JP2008019529A - Flame-retardant fiber blended yarn - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant fiber blended yarn which is a blended yarn of polyester-based fibers and acrylic fibers, has improved flame retardancy, and prevents the formation of drips and the generation of a halogen-containing gas, when burned. <P>SOLUTION: This flame-retardant fiber blended yarn is composed of polyester-based fibers including a silicone-based compound and a compound having imide structures, and acrylic fibers. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a flame-retardant fiber composite composed of a polyester fiber and an acrylic fiber containing a silicone compound and a compound having an imide structure. More specifically, the present invention relates to a flame retardant fiber composite that has improved flame retardancy and suppressed generation of drip and halogen-containing gas during combustion.

  Conventionally, many textile products have been used for clothing, bedding, wallpaper, and interior materials for automobiles, aircraft, railways, ships, and the like. In these textile products, interior materials used in hotels, hospitals, movie theaters, etc. are regulated by the Fire Service Act in order to minimize the damage of fire caused by fires such as matches and cigarettes. Under such circumstances, in order to create a highly safe and comfortable living environment, it is desired to develop a textile product having high flame retardancy.

  Fiber composites composed of polyester fibers and acrylic fibers are widely used in clothing, bedding, and interior materials. However, in applications that cannot be operated without passing the flameproof regulations, a fiber composite of flame-retarded acrylic fiber and polyester fiber is required.

  Conventionally, flame-retardant fiber composites of acrylic fibers and polyester fibers are those using halogen-based flame retardants or halogen-containing acrylics represented by modacrylic fibers copolymerized with acrylic monomers and halogen-based monomers. Many fiber and polyester fibers are known as fiber composites. However, when a fiber composite with a polyester fiber is used, the flame retardancy is reduced, so that a large amount of halogen-based monomer must be copolymerized (Patent Document 1). Copolymerization of a large amount of halogen is a major issue due to environmental problems in recent years, and development of a flame retardant fiber composite having a low halogen compound content is required.

In contrast, Patent Document 2 proposes kneading a non-halogen flame retardant into a polyester fiber. However, all of the proposed non-halogen flame retardants are phosphorus flame retardants. When phosphorus flame retardants are used, the molten polymer drip at the time of combustion, so it can only be used for materials such as ventilation fan filters. It was possible, but could not be used for clothing, bedding, etc.
Japanese Patent Laying-Open No. 2005-179876 (Claim 7) JP-A-2005-288374 (Claim 1, [0007], [Example], [0017] to [0022])

  An object of the present invention is to provide a flame retardant fiber composite in which flame retardancy is improved and generation of drip and halogen-containing gas during combustion is suppressed in a fiber composite of polyester fiber and acrylic fiber. It is what.

  The object of the present invention is achieved by a flame retardant fiber composite comprising a polyester fiber and an acrylic fiber containing a silicone compound and a compound having an imide structure.

  Flame-retardant fiber composite composed of polyester fiber and acrylic fiber containing silicone compound and compound having imide structure improves flame retardancy and suppresses drip generation and halogen-containing gas generation during combustion A flame retardant fiber composite can be obtained.

  The present invention is described in detail below.

  The flame-retardant fiber composite of the present invention is characterized by comprising a polyester fiber and an acrylic fiber containing a silicone compound and a compound having an imide structure.

  The polyester composition constituting the polyester fiber in the present invention is a polyester composition synthesized from a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, and can be fiberized by melt spinning It is a composition.

  Specific examples of such polyesters include polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polyethylene-1,2-bis ( 2-chlorophenoxy) ethane-4,4′-dicarboxylate, poly-L-lactic acid, poly-D-lactic acid and the like. The present invention is suitable for polyethylene terephthalate or polyester copolymers mainly containing ethylene terephthalate units, which are most commonly used.

  These polyesters include dicarboxylic acids such as adipic acid, isophthalic acid, sebacic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, cyclohexanedicarboxylic acid and ester-forming derivatives thereof as copolymerization components. , Diethylene glycol, polyethylene glycol, hexamethylene glycol, neopentyl glycol, polypropylene glycol, dioxy compounds such as cyclohexanedimethanol, oxycarboxylic acids such as p- (β-oxyethoxy) benzoic acid, and ester-former derivatives thereof are copolymerized May be.

  Polyester fibers may be thread-shaped or band-shaped, and the cross-sectional shape of the fiber may be round or irregular (triangular, square, polygonal, flat, hollow, etc.). Moreover, the composite fiber which combined two types or two or more types of polyester compositions may be sufficient. The composite fiber may be a side-by-side type, a core-sheath type, or the like, but it is necessary that at least one polyester containing a silicone compound is included.

The silicone compound used in the present invention is an organosilicon compound, which is a compound having a siloxane bond and an organic group directly bonded to a silicon atom in the same molecule. As the silicone compound, monofunctional R ₃ SiO _0.5 (M unit), bifunctional R ₂ SiO _1.0 (D unit), trifunctional RSiO _1.5 (T unit), tetrafunctional It is comprised from the unit shown by the characteristic _SiO2.0 (Q unit). Specifically, silicone oil, silicone resin, silicone rubber, silane coupling agent, silicone powder, and the like can be considered, but a compound having a siloxane bond and an organic group directly bonded to a silicon atom in the same molecule. This is not necessarily the case. These silicone compounds can be used alone or in combination.

The silicone compound is preferably an organic silicone resin in which RSiO _1.5 (R: hydrogen or organic group) unit is 50 mol% or more and 100 mol% or less in the monomer unit and the organic group R contains a phenyl group. When a silicone resin containing an RSiO _1.5 (R: hydrogen or organic group) unit is contained in the polyester to improve the formability of carbide by some action during combustion, the shape change is suppressed and the non-drip type is obtained. Guessed. Furthermore, since the carbide suppresses the generation of combustible decomposition gas, it is considered that the flame retardancy is also improved. By containing 50 mol% or more of RSiO _1.5 (R: hydrogen or organic group) unit in the silicone resin, the heat resistance of the silicone resin is improved, and by adding it to the polyester, the non-drip property at the time of combustion of the polyester is improved. improves. In addition, it is preferable to include a phenyl group in the RSiO _1.5 unit organic group R constituting the silicone resin because the heat resistance of the silicone resin is improved and the dispersibility in the polyester is improved.

  The weight average molecular weight of the silicone resin of the present invention is preferably 20000 or less because dispersibility in polyester is improved.

  The compound having an imide structure refers to a compound having a structure of —CO—NR—CO— (R: organic group) in the molecular structure. An organic group here means a C1-C12 alkyl group, an alkene group, and aromatic (a benzene ring, a condensed benzene ring, a non-benzene type aromatic ring).

  Specific examples of compounds having such an imide structure include cyclic diacylamines such as phenylphthalimide, cyclohexane-1,2-dicarboximide, cyclohex-3-ene-1,2-dicarboximide, and acetyl. Acyclic diacylamines such as (benzoyl) azane, bis (cyclohexanecarbonyl) azane, diacetyl (cyclopentyl) azane, acetyl (benzoyl) (3-chloropropanoyl) azane, imides such as polyimide, polyamideimide and polyetherimide Examples thereof include, but are not limited to, a compound having an imide structure in the intramolecular structure.

  The compound having an imide structure is preferably a polymer having thermoplasticity from the viewpoint of processability. That is, an imide polymer having a glass transition temperature of 130 ° C. or more and 300 ° C. or less is preferable, and specific examples thereof include imide polymers such as polyimide, polyamide imide, and polyether imide. Ether imide is preferred.

  In the present invention, the polyester fiber contains a silicone compound and a compound having an imide structure. This means that a silicone compound and a compound having an imide structure are dispersed and / or compatible in the polymer constituting the fiber. The contained state is preferably uniform and finely present in the single fiber from the viewpoint of carbide formation because the contact surface with the polymer is high, and both the intended yarn strength and the effects and functions of the present invention are provided. It is not particularly limited as long as it is within a range.

  The content of the silicone compound contained in the polyester fiber only needs to be an effective content that can provide both the yarn strength necessary for developing the basic performance of the present invention and the effects and functions of the present invention. From the viewpoint of fiber properties, it is preferably 0.5% by weight or more and 30% by weight or less. The content of 0.5% by weight or more is preferable because the formation of carbides is promoted and a non-drip type tends to be obtained. Further, the content of 30% by weight or less is preferable because the dispersibility in the polymer tends to be good, the yarn strength is sufficiently expressed, and the strength of the fiber composite is not lowered.

The content of the compound having an imide structure contained in the polyester fiber only needs to be an effective content that can provide both the yarn strength necessary to express the basic performance of the present invention and the effects and functions of the present invention. . From the viewpoint of fiber properties, it is preferably 0.5% by weight or more and 50% by weight or less. The content of 0.5% by weight or more is preferable because the formation of carbides is promoted and a non-drip type tends to be obtained. Further, when the amount is 50% by weight or less, the dispersibility in the polymer tends to be good, the yarn strength is sufficiently expressed, and the strength of the fiber composite does not tend to decrease. It is preferable because the retention performance can be sufficiently expressed. The acrylic fiber of the present invention is a fiber composed of an acrylic polymer.

  The acrylic polymer is not particularly limited as long as it is an acrylic polymer having fiber-forming properties, that is, an acrylic polymer and a copolymer containing 80% by weight or more of acrylonitrile (AN). For example, an acrylic polymer comprising 0 to 20% by weight of an unsaturated vinyl compound copolymerizable with 80 to 100% by weight of acrylonitrile can be used. From the viewpoint of spinnability, devitrification resistance, dyeability, etc., those containing 90% by weight or more of AN and having a copolymerization amount of 10% by weight or less are preferred.

  The copolymer component in this acrylic polymer includes, for example, vinyl acids such as acrylic acid, methacrylic acid and their lower alkyl esters, itacones, acrylamide, methacrylamide, vinyl acetate, vinyl chloride, styrene, and vinylidene chloride. In addition to the compounds, the same or different types of acidic monomers such as unsaturated sulfonic acids such as vinyl sulfonic acid, acrylic sulfonic acid, methacryl sulfonic acid, parastyrene sulfonic acid, and salts thereof can be used.

  In the present invention, by including a silicone compound and a compound having an imide structure in a polyester fiber, carbonization of the polyester portion is significantly accelerated at the time of combustion, while acrylic fiber burns violently at the time of flame contact but keeps the flame away. It has the feature of self-extinguishing by fire, and it has been found that the acrylic fiber is blocked from the flame by the carbonized polyester, which prevents the combustion of the acrylic fiber and exhibits flame retardancy as a fiber composite. It is.

  Examples of the flame retardant fiber composite include yarn-shaped products such as mixed yarn and blended yarn, fabric-shaped products such as woven fabric, knitted fabric, and nonwoven fabric, and cotton-shaped products.

  In the case of a thread-shaped composite, the polyester fibers and acrylic fibers may be short fibers, long fibers, or a mixture of short fibers and long fibers.

  In the case of woven fabrics, in addition to woven fabrics composed of thread-shaped composites, the above-mentioned polyester fibers for warps, the woven fabrics made of acrylic fibers for wefts, or the woven fabrics made of acrylic fibers for warps and above-mentioned polyester fibers for weft It may be.

  The mixing ratio of the polyester fiber and acrylic fiber of the present invention is not particularly limited as long as the functionality of the fiber composite is not impaired, but the proportion of the polyester fiber in the composite is less than 20 weights. In such a case, the flame retardancy tends to decrease, so 20% by weight or more is preferable, and 50% by weight or more is more preferable.

  In the flame-retardant fiber composite of the present invention, the halogen element content is preferably 0% by weight or more and 1.0% by weight or less because the amount of halogen-containing gas generated during combustion is small. If the halogen element is contained, a halogen-containing gas is generated when the fiber composite is combusted. Therefore, it is more preferable that the halogen element is not substantially contained in view of environmental load.

  The flame retardant fiber composite of the present invention includes hindered phenol-based, amine-based, phosphite-based, thioester-based antioxidants, benzotriazole-based, benzophenone-based, cyanoacrylate-based ultraviolet absorbers, infrared absorbers, etc. , Cyanine, stilbene, phthalocyanine, anthraquinone, perinone, quinacridone organic pigments, inorganic pigments, fluorescent brighteners, calcium carbonate, silica, titanium oxide particles, antibacterial agents, electrostatic agents, etc. An additive may be contained.

  In addition, the flame retardant fiber composite of the present invention can be subjected to various post-processing.

  From the above, the flame retardant fiber composite of the present invention can be suitably used as a flame retardant material for applications such as clothing, bedding, and interior materials.

Hereinafter, the present invention will be described more specifically with reference to examples. Each measurement and evaluation in the examples was performed as follows.
<Flammability evaluation>
A. According to JIS L1091 (1992) D method, the presence / absence of drip during and after flame contact and the number of flame contact were evaluated.

・ No drip: ○
Available: ×
・ Number of flame contact: ○ (3 or more times of flame contact)
: × (less than 3 times of flame contact)
B. According to JIS L1091 (1992) A-4 method, the presence / absence of drip at the time of flame contact / after flame contact and the presence / absence of self-extinguishing property after flame contact were evaluated.

・ No drip: ○
Available: ×
・ Self-extinguishing: ○ (Time to self-extinguish: 0 to less than 3 seconds)
: △ (Time to self-extinguish: less than 3-10 seconds)
: × (Time to self-extinguish: 10 seconds or more)
<Adjustment of silicone compound>
The silicone compounds described in each example are shown in Table 1. The method for preparing the silicone compound was as follows.

A. Adjustment of ratio of M, D, T, and Q units of silicone unit R ₃ SiOCl (corresponding to M unit), R ₂ SiOCl ₂ (corresponding to D unit), RSiOCl ₃ (corresponding to T unit), SiOCl ₄ (Q unit) In a desired molar ratio to produce silicone compounds having different proportions of M, D, T, and Q units.

Further, in order to increase the molecular weight, dehydration condensation was performed at 2 Torr and 180 ° C. for a predetermined time to obtain a silicone compound having a desired degree of polymerization.
B. Ratio of phenyl group and methyl group The above R moieties were substituted with phenyl group and methyl group, respectively, and silicone compounds having different molar ratios of phenyl group and methyl group were prepared.
C. Content of silanol group and phenyl group The reaction time at the time of condensing a silicone compound was adjusted, the ratio of the silanol group and the phenyl group was measured by NMR, and the content was calculated.
D. Molecular weight The reaction time at the time of condensing the silicone compound was adjusted, and the obtained silicone compound was subjected to gel permeation chromatography (GPC), and the weight average molecular weight was measured using polystyrene as a reference substance.

Example 1
A silicone compound 1 having an average molecular weight of 5000, having a branched structure of T units as a silicone compound, a terminal group being a hydroxyl group, and a phenyl group content corresponding to the side chain organic group of the silicone compound being 100 mol%, Ether imide (manufactured by GE) (hereinafter abbreviated as PEI) (Tg = 216 ° C.) and polyethylene terephthalate (hereinafter abbreviated as PET) having an intrinsic viscosity of 0.64 are PET: PEI: silicone compound A = 82.5: A polyester chip containing a silicone compound and PEI was obtained by kneading at a kneading temperature of 300 ° C. at 2.5: 15. This chip is vacuum-dried at 150 ° C. for 10 hours, and is spun at a spinning temperature of 295 ° C. and a spinning speed of 1250 m / min. After drawing heat treatment, crimps are applied, a single yarn fineness of 1.2 dtex, and a fiber length of 38 mm silicone. A polyester fiber short fiber (polyester fiber A) containing a polyester compound and PEI was obtained.

  Next, 10% by weight of the obtained polyester fiber and a 90% by weight acrylic fiber not containing a halogen element having a single yarn fineness of 1.7 dtex and a fiber length of 38 mm were uniformly mixed to obtain a fiber composite.

  A plain woven fabric was prepared using the obtained fiber composite. A weaving density of 78 warps / inch, 65 wefts / inch, and a weaving width of 98 cm was prepared, and the flammability was evaluated.

  As shown in Table 2, it was a flame retardant fiber composite having no drip by the A-4 method and the D method and having excellent self-extinguishing properties.

Examples 2 and 3
It carried out like Example 1 except having changed the mixing rate of the silicone compound 1 mixed with the polyester fiber, and PEI.

  As shown in Table 2, all were flame retardant fiber composites having no drip in the A-4 method and D method and excellent in self-extinguishing properties.

Examples 4-11
The same procedure as in Example 1 was performed except that the silicone compound 1 was changed to the silicone compound shown in Table 2.

  As shown in Table 2, all were flame retardant fiber composites having no drip in the A-4 method and D method and excellent in self-extinguishing properties.

Examples 12 and 13
The same procedure as in Example 1 was performed except that PEI was changed to polyimide or polyamideimide.

  As shown in Table 2, all were flame retardant fiber composites having no drip in the A-4 method and D method and excellent in self-extinguishing properties.

Example 14
The same procedure as in Example 1 was performed except that the acrylic fiber was changed to a modacrylic fiber copolymerized with 2% by weight of chlorine atoms.

  As shown in Table 2, it was a flame retardant fiber composite having no drip by the A-4 method and the D method and having excellent self-extinguishing properties.

Examples 15-17
The same procedure as in Example 1 was performed except that the blending ratio of the polyester fiber and the acrylic fiber was changed to the blending ratio shown in Table 2.

  As shown in Table 2, all were flame retardant fiber composites having no drip in the A-4 method and D method and excellent in self-extinguishing properties.

Comparative Examples 1-3
It carried out like Example 1 except having changed the mixing rate of the silicone compound 1 mixed with the polyester fiber, and PEI.

  As shown in Table 2, drip was observed in the A-4 method and D method, and the self-extinguishing property was also low.

  As shown in Examples 1 to 17, those within the scope of the claims of the present application have good self-digestibility and drip property even in a combustion test according to JIS L1091 A-4 method.

  On the other hand, as shown in Comparative Examples 1 to 3, what deviated from the claims of the present application was inferior in both self-extinguishing properties and drip properties.

  In other words, those within the scope of claims of the present application have good flame retardancy and drip properties. However, it is understood that those outside the scope of claims of the present application are inferior in flame retardancy and drip.

Claims (5)

A flame retardant fiber composite comprising a polyester fiber and an acrylic fiber containing a silicone compound and a compound having an imide structure. The flame retardant fiber composite according to claim 1, wherein the halogen content in the flame retardant fiber composite is 0 to 1.0% by weight. 3. The monomer unit constituting the silicone compound, wherein RSiO _1.5 (R: hydrogen or organic group) unit is 50 mol% or more and 100 mol% or less, and the organic group contains a phenyl group. The flame-retardant fiber composite described. The flame retardant fiber composite according to any one of claims 1 to 3, wherein the compound having an imide structure is a polymer having a glass transition temperature of 130 ° C or higher and 300 ° C or lower. The flame retardant fiber composite according to any one of claims 1 to 4, wherein the compound having an imide structure is a polyetherimide.