JP3269228B2 - Flame retardant polyolefin fiber and non-woven fabric - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin fiber excellent in both flame retardancy and light resistance at high temperatures, and a nonwoven fabric using the fiber. More specifically, the present invention relates to a polyolefin fiber also having gas discoloration resistance. It relates to a non-woven fabric using this fiber.

[0002]

2. Description of the Related Art Polyolefin-based fibers have excellent physical and chemical properties and are inexpensive. Therefore, they are used in many fields as materials for carpets, geotextiles, oil adsorbents, filters and the like. However, since this fiber is easily burned, it is required to impart flame retardancy such that the burning speed is 100 mm / min or less when used in a vehicle or a house. Also, regarding light resistance, it is possible to sufficiently exhibit light resistance in a high temperature where the temperature of a vehicle parked outdoors in summer reaches several tens degrees Celsius.
It is required to have light resistance of 60 hours or more. As a method for flame retarding polyolefin-based fibers, a method of post-treating the fibers with a flame retardant or a method of mixing a flame retardant with a raw material polymer has been generalized.

As a fiber post-treated with a flame retardant, JP-A-48-13696 discloses a polyolefin-based fiber coated with a phosphorus-containing organic halogen-based flame retardant. According to this method, the fibers can be easily made flame-retardant by using a liquid obtained by diluting a flame retardant with water or the like and post-treating the mat or the like by an impregnation method or a spray method. However, the cost is increased due to the necessity of drying, the flame retardant is in a state of blowing powder on the surface of the treated fiber, or the surface of the fiber is sticky,
Further, there is a problem that the flame retardant coated on the fiber is easily dropped off by washing or the like.

JP-A-58-156019 discloses a mixture of a raw material polymer and a flame retardant having a decomposition temperature higher than the spinning temperature by 100 ° C. or more and a fine particle flame retardant mixed with a polyolefin resin. A bicomponent fiber is disclosed. However, the organic halogen-based flame retardant used here has a problem of deteriorating the light resistance of the fiber.

JP-A-4-333612 discloses a brominated flame retardant, an antimony-based flame retardant auxiliary, a hindered amine light-resistant agent, and a nickel-based light-resistant agent. Mixed polyolefin-based fibers are disclosed. This fiber is used in combination with two types of light stabilizers, so the light resistance of the fiber is improved.However, since the nickel compound used as the light stabilizer is green, the fiber is colored green, There have been problems such as the fact that these light stabilizers may react with antioxidants and the like to color the fibers.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have conducted research on polyolefin fibers having both excellent flame retardancy and high light resistance at high temperatures. As a result, by adding a specific halogen-containing organophosphorus flame retardant, an antimony-based flame retardant aid and a specific light stabilizer to the polyolefin resin, not only the intended purpose can be achieved, but also the alkyl phosphate salt The present inventors have found that a fiber having excellent gas discoloration resistance can be obtained by performing a surface treatment with, and the present invention has been completed. As is apparent from the above description, an object of the present invention is to provide a polyolefin-based fiber excellent in both flame retardancy and light resistance at high temperatures, and a nonwoven fabric using this fiber. Another object of the present invention is to provide a polyolefin-based fiber having gas discoloration resistance and a non-woven fabric using the fiber.

[0007]

According to the present invention, (1) tris (tribromoneopentyl) phosphate is used as a flame retardant in an amount of 0.7 to 6% by weight based on the whole fiber, and an antimony compound is used as a flame retardant aid. 0.35 to 6% by weight, and poly [[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2 , 6,6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]]
1.5% by weight of a flame-retardant polyolefin-based fiber,
(2) The flame-retardant polyolefin-based fiber according to (1), which is a conjugate fiber, and (3) a phosphorous-based antioxidant as a light-proofing aid containing 0.05 to 1% by weight. The flame-retardant polyolefin-based fiber according to any of the above, and (4) the flame-retardant additive according to (3), wherein the light-proof auxiliary agent is bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. A polyolefin-based fiber, (5) the light-fastening aid is 4,4′-butylidene-bis (3-methyl-6
(3) a flame-retardant polyolefin fiber according to (3), which is (tertiary butylphenyl-di-tridecyl) phosphite; (6) 0.01 to 1% by weight of an alkyl phosphate salt as a surface-treating agent (1). (5) the flame-retardant polyolefin-based fiber according to any one of (5), (7) the flame-retardant polyolefin-based fiber according to (6), wherein the surface treatment agent is an alkyl phosphate salt having 12 to 18 carbon atoms, 8)
A flame-retardant polyolefin-based nonwoven fabric using the flame-retardant polyolefin-based fiber according to any one of (1) to (7).

The flame-retardant polyolefin fiber of the present invention
When the burning speed is 100 mm / min or less and the light resistance at high temperature is 160 hours or more, both flame retardancy and light resistance are excellent. The flame-retardant polyolefin-based fiber of the present invention is a polyolefin-based resin containing a specific halogen-containing organophosphorus-based flame retardant and a specific light-fast agent, etc., by various melt spinning methods, for example, a regular spinning method and a composite spinning method. It can be manufactured by spinning using a spun bond method, a melt blow method, or the like, and imparting stretching, crimping, or the like as necessary. The fineness of this fiber is about 0.5 to 1000 d / f for staples and multifilaments, and about 5 d / f for monofilaments.
It can be 0 to 5000 d / f.

Examples of the polyolefin resin usable in the present invention include α-olefin homopolymers such as polypropylene, polyethylene, polybutene-1, and poly-4-methylpentene-1, binary propylene and α-olefin other than propylene. Examples include terpolymers and mixtures of these polymers. These polyolefin resins have a melting point of about 11 from the viewpoints of spinnability and card passing property.
Those having a temperature of 5 ° C. or more and being crystalline are preferred.

The flame retardant used in the present invention is tris (tribromoneopentyl) phosphate. This flame retardant has a melting point of about 183 ° C and a decomposition temperature of about 320 ° C.
This flame retardant is mixed in an amount of 0.7 to 6% by weight based on the whole fiber. If the amount is less than 0.7% by weight, the flame-retardant effect cannot be obtained. If the amount exceeds 6% by weight, the spinnability of the fiber is deteriorated, so that fine fibers cannot be obtained. The preferable mixing amount of the flame retardant in the fiber fineness is about 0.7 to 4% by weight when the fineness is about 1 to 20 d / f, and about 1 to 4 when the fineness is about 21 d / f or more. 6% by weight.

The antimony compound used as a flame-retardant aid in the present invention is an antimony oxide, preferably antimony trioxide or antimony pentoxide. The mixing amount of the flame retardant aid is 0.35 to 6% by weight based on the whole fiber. If the mixing amount is less than 0.35% by weight,
If it exceeds 6% by weight, either the flame retardancy or the spinnability deteriorates, similarly to the case of the flame retardant, which is not preferable.

The light stabilizer used in the present invention is poly [[6-
(1,1,3,3-tetramethylbutyl) imino-1,
3,5-Triazine-2,4-diyl] [(2,2,
6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]]. This light stabilizer is mixed with 0.15 to 1.5% by weight based on the whole fiber. If the amount of the light stabilizer is less than 0.15% by weight, the light resistance at a high temperature is not improved, and if it exceeds 1.5% by weight, the light resistance reaches saturation. Also makes no sense. Further, in the present invention, this light stabilizer, other light stabilizers that do not adversely affect the flame retardancy and coloring of the fiber, for example,
2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzotriazole, (2,2 ′, 6,6 ′ -Tetramethyl-4-piperidyl) sebacate and the like.

In the present invention, a flame-retardant polyolefin-based fiber having further improved light resistance at high temperatures is obtained by using a phosphorus-based compound, which is usually used as an antioxidant for fibers, in combination with the light-resistant agent as a light-resistant auxiliary. be able to. Examples of such a light fastness assistant include trilauryl trithiophosphite, 4,4'-butylidene-bis (3-
Methyl-6-tert-butylphenyl-di-tridecyl) phosphite, bis (p-octyl) phenyl-
Bis [2-tert-butyl-5-methyl-α- (3
-Tert-butyl-6-methyl-4-hydroxyphenyl] 1,6-hexanediol diphosphite fatty acid zinc monocarboxylate, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, Examples thereof include di-stearyl-pentaerythritol-diphosphite and tris (di-nonylphenyl) phosphite. The mixing amount of this light-resistance aid is
It is 0.05 to 1% by weight based on the whole fiber. If the mixing amount is less than 0.05% by weight, the effect of improving light resistance is not recognized, and if it exceeds 1% by weight, spinnability is deteriorated. Further, a more preferable range of the mixing amount of the light resistance aid is about 0.07 to 0.8% by weight based on the whole fiber.

In the present invention, by using an alkyl phosphate salt as the surface treating agent, a flame-retardant polypropylene fiber having excellent gas discoloration resistance can be obtained. Examples of the surface treatment agent include alkyl phosphate salts having 12 to 18 carbon atoms, such as potassium lauryl phosphate, potassium myristyl phosphate, potassium cetyl phosphate, potassium stearyl phosphate, and the sodium salts of the above alkyl phosphates. This surface treatment agent is used in an amount of 0.01 to 1 with respect to the whole fiber.
% By weight. If the amount of adhesion is less than 0.01% by weight, the effect of gas discoloration resistance is not sufficient, and if it exceeds 1% by weight, the fiber becomes sticky, which is not preferable.

When the flame-retardant polyolefin-based fiber of the present invention is a composite fiber, examples thereof include composite types such as a sheath-core type, a side-by-side type, a sea-island type, and a multi-split type. The above-mentioned various additives can be mixed in the same amount with each component of the composite, or the mixing amount of the additives can be changed for each component. Various modifiers such as a matting agent, an antistatic agent, a conductive agent, and a pigment can be mixed with any or all of the composite components. In the case of a conjugate fiber, the amount of the various additives mixed is such that the total of each additive mixed with the conjugate component is within the above range with respect to the entire fiber.

The non-woven fabric obtained by the needle punching method and the tufted carpet obtained by the tufting method using the flame-retardant polyolefin fiber of the present invention are:
Since the burning speed is 100 mm / min or less and the light resistance is 160 hours or more, it can be used for vehicle interior materials, rugs of houses and buildings, and the like.

Hereinafter, the present invention will be described in detail with reference to examples. The evaluation of physical properties and the like in each example was performed by the following methods.

Flame retardancy: The burning rate (mm / min) of a needle-punched nonwoven fabric having a basis weight of 300 g / m ² was measured by a method according to FMVSS-302 (“flammability of interior materials”).
From this burning rate, the flame retardancy was determined as follows. 1
Six samples were tested for each type of sample. After removing the test flame, if the burning distance was 50 mm or less and all six self-extinguished within 60 seconds, the fire was regarded as self-extinguishing (SE) and the flame retardance was passed. In addition, after six specimens were tested and the test flame was removed, the average burning rate (mm / min) was calculated for all the specimens whose burning distance was 50 mm or less and self-extinguished within 60 seconds. When the average burning speed was 100 mm / min or less, it was determined to be acceptable for flame retardancy, and when it was 100 mm / min or more, it was determined to be unacceptable.

Light resistance: A needle-punched nonwoven fabric having a basis weight of 300 g / m ² was irradiated with ultraviolet rays at a temperature of 83 ° C. using a carbon arc type light resistance tester. The surface of the fiber was lightly scratched with a nail every 20 hours, and the irradiation time until the fiber was easily turned into a powder was measured.

Gas discoloration resistance: A needle-punched nonwoven fabric having a basis weight of 300 g / m ² was cut into a size of 40 × 40 cm and placed on a desk in a warehouse facing a road where many vehicles pass. After 150 days, the discoloration of the nonwoven fabric was measured according to JIS-
Judgment was carried out using the gray scale for contamination specified in L0805 (grade 1: large contamination to class 5: small contamination). All samples were tested at the same time.

Examples 1-4 and Comparative Examples 1 and 2 Tris (tribromoneopentyl) phosphate as a flame retardant was added to polypropylene powder having a melt flow rate of 21 (230 ° C., 10 minutes) and a melting point of 163 ° C. Antimony trioxide as a flame retardant aid and poly [[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] as a lightfastener
[(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] were mixed in the respective weight ratios shown in Table 1 to give a total of 100
It was blended to give a weight percent and pelletized. This pellet was melt-spun using a spinneret having a hole diameter of 1.5 mm and a number of holes of 60 at a discharge rate of 180 g / min, a spinning speed of 500 m / min, and a temperature of 230 ° C. to obtain an undrawn yarn. In each case, potassium lauryl phosphate was attached as a surface finishing agent in an amount of 0.2% by weight. This undrawn yarn is drawn at a temperature of 80 ° C. at a draw ratio of 3.0 times, a crimp of about 12 peaks / 25 mm is given by a crimper, the fiber length is cut to 51 mm, and the single yarn fineness is 18 A staple of 0.0d / f was obtained. The staple was carded using a card machine to obtain a web, and a nonwoven fabric having a basis weight of 300 g / m ² was obtained by a needle punch method. Table 1 shows the evaluation results of the flame retardancy, light resistance and gas discoloration resistance of these nonwoven fabrics.

Examples 1 to 4 in which the flame retardant, light-proofing agent and the like specified in the present invention are used, and the mixing amount is within the range specified in the present invention, are all excellent in flame retardancy and light resistance. Was 160 hours or more, which was very excellent. Also,
All of these had good gas discoloration resistance because the surface treatment agent was attached.

On the other hand, Comparative Example 1 in which the mixing amount of the flame retardant was less than 0.7% by weight and the mixing amount of the light-proofing agent was less than 0.15% by weight had good gas discoloration resistance. Both flammability and light resistance were poor. Comparative Example 2 in which the amount of the flame retardant exceeds 6% by weight also had good gas discoloration resistance, but also had poor light resistance.

Comparative Examples 3 and 4 A polypropylene compound was obtained using the same additives as in Example 1 except that decabromodiphenyl oxide was used as the flame retardant. After pelletizing this compound,
The same steps as in Example 1 were performed, and the basis weight was 300 g / m.
² was obtained (Comparative Example 3). Further, the flame retardant is decabromodiphenyl oxide, and the antioxidant tetrakis [methylene 3- (3,5-ditert-butyl-4-hydroxy-hydrocinnamate)] methane is 0.22% by weight as a lightfastness assistant. Except for the addition, the same additives as in Example 1 were used to obtain a polypropylene compound. After pelletizing each of the compounds, the same process as in Example 1 was performed to obtain a basis weight of 300 g / m ^2.
(Comparative Example 4). Flame retardancy of these nonwovens,
Table 1 shows the evaluation results of the light resistance and the gas discoloration resistance. The fibers of Comparative Examples 3 and 4 were inferior in light resistance. From these results, it was found that tetrakis [methylene 3- (3,5-ditert-butyl-4-hydroxy-hydrocinnamate)] methane, which is an antioxidant used in Comparative Example 4, did not exhibit an effect as a light fastness assistant. There was found. The fibers of Comparative Examples 3 and 4 were prepared by adding the same surface treating agent as in Example 1 to 0.2.
Although 0% by weight was attached, the fiber of Comparative Example 4 was colored pink in a gas discoloration test.

Examples 5 and 6 In addition to the same additives as in Example 1, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphos, which is an antioxidant, is further used as a light-fastening aid. The polypropylene compound was obtained by mixing 0.2% by weight of the fight. After pelletizing this compound, the same process as in Example 1 was performed to obtain a nonwoven fabric with a basis weight of 300 g / m ² (Example 5). Further, in addition to the same additives as in Example 1, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, which is an antioxidant, is further added as a light resistance auxiliary. A one-to-one mixture of amine 2-ethylhexoate was added to 0.1.
22% by weight (0.11% by weight as phosphorus antioxidant)
The mixture was mixed to obtain a polypropylene compound. After pelletizing this compound, the same process as in Example 1 was performed to obtain a nonwoven fabric having a basis weight of 300 g / m ² (Example 6). Table 1 shows the evaluation results of the flame retardancy, light resistance, and gas discoloration resistance of this nonwoven fabric. The fibers obtained in Examples 5 and 6 have remarkably excellent light resistance by using a phosphorus-based antioxidant in combination with a light resistance agent as a light resistance auxiliary, and also have excellent flame retardancy and gas discoloration resistance. It was good. In addition, the antioxidant used here was effective as a light resistance assistant.

Example 7 The melt index was 22 instead of polypropylene.
(190 ° C., 10 minutes), and the same additives as in Example 1 were used except that high-density polyethylene powder having a melting point of 134 ° C. was mixed and pelletized. 0.8m hole diameter
m, using a sheath-core composite spinneret having 100 holes,
Using the compound on the sheath side and the compound used in Example 2 on the core side, with a compounding ratio of 1 to 1 (weight), the discharge rate of both the sheath and core was 180 g / min, and the spinning speed was 852.3 m / m.
Then, the mixture was melt-spun at a temperature of 250 ° C. to obtain a sheath-core composite fiber. This undrawn yarn is drawn at a temperature of 90 ° C. at a draw ratio of 2.6 times, a crimp of about 14 peaks / 25 mm is crimped with a crimper, and cut to a fiber length of 64 mm. Was 7.2 d / f. The staple was carded using a card machine to obtain a web, and a nonwoven fabric having a basis weight of 300 g / m ² was obtained by a needle punch method. The nonwoven fabric was heat-treated at 145 ° C. for 4 minutes using a hot air drier so that the intersections of the fibers were thermally fused. Table 2 shows the evaluation results of the flame retardancy, light resistance, and gas discoloration resistance of this nonwoven fabric. This nonwoven fabric had self-extinguishing (SE) flame retardancy, light resistance of 420 hours, and gas discoloration of quaternary. This non-woven fabric could be used for vehicles and residential rugs, with or without laminating polyethylene or foamed polyurethane on the back. This non-woven fabric could be molded to conform to the irregularities of the vehicle by compression molding after heating.

Comparative Example 5 A polypropylene compound was obtained by using the same additives as in Example 2 above, pelletized, melt-spun in accordance with Example 1, stretched and crimped, and the fiber length was reduced. 51m
m so that the single yarn fineness is 18.0 d / f
Staples. However, to this, 0.20% by weight of a 1: 1 mixture (by weight) of sorbitan monooleate and stearic acid diethanolamide was attached as a surface finish. The staple is carded using a carding machine to obtain a web, and the basis weight is further adjusted by a needle punching method.
A non-woven fabric of 0 g / m ² was obtained. This nonwoven fabric was evaluated for flame retardancy, light resistance, and gas discoloration resistance, and the results are shown in Table 1. This fiber had a flame retardancy of self-extinguishing (SE) and a light resistance of 460 hours, but had a gas discoloration resistance of 1.5 class.

Comparative Example 6 The same additives as in Example 1 were used as additives other than the light-proofing agent, and 0.75% by weight of 2-hydroxy-4-n-octoxybenzophenone and 3,5 0.75% by weight of tertiary butyl-4-hydroxybenzoic acid
Was mixed to obtain a polypropylene compound. After pelletizing this compound, the same process as in Example 1 was performed to obtain a nonwoven fabric having a basis weight of 300 g / m ² . Table 1 shows the evaluation results of the flame retardancy, light resistance, and gas discoloration resistance of this nonwoven fabric. Although the light resistance of the fiber of Comparative Example 6 satisfied the target, coloring of the fiber with the light resistance was observed.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

The flame-retardant polyolefin fiber of the present invention and the nonwoven fabric using this fiber have a burning rate of 100 mm /
Minutes or less, light resistance at high temperatures of 160 hours or more, and both flame retardancy and light resistance were excellent, so that they could be used as rugs for vehicles and houses. Further, those to which the surface treatment agent was attached were excellent in gas discoloration resistance.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI D06M 13/292 D06M 13/292 // C08K 5/34 C08K 5/34 C08L 23/00 C08L 23/00 D06M 101: 20 D06M 101 : 20 (58) Investigation field (Int.Cl. ⁷ , DB name) D01F 6/04-6/06 D01F 6/46 D01F 8/06 D01F 1/07 D04H 1/42 D06M 13/292 C07F 9/09 C08K 5/34-5/357 C08L 23/00-23/06

Claims (8)

(57) [Claims] 1. A total flame retardant containing tris (tribromoneopentyl) phosphate as a flame retardant in an amount of 0.7 to 6%.
% By weight, 0.35% of an antimony compound as a flame retardant aid
~ 6% by weight, poly [[6- (1,1,3,3)
3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6 , 6-Tetramethyl-4-piperidyl)
[Imino]] in an amount of 0.15 to 1.5% by weight. 2. The flame-retardant polyolefin-based fiber according to claim 1, which is a conjugate fiber. 3. A phosphorus-based antioxidant as a light-fast assistant.
The flame-retardant polyolefin-based fiber according to any one of claims 1 to 2, which contains 0.5 to 1% by weight. 4. The flame-retardant polyolefin-based fiber according to claim 3, wherein the light-fast assistant is bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. 5. The flame-retardant polyolefin-based fiber according to claim 3, wherein the light-fast assistant is 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite. 6. The flame-retardant polyolefin fiber according to claim 1, wherein 0.01 to 1% by weight of an alkyl phosphate salt is adhered as a surface treatment agent. 7. The flame-retardant polyolefin-based fiber according to claim 6, wherein the surface treating agent is an alkyl phosphate salt having 12 to 18 carbon atoms. 8. A flame-retardant polyolefin-based nonwoven fabric using the flame-retardant polyolefin-based fiber according to claim 1.