherimide fiber is preferably in the range of 0.3 to 1.5% owf, and more preferably in the range of 0.3 to 0.8% owf. This is because if it is less than 0.3% owf, the dyeing property may be insufficient, and if it is more than 1.5% owf, an excessive amount of dye is supplied, which is not preferable in terms of cost.

<Phosphorus flame retardant>
As the flame retardant, a non-halogen flame retardant is used in consideration of reduction of environmental pollution caused by the halogen-containing flame retardant, and among these, a phosphorus flame retardant is used in the present invention.

  As the phosphorus-based flame retardant, those having a low molecular weight (for example, a molecular weight of 1000 or less) are preferable from the viewpoint of allowing the flame retardant to penetrate into the interior of the polyetherimide fiber. In view of industrial versatility, flame retardancy, color suppression, etc., phosphoric acid, phosphorous acid, metaphosphoric acid, etc. and their derivatives (phosphoric acid, phosphorous acid, metaphosphoric acid, etc. are directly alkylated on the phosphorus atom. Group or a compound to which a phenyl group is bonded), phosphoric acid, phosphorous acid, metaphosphoric acid, etc. or condensates of these derivatives, esters of the condensates (alkyl esters, phenyl esters, etc.), ammonium salts , Amidated compounds, phosphazene compounds and derivatives thereof (phenoxy group, isopropoxy group and the like added to phosphorus) and the like can be suitably used as the phosphoric acid compound. Of these, phosphazene compounds can be more suitably used from the viewpoint of chemical resistance.

  More specifically, methyl phosphate, dimethyl phosphate, trimethyl phosphate, ethyl phosphate, diethyl phosphate, triethyl phosphate, diethyl hexyl phosphate, butyl phosphate, dibutyl phosphate, tributyl phosphate, tricresyl phosphate, trixylenyl host lixylenyl phosphate, Phosphate esters (alkyl esters) such as ethyl diethyl phosphonoacetate, butyl pyrophosphate, butoxyethyl phosphate, 2-ethylhexyl phosphate, di (2-ethylhexyl) phosphate, phenyl phosphate, diphenyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate , Phenyl esters, etc.), triammonium phosphate, phosphorus Ammonium, ammonium hydrogen phosphate, phosphoric acid compound salt such as ammonium dihydrogen phosphate, other phosphate amine compounds, amide phosphoric acid, phenylphosphonic acid, dimethylphenyl phosphonate, and the like diethyl phenyl phosphonate. Also, esters (alkyl esters, phenyl esters) and phosphazene compounds of condensates of phosphoric acid or phosphoric acid derivatives such as methyl polyphosphate, ethyl polyphosphate, propyl polyphosphate, butyl polyphosphate, and phenyl polyphosphate, A phosphazene compound derivative (for example, diphenoxyphosphazene, diisopropoxyphosphazene, etc.) in which two substituents in the phosphorous part of phosphazene are singly or in combination of substituents that can be added such as phenoxy group, isopropoxy group, methoxy group, etc. Can be mentioned.

  The “phosphorous flame retardant” referred to here is a compound containing phosphorus, and from the viewpoint of suppressing a decrease in the glass transition temperature of the polymer constituting the polyetherimide fiber, the polyetherimide fiber The concentration of the phosphorus-based flame retardant contained is preferably 2000 ppm or less in terms of phosphorus concentration.

  Two or more phosphorus-based flame retardants may be used in combination, and a flame retardant other than the phosphorus-based flame retardant may be further used in combination as long as the effects of the present invention are not impaired.

  And in this invention, since such a phosphorus flame retardant acts as an adjuvant of a flame retardant mechanism, the flame retardance of a nonwoven fabric molded object can be improved.

  More specifically, as a mechanism by which the polyetherimide fiber exhibits flame retardancy, when the polyetherimide fiber is exposed to a high temperature, the surface of the polyetherimide fiber has a char called “char”. It is known that a film forms and protects the polyetherimide fiber, but the disperse dye attached to the surface of the polyetherimide fiber is poor in flame retardancy and inhibits the generation of char. It is considered that the flame retardancy of the polyetherimide fiber is lowered.

  However, in the present invention, since the phosphorus-based flame retardant is imparted to the disperse dye, the phosphorus-based flame retardant promotes the formation of char and suppresses the decrease in flame retardancy due to the disperse dye. It is thought that flammability can be improved.

  As described above, in the present invention, by impregnating the surface of the polyetherimide fiber with the disperse dye and the phosphorus flame retardant, the polyetherimide fiber is dyed black to obtain a light shielding property, and the phosphorus flame retardant. Is present on the fiber surface, it becomes easy to form char on the fiber surface, and as a result, the flame retardancy of the fiber surface is improved.

  In addition, since the phosphorus compound has a low molecular weight, it easily penetrates into the polyetherimide fiber and is added to the carrier (to increase the dye absorbability of the fiber, and the dye diffuses into the fiber. It functions as a dyeing aid having an effect. Therefore, by adding a phosphorus compound, the phosphorus compound penetrates into the polyetherimide fiber, and the structure of the polyetherimide fiber loosens, so that the disperse dye easily penetrates into the polyetherimide fiber. As a result, the dyeability of the polyetherimide fiber is improved.

  In the present invention, it is preferable to use an aromatic phosphate ester compound as the phosphorus flame retardant. This is because the phosphoric acid ester generates a volatile component at the time of combustion, thereby causing heat generation, and as a result, it is possible to suppress a decrease in combustion heat generation.

<Heat resistant fiber>
Further, in the present invention, from the viewpoint of suppressing the thermal shrinkage of the polyetherimide fiber, ensuring the strength of the nonwoven fabric, and further exhibiting excellent flame retardancy, the polyetherimide fiber and the heat resistance You may comprise a nonwoven fabric molded object with the composite material which combined the fiber.

  The heat-resistant fiber is not particularly limited, but it is preferable to use a heat-resistant fiber that does not contain a halogen in order to suppress generation of toxic gas at the time of fire or incineration and the amount of smoke generated as much as possible.

  Examples of the heat-resistant fiber not containing halogen include at least one selected from meta-aramid fiber, para-aramid fiber, phenol fiber, polyamide-imide fiber, polybenzimidazole fiber, polyarylate fiber, cellulose fiber, and nylon fiber. It is preferable to be composed of types. Note that some of these heat-resistant fibers may be subjected to copolymerization, modification group introduction, chemical modification, or the like as long as the effects of the present invention are not impaired.

  Moreover, in the nonwoven fabric molded body of the present invention, when a composite fiber composed of a polyetherimide fiber and a heat resistant fiber is used as a constituent fiber, the mass ratio of the polyetherimide fiber and the heat resistant fiber in the composite fiber That is, (the mass of the polyetherimide fiber / the mass of the heat resistant fiber) is preferably 90/10 to 50/50.

  This is because when the mass ratio of the polyetherimide fiber is lower than 50, the ratio of the heat-resistant fiber having poor flame retardancy increases, so the combustion exothermic property may decrease. This is because if the mass ratio is greater than 90, the strength of the nonwoven fabric may decrease.

<Other ingredients>
Also in the dyeing method in the present invention, a dyeing aid such as a pH adjuster or an emulsifier can be used as long as the effects of the present invention are not impaired, as in the case of normal polyester dyeing.

<Nonwoven fabric molding>
The nonwoven fabric molded body of the present invention is a nonwoven fabric molded body that is excellent in combustion exothermic properties and can achieve both flame retardancy and light shielding properties, and therefore used particularly for applications such as aircraft, automobiles, railways, and ships. can do.

  The method for producing the nonwoven fabric molded body of the present invention is not particularly limited, and examples include spunlace nonwoven fabric, needle punched nonwoven fabric, steam jet nonwoven fabric, dry papermaking method, wet papermaking method, etc. From this point of view, it is preferable to use a dry nonwoven fabric.

  Here, in the nonwoven fabric molded body of the present invention, the LOI (limit oxygen index) value measured in accordance with the JIS L1091 test method is preferably larger than 35 from the viewpoint of ensuring excellent flame retardancy. . This is because when the LOI value is 35 or less, there may be a disadvantage that the nonwoven fabric molded body tends to burn.

In addition, since the nonwoven fabric molded body of the present invention can be applied to aircraft applications in particular, from the viewpoint of ensuring flame retardancy when applied to aircraft applications, the Federal Aviation Administration of the United States Federal Aviation Administration (FAA) Regulation (FAR) Part 25 (Federal Aviation Administration (FAA) Federal Aviation Regulation (FAR) Part 25) measured in accordance with the combustion exotherm test, the total calorific value for 2 minutes after the start of measurement is less than 60 kw min / m ² And more preferably less than 55 kw min / m ² . Further, it is preferable that the maximum amount of heat generated in 5 minutes measured after the start of the measurement is less than 60 kW / ^{m 2,} more preferably less than 55kW / ^{m 2.}

  Similarly, considering the application to aircraft applications, ASTM method E-662-2 (standard for a specific optical density of smoke generated from a solid material from the viewpoint of suppressing the amount of smoke generated during combustion. The smoke density (DS) at the time of combustion measured according to the inspection method) is preferably less than 150, more preferably less than 120.

  Moreover, there is no restriction | limiting in particular in the form of the spun yarn of a polyetherimide type fiber and a heat resistant fiber used for the nonwoven fabric molded body of the present invention, a heat-mixed yarn in a uniformly mixed spun yarn or a core part, and a sheath part. A known spun yarn form such as a core-sheath spun yarn in which polyetherimide fibers are arranged can be used. In addition, the uniform mixing here refers to simple cotton blending, and is not limited to a mixed state of two or more kinds of fibers, and may be incomplete. Although a fabric can be obtained by weaving such spun yarn, the woven structure is not particularly limited as long as it does not impair the effects of the present invention. In the range that does not impair the performance defined in the present invention, fibers other than the above-mentioned spun yarn, for example, conductive fibers and cotton spun yarn are preferably blended at a ratio of 20% by weight or less, more preferably 10% by weight or less. It doesn't matter.

  Next, the manufacturing method of the nonwoven fabric molded object of this invention is demonstrated.

  First, the manufacturing method of the polyetherimide-type fiber which is the main component of the nonwoven fabric molded object of this invention is demonstrated. In the production of the polyetherimide fiber of the present invention, a known melt spinning apparatus can be used. In other words, polyetherimide polymer pellets are melt-kneaded with a melt extruder, the molten polymer is guided to a spinning cylinder, weighed with a gear pump, and the polyetherimide fiber is wound by winding the yarn discharged from the spinning nozzle. can get.

  Here, when the amorphous polymer is stretched, the shrinkage at high temperature increases, so in the polyetherimide fiber used in the present invention, the yarn discharged from the spinning nozzle is not stretched and is wound as it is. It is preferable to take. At that time, the winding speed is not particularly limited, but it is not preferable if molecular orientation occurs on the spinning line, and therefore it is preferable to wind in the range of 500 m / min to 4000 m / min. If it is less than 500 m / min, it is not preferable from the viewpoint of productivity. On the other hand, if it is higher than 4000 m / min, not only the molecular orientation is sufficient to cause shrinkage at high temperatures, but also fiber breakage tends to occur. Therefore, it is not preferable.

  Further, in the production of the polyetherimide fiber used in the present invention, it is preferable not to perform a stretching step in order to ensure the heat resistance of the fiber and the fabric obtained by weaving the fiber. Since polyetherimide fibers are amorphous, entropy shrinkage due to increased molecular motion occurs at high temperatures when stretching is performed in the conventional fiber manufacturing process. Thus, the dimensional stability deteriorates at high temperatures, and it becomes impossible to achieve heat resistance that can withstand actual use. Therefore, in the present invention, a polyetherimide fiber having high heat resistance obtained by not drawing is preferably used while considering the feature of “amorphous”. In addition, there is no restriction | limiting in particular regarding the cross-sectional shape of the polyetherimide type fiber used for the fabric of this invention, Circular, hollow, flat, or atypical cross sections, such as a star shape, may be sufficient.

  Next, a short fiber is produced from the obtained polyetherimide fiber, and this short fiber is put on a card to produce a fiber web composed of the polyetherimide fiber and the heat resistant fiber. Next, the webs are stacked and a nonwoven fabric is obtained using a needle punch method or the like.

  Next, the produced nonwoven fabric is put in a sealable pressure resistant stainless steel container together with a dyeing solution containing a dye, a phosphorus-based flame retardant, a dye dispersant, a pH adjuster, etc., and dyed at a predetermined temperature for a predetermined time. The nonwoven fabric molded body of the invention is produced.

  Dyeing at a temperature in the range of 100 to 150 ° C., preferably 110 to 140 ° C., is preferable because dark dyeing is possible and fiber property deterioration due to dyeing is suppressed. When the dyeing temperature is lower than 100 ° C, the dyeing property becomes insufficient. When the dyeing temperature exceeds 150 ° C, the dye penetrates into the polymer constituting the polyetherimide fiber, and the glass transition temperature of the polymer is lowered. Inconvenience may occur.

  In the present invention, as a dyeing apparatus, a winch, a zicker, a beam, a liquid dyeing machine, or the like can be used. From the viewpoint of uniformly dyeing the entire nonwoven fabric, a high-temperature high-pressure liquid dyeing machine is used. It is preferable to do this.

  Further, after dyeing treatment, the dyed dyed product is immersed in a reduction cleaning bath (an aqueous solution containing an alkali such as caustic soda, a reducing agent such as hydrosulfite, a surfactant, etc.) by a general method. Reduction cleaning is performed to remove impurities such as dye attached to the fiber surface.

  Hereinafter, the present invention will be described based on examples. In addition, this invention is not limited to these Examples, These Examples can be changed and changed based on the meaning of this invention, and they are excluded from the scope of the present invention. is not.

Example 1
<Preparation of non-woven fabric molding>
A polyetherimide resin (manufactured by Servic Innovative Plastics, trade name: Ultem 9011) was put into a single screw extruder, and kneaded with a screw while being melted at 390 ° C., and weighed with a gear pump. Next, 2640 dtex / 1200 f of polyetherimide fiber was obtained by discharging from a nozzle having a diameter of 0.3 mm under conditions of a discharge amount of 400 g / min and winding at a speed of 1500 m / min.

  The polyetherimide resin used in this example is an amorphous polyetherimide resin, the weight average molecular weight Mw is 32,000, the number average molecular weight Mn is 14500, and the molecular weight distribution Mw / Mn is 2.2. It was.

  Next, after crimping the obtained polyetherimide fiber, it was cut to produce a short fiber having a fiber length of 76 mm.

Next, this short fiber is put on a card, and a fiber web (weighing 150 g / m) made of Kevlar 29 (fiber length 76 mm, manufactured by DuPont, hereinafter abbreviated as “Kev”) which is a polyetherimide fiber and para-aramid fiber. m ² ) was prepared. The mass ratio of the polyetherimide fiber and the heat-resistant fiber (the mass of the PEI fiber / the mass of Kev) was set to 80/20. Next, seven sheets of this web were piled up and the nonwoven fabric was obtained using the needle punch method.

  Next, the produced non-woven fabric was made of black dye (manufactured by Nippon Kayaku Co., Ltd., trade name: Kayalon Polyester Black ECXN 300, concentration: 0.5 owf), phosphorus flame retardant (made by Meisei Chemical Co., Ltd., trade name) : Phoscon FR-SEU, composition: aromatic phosphate ester compound, concentration: 2.5 owf (1000 ppm in terms of phosphorus concentration)), dye dispersant (manufactured by Nikka Chemical Co., Ltd., trade name: Disper TL, concentration: 1 g / L), and a pH adjusting agent (Mitima Chemical Co., Ltd., trade name: Ultra MT level, concentration: 1 g / L) together with a staining solution that can be sealed, and sealed at 130 ° C. for 40 minutes. Stained.

  And the nonwoven fabric molded object whose thickness is 2 mm was produced by hot-pressing the dyed nonwoven fabric at 240 degreeC using a hot press machine.

<Measurement of LOI (oxygen limit index)>
Based on the test method of JIS L1091, LOI (oxygen limit index) of the produced nonwoven fabric molded body was measured. The results are shown in Table 1.

<Measurement of combustion smoke concentration>
Based on ASTM method E-662-2-03, the optical density (Ds) of smoke generated when the produced nonwoven fabric molded body was exposed to a flame state was measured using a light transmittance measurement method. The results are shown in Table 1.

<Combustion exothermic evaluation>
In the calorific heat test (OSU 65/65 test) of the US Federal Aviation Regulation (FAR) Part 25 of the US Federal Aviation Administration (FAA), the total calorific value [kW min / m for 2 minutes after the start of calorimetric measurement in the produced nonwoven fabric body ² ] and the maximum calorific value [kW / m ² ] in 5 minutes after the start of measurement. The results are shown in Table 1.

<Light shielding evaluation>
A non-woven fabric prepared by preparing a lamp (MORITEX MHF-G150LR) having an illuminance of 80 kLx and a color temperature of 3400 K as a light source simulating sunlight (illuminance: 32 to 100 kLx, color temperature: 2000 K in the morning and evening, 5000 to 6000 K in the daytime) A light source was installed at a distance of about 1.5 cm from the light and projected onto the nonwoven fabric. Next, a digital camera was installed at a distance of about 10 cm opposite to the light source, and the nonwoven fabric was photographed. The imaged area was approximately 12 cm × 12 cm. And what rejected the thing by which the position of the light source was confirmed by the transmitted light was made unacceptable, and what was not confirmed was made acceptable. The results are shown in Table 1.

(Example 2)
A nonwoven fabric molded body was produced in the same manner as in Example 1 except that the concentration of the phosphorus-based flame retardant was changed to 0.75% owf (300 ppm in terms of phosphorus concentration).

  Next, in the same manner as in Example 1 described above, LOI (oxygen limit index) measurement, combustion smoke concentration measurement, combustion exothermic evaluation, and light shielding evaluation were performed. The results are shown in Table 1.

(Example 3)
A nonwoven fabric molded body was produced in the same manner as in Example 1 except that the concentration of the black dye was changed to 0.3% owf.

  Next, in the same manner as in Example 1 described above, LOI (oxygen limit index) measurement, combustion smoke concentration measurement, combustion exothermic evaluation, and light shielding evaluation were performed. The results are shown in Table 1.

Example 4
A nonwoven fabric molded body was produced in the same manner as in Example 1 except that the mass of polyetherimide fiber / the mass of Kevlar 29 was set to 90/10.

  Next, in the same manner as in Example 1 described above, LOI (oxygen limit index) measurement, combustion smoke concentration measurement, combustion exothermic evaluation, and light shielding evaluation were performed. The results are shown in Table 1.

(Example 5)
A nonwoven fabric molded body was produced in the same manner as in Example 1 except that the concentration of the phosphorus flame retardant was 5.0% owf (2000 ppm in terms of phosphorus concentration).

  Next, in the same manner as in Example 1 described above, LOI (oxygen limit index) measurement, combustion smoke concentration measurement, combustion exothermic evaluation, and light shielding evaluation were performed. The results are shown in Table 1.

(Example 6)
A nonwoven fabric molded body was produced in the same manner as in Example 1 except that the concentration of the black dye was 1.5% owf.

  Next, in the same manner as in Example 1 described above, LOI (oxygen limit index) measurement, combustion smoke concentration measurement, combustion exothermic evaluation, and light shielding evaluation were performed. The results are shown in Table 1.

(Example 7)
A nonwoven fabric molded body was produced in the same manner as in Example 1 except that the mass of polyetherimide fiber / the mass of Kevlar 29 was set to 50/50.

  Next, in the same manner as in Example 1 described above, LOI (oxygen limit index) measurement, combustion smoke concentration measurement, combustion exothermic evaluation, and light shielding evaluation were performed. The results are shown in Table 1.

(Comparative Example 1)
A nonwoven fabric molded body was produced in the same manner as in Example 1 except that the phosphorus-based flame retardant was not used.

  Next, in the same manner as in Example 1 described above, LOI (oxygen limit index) measurement, combustion smoke concentration measurement, combustion exothermic evaluation, and light shielding evaluation were performed. The results are shown in Table 1.

(Comparative Example 2)
10 parts by mass of 1% carbon black masterbatch based on polyetherimide resin (Survic Innovative Plastics, trade name: Ultem 9011) and 90 parts by mass of polyetherimide resin were charged into a single screw extruder at 390 ° C. What was kneaded with a screw while melting was weighed with a gear pump. Next, a 2640 dtex / 1200 f carbon black-containing polyetherimide system is discharged by discharging from a nozzle with a diameter of 0.3 mm under the condition of 400 g / min. Fiber was obtained. And the nonwoven fabric molded object was manufactured like Example 1 except not having performed the dyeing | staining process by a dye dispersing agent, and not adding a phosphorus flame retardant.

  Next, in the same manner as in Example 1 described above, LOI (oxygen limit index) measurement, combustion smoke concentration measurement, combustion exothermic evaluation, and light shielding evaluation were performed. The results are shown in Table 1.

(Comparative Example 3)
A nonwoven fabric molded body was produced in the same manner as in Example 1 except that the dyeing treatment was not performed and the phosphorus-based flame retardant was not added.

  Next, in the same manner as in Example 1 described above, LOI (oxygen limit index) measurement, combustion smoke concentration measurement, combustion exothermic evaluation, and light shielding evaluation were performed. The results are shown in Table 1.

(Comparative Example 4)
A fiber web (weight per unit area 150 g / m ² ) was prepared using Nomex (manufactured by DuPont) which is a meta-aramid fiber. Next, seven sheets of this web were piled up and the nonwoven fabric was obtained using the needle punch method.

  And the nonwoven fabric molded object was manufactured like Example 1 except not having dyed.

  Next, in the same manner as in Example 1 described above, LOI (oxygen limit index) measurement, combustion smoke concentration measurement, combustion exothermic evaluation, and light shielding evaluation were performed. The results are shown in Table 1.

(Comparative Example 5)
A nonwoven fabric molded body was produced in the same manner as in Example 1 except that the dyeing treatment was not performed.

  Next, in the same manner as in Example 1 described above, LOI (oxygen limit index) measurement, combustion smoke concentration measurement, combustion exothermic evaluation, and light shielding evaluation were performed. The results are shown in Table 1.

  As shown in Table 1, in Examples 1 to 7 containing a phosphorus-based flame retardant, compared with Comparative Examples 1 to 5, it is excellent in combustion exothermicity, and it is possible to achieve both flame retardancy and light shielding properties. I can say that.

  On the other hand, in Comparative Examples 1 to 4 containing no phosphorus flame retardant, the LOI (Limited Oxygen Index) value is 35 or less, and the flame retardancy is poor. In Comparative Examples 3 to 5, It can be said that it is not suitable for aircraft use because it does not have light-shielding properties.

  As described above, the present invention is suitable for a nonwoven fabric molded article containing polyetherimide fibers.

Claims (8)

  A nonwoven fabric molded article containing a polyetherimide fiber and provided with a phosphorus flame retardant and a disperse dye.   A nonwoven fabric molded body in which the content of the disperse dye in the polyetherimide fiber is 0.3 to 1.5% owf and the content of the phosphorus flame retardant is 2000 ppm or less in terms of phosphorus concentration.   The nonwoven fabric molded article according to claim 1 or 2, wherein the phosphorus-based flame retardant is an aromatic phosphate ester compound.   The nonwoven fabric molded body according to any one of claims 1 to 3, wherein a LOI (limit oxygen index) value measured in accordance with a JIS L1091 test method is larger than 35. The total calorific value for 2 minutes after the start of measurement, measured in accordance with the Federal Aviation Administration (FAR) Part 25 combustion exotherm test of the US Federal Aviation Administration (FAA), is less than 60 kw min / m ² and measured. nonwoven molded article according to any one of the maximum amount of heat generated at 5 min after the start is less than 60 kW / m ² according to claim 1 to claim 4.   The non-woven fabric molded article according to any one of claims 1 to 5, wherein the smoke density (DS) at the time of combustion measured in accordance with ASTM method E-662-2-03 is less than 150.   Non-woven fabric molding in which the constituent fiber is a composite fiber composed of the polyetherimide fiber and the heat resistant fiber, and the mass ratio of the polyetherimide fiber and the heat resistant fiber is 90/10 to 50/50 in the composite fiber body.   It is a dry-type nonwoven fabric, The nonwoven fabric molded object of any one of Claims 1-7.