JP2007182664A - Flame-retardant fiber composite - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To impart a flame-retardant component to a fiber composite composed of polyester-based fibers containing a silicone resin and cellulosic fibers and to thereby provide the flame-retardant fiber composite composed of the polyester-based fibers and the cellulosic fibers exhibiting ultrahigh flame retardance. <P>SOLUTION: The flame-retardant fiber composite is composed of the polyester-based fibers containing the silicone resin and the cellulosic fibers. The flame-retardant component in an amount of ≥1,000 to ≤20,000 ppm converted into a flame-retardant element is applied. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention provides a fiber composite composed of a polyester fiber and a cellulose fiber exhibiting extremely high flame retardancy by imparting a flame retardant component to a fiber composite composed of a polyester fiber containing a silicone resin and a cellulose fiber. It is about the body.

  Examples of fiber composites composed of polyester fibers and cellulosic fibers include polyester and cotton, fabrics composed of polyester and rayon, and are widely used in clothing, bedding and interior materials. However, in applications that require flameproof performance, flame retardant polyester fibers or cellulosic fibers have been used exclusively. This is because the composite of polyester fiber and cellulosic fiber in the prior art is much more flammable than expected from the single flammability of polyester fiber or cellulosic fiber, and this tendency is difficult for each material. This is because it is more prominent when imparting flammability. In other words, the conventional flame retardant technology for polyester fibers is based on promoting melting and dropping (drip) during combustion, while cellulose fibers provide flame retardancy by carbonization during combustion. For this reason, when these materials are combined, the flame retarding performance of each other is canceled out, and a so-called SCAFOLDING effect is generated in which each material is more easily combusted than in the case of a single material.

  Conventionally, as a method for increasing the flame retardancy of polyester fibers, there is less environmental impact due to the method of exhausting or adhering halogen-based flame retardants to the fibers by the bath method or pad method, and the increased awareness of global environmental conservation. As a flame retardant processing technique, a method of attaching a phosphorus flame retardant has been proposed. However, these methods are processing methods that produce flame retarding behavior called drip type that promotes melting by flame contact and quickly leaves the heat source, and are used for blended fiber products that inhibit melting and other functions. There was a problem that it was difficult to combine.

  On the other hand, various methods have been proposed for flame retarding technology of cellulosic fibers. Among them, tetrakis (hydroxymethyl) phosphonium salt and N-methylol (dimethyl) phosphonopropionamide are attached as effective methods. A method (Non-Patent Document 1) is known.

  However, for example, in the case where the above-mentioned tetrakis (hydroxymethyl) phosphonium salt is processed into a fiber composite of polyester fiber and cellulose fiber (Patent Document 1), in order to provide sufficient flame retardancy, a large amount There was a problem that a flame retardant had to be provided, and the properties of the fabric such as texture and light resistance were deteriorated.

  Further, there is a flame-retardant composite fiber in which tetrakis (hydroxymethyl) phosphonium salt is treated into a cellulose fiber, and a cyclic phosphate ester or hexacyclobromododecane is treated into a polyester fiber (see Patent Document 2). In order to impart the flame retardancy that should be achieved, a large amount of flame retardant is required, and the texture is lowered.

  Further, a flame retardant fiber composite formed by forming a fiber composite with a cellulose fiber using a polyester fiber copolymerized with a bifunctional phosphorus compound, and then post-processing with tetrakis (hydroxymethyl) phosphonium salt or the like However, there is a problem that the target flame retardancy performance cannot be obtained unless a large amount of flame retardant is applied during post-processing.

In recent years, a technique has been found in which a silicone compound is added to a polyester fiber without using a halogen compound or a phosphorus compound as a flame retardant aid, thereby enhancing the poor melting property (patent) References 4, 5). However, even when this polyester fiber is combined with a cellulosic fiber, the drip is suppressed by the flame retardancy test method D (flame test) of the JIS L 1091 fiber product, which is a test in a state where it is protected by a coil during combustion. Although observed, there was a problem of low self-extinguishing properties.
JP-A-6-101176 Japanese Patent Laid-Open No. 2-500454 JP-A-62-276039 JP-A-8-209446 JP 2005-97819 A “Dyeing Industry” No. 22 (No. 10) 559-568

  In view of the present situation described above, the present invention provides a flame retardant component to a fiber composite composed of a polyester fiber and a cellulose fiber containing a silicone resin in a fiber composite of a polyester fiber and a cellulose fiber. An object of the present invention is to provide a fiber composite having extremely high flame retardancy.

  In order to achieve this object, the present invention has the following configuration.

  A flame retardant fiber composite obtained by adding a flame retardant component to a fiber composite composed of a polyester fiber containing a silicone resin and a cellulose fiber.

  According to the present invention, in a fiber composite composed of a polyester fiber containing a silicone resin and a cellulose fiber, a fiber composite exhibiting extremely high flame retardancy can be obtained by adding a flame retardant component. .

  Hereinafter, the best mode of the flame-retardant fiber composite of the present invention will be described in detail.

  The polyester polymer constituting the polyester fiber used in the present invention is a condensate of dicarboxylic acid and diol represented by polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polytetramethylene terephthalate and the like.

  Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4′-diphenylcarboxylic acid, bis- (4-carboxyphenyl) sulfone, 1,2- Bis (4-carboxyphenyl) ether, 1,2-bis (4-carboxyphenyl) sulfone, 1,2-bis (4-carboxyphenyl) ethane, 5-sodium sulfoisophthalic acid, diphenyloxide-p, p'- Examples include ester-forming derivatives such as dicarboxylic acids, p-phenylenediacetic acid, diphenyloxide-p, p'-dicarboxylic acid, trans-hexahydroterephthalic acid and their alkyl esters, aryl esters, and ethylene glycol esters.

  Examples of the diol include ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, trimethylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol S and its Examples include ethylene glycol, polyethylene glycol adduct, diethylene glycol, and polyethylene glycol.

  Such a polyester-based polymer may be copolymerized with the main components dicarboxylic acid and diol using another dicarboxylic acid or diol as a third component. Specific examples of the third component include isophthalic acid, isophthalic acid sulfonate, and adipic acid, but are not limited thereto.

  The polyester polymer may be polylactic acid which is a non-petroleum polyester compound.

  Examples of the cellulose fiber of the present invention include natural fibers such as cotton and hemp, regenerated cellulose fibers such as viscose rayon and acetate rayon, and semisynthetic fibers such as acetate (diacetate) and triacetate. It is not limited to.

The silicone resin of the present invention is a kind of organosilicon compound. Among compounds having a siloxane bond and an organic group bonded to a silicon atom in the same molecule, R is hydrogen or an organic group. R ₃ SiO _0.5 (M unit), bifunctional R ₂ SiO _1.0 (D unit), trifunctional RSiO _1.5 (T unit), tetrafunctional SiO _2.0 (Q unit) ) Is an organosilicon compound containing at least RSiO _1.5 (R: hydrogen or an organic group). In the present invention, at least a T unit may be contained, and a silicone resin composed of a combination of one or more of an M unit, a D unit, and a Q unit may be used.

Also,
In the units constituting the silicone resin, it is preferable that RSiO _1.5 is 85 mol% or more based on all the structural units. When RSiO _1.5 is contained in the silicone resin in an amount of 85 mol% or more, the heat resistance and carbonization when a fiber composite is obtained is improved, and more preferably 99 mol% or more.

The content of RSiO _1.5 can be measured by ²⁹ Si-NMR, and the content can be measured from the peak area ratio attributed to RSiO _1.5 .

In the present invention, it is preferable that R is an organic silicone resin in which an organic group is present. If it is a methyl group or a phenyl group, dispersibility with respect to polyester is improved, and flame retardancy when a fiber composite is obtained is also improved. Therefore, a phenyl group is particularly preferable. The content of the phenyl group is preferably 85 mol% or more, more preferably 99 mol% or more in the side chain organic group excluding the terminal group of the silicone resin, from the viewpoint of dispersibility and flame retardancy. As the organic group other than the phenyl group, various organic groups can be selected as long as various properties of the silicone resin are not deteriorated.
Moreover, the content rate of a phenyl group can be measured by ²⁹ Si-NMR, and the content rate can be measured from the peak area ratio attributed to C ₆ H ₅ SiO _1.5 .

  The weight average molecular weight of the silicone resin of the present invention can be measured by GPC (gel permeation chromatography) and refers to a value determined in terms of polystyrene. From the viewpoint of dispersibility and heat resistance, the weight average molecular weight is in the range of 1500 to 200000, and more preferably in the range of 3000 to 100,000.

  In addition, the amount of silanol groups in the silicone compound of the present invention is 2% or more and 10% or less, more preferably 3% or more and 7% or less by weight.

  By making the amount of silanol groups within this range, the polyester fiber and the silicone compound form a crosslinked structure during combustion and promote carbonization of the polyester resin, so that drip can be suppressed.

  If the amount of silanol group is below this range, the effect of drip suppression will be low, which is not preferable, and if it exceeds this range, the effect of drip suppression will reach equilibrium, gelling when melt-kneaded with polyester resin, This is not preferable because the processing characteristics are deteriorated.

For the measurement of the amount of silanol groups, the peak area of SiO _2.0 , RSiO _1.5 , R ₂ SiO _1.0 , and R ₃ SiO _0.5 derived from a structure not containing a silanol group in ²⁹ Si-NMR (integral Value) and a structure containing silanol groups derived from Si (OH) ₄ , SiO _0.5 (OH) ₃ , SiO _1.0 (OH) ₂ , SiO _1.5 (OH), RSi (OH) ₃ , RSiO Ratio of peak area (integrated value) of _0.5 (OH) ₂ , RSiO _1.0 (OH), R ₂ Si (OH) ₂ , R ₂ SiO _0.5 (OH), R ₃ Si (OH) From this, it is possible to calculate the amount of silanol groups.

For example, if the ratio of the integral values of RSiO _1.5 and RSiO _1.0 (OH) is 1.5 (RSiO _1.5 ): 1.0 (RSiO _1.0 (OH)), the following formula 1 Can be sought.

  Further, the content of the silicone resin contained in the polyester fiber is preferably 0.5% by weight or more and 30% by weight or less, more preferably 2.5% by weight from the viewpoint of mechanical properties when the fiber or composite is used. Above 10% by weight.

  The polyester fiber of the present invention contains a silicone resin, which means that the silicone resin is dispersed and / or compatible in the polymer constituting the fiber. It is not particularly limited as long as both the mechanical properties and the flame retardancy performance are obtained when it is made into a fiber or a composite, but it is particularly flame retardant if it is uniformly or finely dispersed or compatible in a single fiber. From the viewpoint of

  In the present invention, the fiber composite contains a flame retardant component, and the flame retardant element equivalent amount in the flame retardant component is preferably 1000 ppm or more and 20000 ppm or less, and the flame retardant element is observed by an X-ray microanalyzer (XMA). The value obtained by

  In the present invention, the flame retardant component may be contained only in the polyester fiber, or may be contained only in the cellulose fiber. Most preferably, it is contained in both the polyester fiber and the cellulosic fiber from the viewpoint of flame retardancy.

  The flame retardant component used in the present invention is a compound containing a halogen element, an alkali metal element, Mg, an alkaline earth metal element, Zn, B, Al, N, P, and Sb.

  In the present invention, the fiber composite contains a flame retardant component, which is desirable because it can sufficiently exhibit the flame retardant effect. From the viewpoint of maintaining a good fabric texture, the amount of flame retardant element in the flame retardant component is the fiber composite. On the other hand, it is preferably 1000 ppm or more and 20000 ppm or less, and more preferably 2000 ppm or more and 10,000 ppm or less.

  Specific examples of the flame retardant component include halogen compounds having a flame retardant action such as generation of non-flammable gas. Specific examples include brominated bisphenols, brominated aromatic dicarboxylic acids, polybrominated benzene and derivatives thereof, and brominated biphenyl derivatives.

  Moreover, the inorganic type compound which has a flame retarding effect, such as reducing surface temperature, is mentioned. Specific examples include calcium carbonate, magnesium hydroxide, magnesium carbonate, stannic oxide, metastannic acid, and stannous hydroxide.

Furthermore, by carbonization layer formation

Examples thereof include phosphorus-based compounds having flame retarding effects such as heat blocking and oxygen blocking. Specifically, triphenyl phosphate, resorcinol bis (diphenyl phosphate), and bisphenol A bis (diphenyl phosphate) phosphate esters, or N-methylol / dimethylphosphonopropionamide, ethylenedimethylphosphonic acid, benzene Examples thereof include phosphonic acid derivatives of phosphonic acid derivatives, phosphoric acid or phosphorous ester, phosphine derivatives, and the like.

  In the present invention, it is preferable to use a compound that does not contain a halogen-based element, that is, a so-called non-halogen-based compound in consideration of environmental load. As such a non-halogen compound, a phosphorus compound is preferably used. Specifically, a cyclic phosphonate is preferable from the viewpoint of flame retardancy, and the phosphorus element equivalent amount is 2500 ppm or more and 5000 ppm or less with respect to the fiber composite.

  In the present invention, by adding a flame retardant component to a fiber composite of a polyester fiber containing a silicone resin and a cellulosic fiber, carbonization of the polyester fiber portion is remarkably accelerated at the time of combustion. Since it is carbonized, both fibers of the fiber composite of the present invention are carbonized, that is, non-drip, and can achieve high flame retardancy.

  When the flame-retardant fiber composite of the present invention is used, it is possible to achieve a self-extinguishing state without melting and dropping in the flame-retardant test specified by the JIS L 1091 D method (coil method). The JIS L 1091 D method (coil method) is a combustion test method for textiles that melt and drip during combustion. Here, “not melted and dripped” means that the test piece does not fall due to melting during or after flame contact with the sample piece, and “self-extinguishing” means that the flame naturally disappears after flame contact.

  Furthermore, in the present invention, it is preferable to self-extinguish without adding a flame retardant component so as to prevent melting and dropping in the flame retardancy test defined by the JIS L 1091 A-4 method (vertical method). JIS L 1091 is a fiber product combustion test method, which is called the vertical method among the test methods existing for each applicable variety from method A (method A-1 to method A-4) to method D. It is a method suitable for checking the presence or absence of drip. Here, “not melted and dripped” means that the test piece does not fall due to melting during or after flame contact with the sample piece, and “self-extinguishing” means that the flame naturally disappears after flame contact.

  Next, the manufacturing method of the fiber composite of the present invention will be described in detail.

  First, regarding the polyester fiber, as a method of applying the silicone resin to the polyester fiber, for example, a method of adding a silicone resin at the time of polymerization of polyester, a polyester chip and a silicone resin are kneaded by a kneader such as a biaxial extruder. Examples thereof include a method and a method of adding a silicone resin at the time of spinning of the polyester, but are not limited thereto as long as the silicone resin can be imparted to the polyester.

  Next, as a method for producing a polyester fiber containing a silicone resin, a normal yarn making process and a drawing process can be employed. In addition, a high-speed spinning and composite spinning can be used in the spinning process, and a method in which the spinning process and the stretching process are continuously performed in the stretching process can be used.

  Further, in the case of a non-woven fabric, it may be directly connected to the spinning process, and in the case of a woven or knitted fabric, it may be made into a fiber form required by a known method after spinning.

  Examples of the polyester fiber and cellulosic fiber of the present invention include, but are not limited to, a thread-shaped product, a belt-shaped product, a fabric-shaped product such as a woven fabric, a knitted fabric, and a nonwoven fabric, and a cotton-shaped product. The fiber cross-sectional shape may be round or irregular (triangular, square, polygonal, flat, hollow, etc.).

    A fiber composite of a polyester fiber and a cellulose fiber is a fiber composite obtained by knitting, knitting, knitting yarn, mixed yarn, or the like. For example, cellulose fibers such as cotton spun yarn and hemp spun yarn are used as warp yarn or weft yarn to make polyester fiber filaments and woven fabrics, or polyester fibers and cellulose fibers by cross-twisting or blending It is good also as a textile fabric using the thread | yarn which compounded the fiber for both length and width.

  As a method for applying a flame retardant component to a fiber composite, a method of copolymerizing and blending with a polyester fiber, a method of applying by high-order processing after yarn production, a method of performing high-order processing on a cellulose fiber, a silicone resin Although the method of high-order processing to the composite of the polyester-type fiber and cellulose-type fiber to contain can be utilized, you may provide by any method.

  In addition, 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 Absorbent, cyanine, stilbene, phthalocyanine, anthraquinone, perinone, quinacridone and other organic pigments, inorganic pigments, fluorescent brighteners, calcium carbonate, silica, titanium oxide particles, antibacterial agents, electrostatic agents Such additives may be contained.

  Moreover, the flame-retardant fiber composite of the present invention can be subjected to various post-processing. For example, functions such as water repellency, hydrophilicity, antistatic properties, deodorizing properties, antibacterial properties, and deep color properties are imparted by processing in bath, exhaustion processing, coating processing, pad-dry processing, and pad-steam processing. be able to.

Hereinafter, the present invention will be described more specifically with reference to examples.
Preparation and evaluation of fibers and fiber composites in the examples were performed as follows.
1. Preparation of silicone resin-containing polyester fiber A chip was prepared by kneading a silicone resin and a polyester polymer in a desired weight ratio with a biaxial extruder at a kneading temperature of 280 ° C., a screw rotation speed of 300 rpm, and L / D: 30. . Next, this chip was vacuum-dried at 150 ° C. for 12 hours in a vacuum dryer, and then spun under the conditions of a spinning temperature of 285 ° C., a spinning speed of 1250 m / min, and a nozzle diameter of 0.23 mm-6H (hole) to obtain an undrawn yarn. It was. Next, the obtained undrawn yarn was combined into 24 filaments, and then drawn under conditions of a drawing temperature of 85 ° C. and a draw ratio of 3.3 times to obtain a drawn yarn. In addition, the silicone resin used here used the silicone resin of Table 1 so that it might become a desired amount, respectively.
2. Preparation of fiber composite of polyester fiber and cellulosic fiber A polyester-based drawn yarn containing a predetermined amount of silicone resin is mixed with a No. 40 twin yarn to obtain the following twisted yarn, and 65% polyester / cotton A tubular knitted fabric of 35% by weight (weight per unit area: 170 g / m ² ) was produced.

Subsequently, the flame retardant components shown in Table 2 were applied by a thermosol method or a bath exhaustion method so as to obtain a desired amount.
3. Evaluation method of fiber strength As a method of measuring yarn strength, Tensilon UCT-100 type manufactured by Orientec Co., Ltd. was used, a tensile test was performed under the conditions of a sample length of 20 cm and a tensile speed of 100 mm / min, and the stress at which the maximum load was shown. Was the fiber strength (cN / dtex).
4). Combustion test Combustion test According to JIS L 1091 (1992) D method, the presence / absence of drip during and after flame contact and the number of flame contact were evaluated.

    -Non-drip property: The number of drip after flame contact was evaluated.

    -Self-extinguishing property: The number of flame contact was evaluated.

In addition, as the acceptance criteria, the number of drip times is 0, and the number of flame contact times is 3 or more.
B. According to JIS L 1091 (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.

    -Non-drip property: The number of drip after flame contact was evaluated.

    -Self-extinguishing property: After flame contact time (time until self-extinguishing) was evaluated.

    In addition, as the acceptance criteria, the number of drip times was 0 or 1 and the after flame time was 10 seconds or less.

Example 1
A silicone resin (product name: 217 Flake, Toray Industries, Inc.) containing 100 mol% of organic groups R being phenyl groups and 100 mol% of constituent units being RSiO _1.5 , having a weight average molecular weight of 3000 and silanol ends of 6.0 wt%. -Dow Corning Silicone Co., Ltd.) was dehydrated and condensed at 2 Torr and 180 ° C. for 6 hours to prepare Silicone A.

Polyethylene terephthalate chip (intrinsic viscosity: 0.64) is used as the polyester polymer, and after preparing a drawn yarn containing 5.0% by weight of silicone A, a twisted yarn with a cotton yarn that is a cellulose fiber is obtained. Thus, a fiber composite was obtained.
Next, the above-mentioned fiber composite is exhausted into the interior of the fiber by a thermosol method at 190 ° C. for 2 minutes so that the phosphorous element is added to the fiber composite at 4000 ppm by the flame-retardant component A, and the flame-retardant fiber composite Got the body.

    As shown in Table 4, the yarn strength of the polyester fiber is good. In the flame retardant evaluation of the obtained fiber composite, the D method is cleared, and there is no drip by the A-4 method. It was excellent.

Examples 2-6
As shown in Table 3, polyester fibers and fiber composites were obtained in the same manner as in Example 1 except that the types and contents of the silicone resin and the flame retardant component were changed.

  As shown in Table 4, the yarn strength of the polyester fiber is good. In the flame retardant evaluation of the obtained fiber composite, the D method is cleared, and there is no drip by the A-4 method. It was excellent.

Example 7
A polyester fiber and a fiber composite were obtained in the same manner as in Example 1 except that Silicone E was used.

  As shown in Table 4, the obtained polyester fiber has good yarn strength, and the obtained fiber composite has a non-drip property in the flame retardancy evaluation, although there is one drip in the A-4 method. It was excellent in self-extinguishing properties.

Examples 8 and 9
A polyester fiber and a flame retardant fiber composite were obtained in the same manner as in Example 1 except that the polyethylene terephthalate chip was changed to polypropylene terephthalate or polybutylene terephthalate.

  As shown in Table 4, the yarn strength of the polyester fiber is good. In the flame retardant evaluation of the obtained fiber composite, the D method is cleared, and there is no drip by the A-4 method. It was excellent.

Example 10
L-lactide was mixed with 150 ppm of tin octylate, polymerized in a reaction vessel equipped with a stirrer at a temperature of 192 ° C. for 10 minutes in a nitrogen atmosphere, further chipped with a twin screw extruder, and then a temperature of 140 ° C. Was subjected to solid phase polymerization in a nitrogen atmosphere to obtain a poly-L-lactic acid polymer having a weight average molecular weight of 151,000. A polyester fiber and a flame retardant fiber composite were obtained in the same manner as in Example 1 except that this polylactic acid was used.

  As shown in Table 4, the yarn strength of the polyester fiber is good. In the flame retardant evaluation of the obtained fiber composite, the D method is cleared, and there is no drip by the A-4 method. It was excellent.

Comparative Example 1
After producing a drawn yarn containing only 10% by weight of a polyethylene terephthalate chip and silicone E inside the fiber, a twisted yarn with a cotton yarn which is a cellulosic fiber was obtained to obtain a fiber composite.

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

Comparative Example 2
After producing a drawn yarn of only a polyethylene terephthalate chip, a twisted yarn with a cotton yarn which is a cellulosic fiber was obtained to obtain a fiber composite. Next, the above fiber composite was exhausted into the fiber by a thermosol method at 190 ° C. for 2 min so as to impart 11000 ppm of phosphorus element to the fiber composite with the flame retardant component A, and the flame retardant of the present invention. A functional fiber composite was obtained.

  As shown in Table 4, it was drip by the D method and the A-4 method, and the non-drip property was low.

Claims (5)

  A flame retardant fiber composite comprising a polyester fiber containing a silicone resin and a cellulose fiber, wherein the flame retardant component contains 1000 ppm or more and 20000 ppm or less in terms of flame retardant element. 2. The flame-retardant fiber composite according to claim 1, wherein in the monomer unit constituting the silicone resin, RSiO _1.5 (R: hydrogen or organic group) unit is 85 mol% or more.   The flame-retardant fiber composite according to claim 1, wherein at least a part of the organic group R of the silicone resin is a phenyl group.   The flame-retardant fiber composite according to any one of claims 1 to 3, wherein the silicone resin has a weight average molecular weight of 1500 or more and 200,000 or less.   The flame-retardant fiber composite according to any one of claims 1 to 4, wherein the flame-retardant element is a non-halogen element.