JP2005097819A - Polyester-based fiber structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester-based fiber structure capable of preventing deterioration of mechanical characteristics and having improved flame-retardant properties and dripping properties. <P>SOLUTION: This fiber structure is composed of a polyester-based fiber, wherein the polyester-based fiber structure contains a silicone-based compound and the silicone-based compound has a dispersion diameter in the range of 0.1-1,000 nm. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to a polyester fiber structure that can be suitably used as a flame retardant material for a fiber structure. More specifically, the present invention relates to a drip as a combustion characteristic with less deterioration in the yarn physical properties of the polyester fiber structure. The present invention relates to a polyester fiber structure having improved properties and flame retardancy.

  Conventionally, polyethylene terephthalate fibers, polybutylene terephthalate fibers, and polypropylene terephthalate fibers, which are polyester fibers, have been widely used for mechanical properties, high-order processability, color development, texture, price, etc., for clothing and industrial materials. Many are used. In recent years, non-petroleum polyester fibers such as polylactic acid fibers have begun to be put on the market, and the usefulness of polyester fibers is increasing. Accordingly, there is a strong demand for flame retardancy in terms of fire prevention. Therefore, many flame retardant polyester fibers have been proposed. Examples include exhausted halogen-based flame retardant in post-processing (for example, see Patent Document 1), and kneaded or copolymerized phosphorus-based flame retardant (for example, see Patent Document 2). The flame-retarding technology has problems such as lowering of yarn-making property, lowering of mechanical properties, generation of toxic gas during combustion, texture hardening, etc., and the combustion behavior is all drip (melting dripping). There was a risk of the next fire, and there were unsolved problems.

  In order to solve these problems, an example in which silicone oil having a functional group in the side chain was added to the polyester fiber structure to improve the drip suppression effect, suppress the generation of toxic gas, and prevent the deterioration of mechanical properties ( For example, see Patent Document 3), by incorporating a silicone oil having a functional group and an organophosphorus compound in a polyester fiber structure, improvement of drip suppression effect, suppression of generation of toxic gas, and prevention of deterioration of mechanical properties were examined. Although there are some examples (see, for example, Patent Document 4), there is no example in which the dispersion state of the silicone compound is controlled to prevent the deterioration of the yarn-making property and mechanical properties and the flame retardancy, and knowledge about the dispersion state of the silicone compound Has never been known before.

  On the other hand, it is known that a silicone compound is contained in a polyester fiber structure. For example, a polyorganosiloxane diol having a molecular weight of 600 to 150,000 is added to a polyethylene terephthalate fiber structure in order to impart water repellency ( For example, refer to Patent Document 5), polyester systems such as those obtained by adding a polyorganosiloxane having a molecular weight of 600 to 200,000 and a silane coupling agent in a polyester fiber structure to improve dyeability (for example, refer to Patent Document 6). There is knowledge about silicone compounds contained in fiber structures.

However, there is now knowledge that the dispersion state of the silicone compound contained in the polyester fiber structure can be dispersed in various states to improve various effects due to the decrease in fiber properties and the addition of the silicone compound. Was not known until.
JP 62-57985 A Japanese Patent Laid-Open No. 50-56488 JP-A-8-209446 JP-A-9-268423 JP 61-12914 A JP 61-1113820 A

  An object of the present invention is to provide a highly flame-retardant polyester fiber structure capable of preventing the problem of yarn-making property and lowering of mechanical properties and suppressing drip during combustion. Is.

The present invention adopts the following configuration in order to solve the above problems. That is,
(1) A fiber structure comprising polyester fibers, wherein the fiber structure contains a silicone compound, and the average dispersion diameter of the silicone compound is in the range of 0.1 nm to 1000 nm. Polyester fiber structure.

  (2) The polyester fiber structure according to (1), wherein the silicone compound contains a phenyl group.

  (3) The polyester fiber structure according to (1) or (2), wherein the silicone compound is a silicone resin.

  According to the present invention, the use used as a flame retardant material, specifically, for example, there is little decrease in yarn properties in clothing use, non-clothing use, industrial use, etc. An excellent polyester fiber structure can be provided.

  Hereinafter, the present invention will be described in detail.

  The polyester fiber structure of the present invention is characterized in that the fiber structure contains a silicone compound, and the average dispersion diameter of the silicone compound is in the range of 0.1 nm to 1000 nm. .

  The polyester fiber structure referred to in the present invention is a polymer synthesized from a dicarboxylic acid such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate or the like and an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, as well as poly-L-lactic acid. It is a non-petroleum polyester compound of poly-D-lactic acid.

  Further, the silicone compound in the present invention is an organosilicon compound, and has a siloxane bond and an organic group bonded to a silicon atom in the same molecule. Specific examples include silicone oils, silicone resins, silicone rubbers, silane coupling agents, silicone powders, etc., but not limited as long as they have a siloxane bond and an organic group bonded to a silicon atom in the same molecule. . These silicone compounds can be used alone or in combination.

  It is presumed that the silicone compound forms a crosslinked structure with a decomposition product generated when the polyester burns, and exhibits non-drip properties. At the same time, since the cracked gas is suppressed, the flame retardancy can be improved without generating a toxic gas. That is, the polyester fiber structure to which the silicone compound is added is cross-linked by the heat at the time of combustion, decomposition is suppressed by the cross-linked structure, non-drip (carbonization promotion), and further, carbonization is promoted to form a carbonized layer. Thus, flame retardancy can be improved.

  In the present invention, the dispersion diameter of the silicone compound is in the range of 0.1 nm to 1000 nm. When the average dispersion diameter of the silicone-based compound exceeds 1000 nm, it is not preferable from the viewpoints of spinning properties, mechanical properties, flame retardancy, and non-drip properties. That is, by making the average dispersion diameter of the silicone compound within the scope of the present invention, it is possible to prevent the deterioration of the mechanical properties due to the coarsening of the silicone compound in terms of preventing the deterioration of the mechanical properties. It is possible to solve the problems of spinning and mechanical properties that were problems, and in terms of improving flame retardancy and drip, the surface area of the silicone compound in the polyester fiber structure is increased, and the polyester during combustion It has been found that cross-linking with the degradation product of the fiber structure can be promoted.

  Further, the average dispersion diameter of the silicone compound is preferably in the range of 0.1 nm to 800 nm, more preferably in the range of 0.1 nm to 500 nm, from the viewpoints of yarn production, mechanical properties, flame retardancy, and drip improvement.

  The average dispersion diameter of the silicone compound can be measured by observing the fiber cross section with a TEM (transmission electron microscope). The average dispersion diameter as used in the present invention means that 5 single fibers are arbitrarily selected, and the dispersion diameter of the silicone compound is within a range of 1000 to 500,000 times the magnification of the cross section in a direction perpendicular to the fiber axis of the single fiber. The average value of the maximum diameter Y in the vertical direction and the maximum diameter X in the horizontal direction of the silicone compound observed at a magnification that can be observed is the dispersion diameter (see FIG. 1). Any shape such as a square may be used. In the present invention, ten of the silicone compounds having the largest dispersion diameter are selected from the silicone compounds observed under the above-mentioned conditions, and the average value of the dispersion diameters is defined as the average dispersion diameter of the silicone compounds.

  In the present invention, the maximum dispersion diameter of the silicone compound is preferably 1000 nm or less. The maximum dispersion diameter here refers to the dispersion diameter having the largest dispersion diameter of the silicone compound observed by the above method. If the maximum dispersion diameter exceeds 1000 nm, the silicone compound becomes a foreign substance, resulting in a decrease in mechanical properties.

  In the present invention, the dispersion state of the silicone-based compound in the fiber axis direction is not particularly limited, but it is the same or longer than the average dispersion diameter in the direction perpendicular to the fiber axis.

  In the present invention, the silicone compound preferably contains a phenyl group. By including a phenyl group in the silicone compound, the organic property of the silicone compound is improved, so that the dispersibility with the polyester fiber structure can be improved. Moreover, since the heat resistance of a silicone type compound can be improved by containing a phenyl group, it is preferable also from a flame-retardant viewpoint. In addition to the phenyl group, an aromatic group having high heat resistance such as naphthalene or anthracene may be used.

  The content of the phenyl group is preferably 10 mol% or more, more preferably 30 mol, in the side chain organic group excluding the terminal organic group of the silicone compound from the viewpoint of flame retardancy and dispersibility. % Or more and 100 mol% or less.

In the present invention, the silicone compound is preferably a silicone resin. The silicone compound has at least four branch units of R ₃ SiO _0.5 (M unit), R ₂ SiO _1.0 (D unit), RSiO _1.5 (T unit), and SiO _2.0 (Q unit). It is comprised from either and the silicone resin here is a thing containing T unit. Since the heat resistance of a silicone type compound improves because a silicone type compound contains T unit, it is preferable from a flame-retardant viewpoint. The above-mentioned R is an organic group.

  Further, the content of the T unit is preferably 10 mol% or more, more preferably 30 mol% or more, based on the entire silicone compound from the viewpoint of heat resistance of the silicone compound.

  Moreover, it is preferable that the silicone type compound of this invention contains the 1 type (s) or 2 or more types chosen from an alkyl group, an alkoxy group, a phenyl group, a hydroxyl group, an epoxy group, a vinyl group, and an amino group as a terminal group. The term “end group” as used herein refers to a terminal functional group of a siloxane chain, and among them, an alkyl group, an alkoxy group, and a hydroxyl group are preferable from the viewpoint of dispersibility.

  Specific examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.

  Examples of the alkoxy group include, but are not limited to, a methoxy group and an ethoxy group.

  The addition amount of the silicone compound of the present invention is preferably such that the weight ratio of the polyester to the silicone compound is 99.9: 0.1 to 70:30, more preferably 99.5: 0.5 to The range is 80:20. When the weight ratio of the polyester and the silicone compound is smaller than 99.9: 0.1, the non-drip property and the flame retardant effect are lowered. When the weight ratio exceeds 70:30, the average dispersion diameter of the silicone compound is increased and the yarn-forming property. Cause deterioration of mechanical properties and mechanical properties.

  Moreover, the weight average molecular weight of the silicone compound of the present invention is preferably in the range of 100 to 500,000, and more preferably in the range of 500 to 100,000, from the viewpoint of dispersibility. The average molecular weight of the silicone compound can be measured by GPC (gas chromatography) and can be determined in terms of polystyrene.

  The polyester fiber structure of the present invention preferably has a LOI (Limited Oxygen Index) of 22 or more, more preferably 24 or more and 50 or less. The LOI referred to here is the minimum oxygen concentration necessary for the substance to burn, and can be measured by JISK-7201 (polymer material combustion test method by oxygen index method).

  If this LOI is less than 22, the flame retardant effect is small, which is not suitable as a flame retardant fiber material.

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

  Examples of the method of applying the silicone compound into the polyester include a method of adding the silicone compound at the time of polymerization of the polyester, a method of kneading the polyester chip and the silicone compound with a kneader such as a biaxial extruder, or the polyester Although the method of adding a silicone type compound at the time of spinning etc. is mentioned, if a silicone type compound can be provided in polyester, it will not restrict to this.

  As a method for producing a polyester fiber structure containing a silicone compound, a normal polymerization process, yarn production process, and drawing process can be employed, and the process is not affected. In addition, a special process may be used. For example, solid phase polymerization or continuous polymerization may be used in the polymerization process, high speed spinning or composite spinning may be used in the spinning process, and a method in which the spinning process and stretching process are continuously performed in the stretching process.

  In addition, the fiber cross section of the fiber structure is not limited to a round cross section, but may be a cross section having a triangular shape, a square shape, a polygonal shape, a flat shape, a hollow cross section or the like.

  The polyester fiber structure of the present invention includes hindered phenols, amines, phosphites, thioesters and other antioxidants, benzotriazoles, benzophenones, cyanoacrylates, UV absorbers, infrared absorption Agents, cyanine, stilbene, phthalocyanine, anthraquinone, perinone, quinacridone, and other organic pigments, inorganic pigments, fluorescent brighteners, calcium carbonate, silica, titanium oxide particles, antibacterial agents, electrostatic agents, etc. The additive may be contained.

  Moreover, since the polyester fiber structure of the present invention is not affected by post-processing, various post-processing can be performed. For example, functions such as water repellency, hydrophilicity, antistatic properties, deodorizing properties, antibacterial properties, and deep color properties are imparted by processing in the bath, exhaustion processing, coating processing, pad-dry processing, pad-steam processing, etc. be able to.

  The polyester fiber structure of the present invention can be used in combination with conventional flame retardant techniques. For example, copolymerization or blending or post-processing such as halogen flame retardants and phosphorus flame retardants can be employed.

  Examples of the polyester fiber structure in the present invention include those in the form of a fabric such as a thread or woven fabric, a knitted fabric or a non-woven fabric, or a fiber product made of these.

  That is, the carbonized polyester fiber structure of the present invention can be suitably used as a flame retardant material, particularly for clothing use, industrial use, interior, curtain, chair upholstery and the like.

  Hereinafter, the present invention will be described more specifically with reference to examples.

  Each measurement and evaluation in the examples was performed as follows.

<Dispersion diameter of silicone compound>
Apparatus: Transmission electron microscope (H-7100FA, manufactured by Hitachi)
Measurement conditions: acceleration voltage 100 kV
Sample preparation: Ultra-thin section method Cutting direction: Crossing (fiber cross-section direction)
<Thread properties (undrawn yarn)>
Using Tensilon UCT-100 manufactured by Orientec Co., Ltd., a tensile test was performed under the conditions of a sample length of 5 cm and a tensile speed of 200 mm / min, and the stress at the point showing the maximum load was defined as the fiber strength (cN / dtex). Further, the elongation at break was defined as the elongation (%) of the fiber.

<Thread properties (drawn yarn)>
Using Tensilon UCT-100 manufactured by Orientec Co., Ltd., 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 the point showing the maximum load was defined as the fiber strength (cN / dtex). Further, the elongation at break was defined as the elongation (%) of the fiber.

<Combustion test>
A cylindrical knitted fabric sample was evaluated by the number of times of flame contact (average number of times of ignition of five samples) and the drip property at the time of burning or extinguishing by the number of times of melt dropping by the JISL-1091D method.

Example 1
A silicone compound having a branched structure of T units as a silicone compound, a terminal group being a hydroxyl group, a phenyl group content of 100 mol% with respect to a side chain organic group of the silicone compound, and a weight average molecular weight of about 2000. Kneading temperature is 280 ° C., screw rotation speed is 300 rpm, L / D: 30, and the polyester polymer is IV: 0.64 polyethylene terephthalate chip and polyester terephthalate: silicone compound at a weight ratio of 90:10. Then, a master chip was produced. Next, this master chip was dried in a vacuum dryer at 150 ° C. for 12 hours, 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−6 H (hole). After being obtained, the fineness, strength, and elongation were measured as the yarn physical properties. Next, the obtained undrawn yarn was combined into 26 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. Was measured.

  The results are shown in Table 1. Both the undrawn yarn and the drawn yarn had almost the same physical properties as Comparative Example 1, that is, regular polyester, and had good mechanical properties.

  Table 2 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was about 9 nm, the maximum dispersion diameter was 18 nm, and the dispersion characteristics were excellent.

  In addition, Table 2 shows the results of producing a tubular knitted fabric from the drawn yarn and evaluating the flame retardancy by a combustion test. As a result, there was no drip, the number of times of flame contact was 5, and the flame retardancy was excellent.

Example 2
Silicone compound having a branched structure of T units as a silicone compound, a terminal group being a hydroxyl group, a phenyl group content of 80 mol% with respect to a side chain organic group of the silicone compound, and a weight average molecular weight of about 2000 A drawn yarn was obtained in the same manner as in Example 1 except that was used.

  The results are shown in Table 1. Both the undrawn yarn and the drawn yarn had almost the same physical properties as Comparative Example 1, that is, regular polyester, and had good mechanical properties.

  Table 2 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was about 110 nm, the maximum dispersion diameter was 190 nm, and the dispersion characteristics were excellent.

  In addition, Table 2 shows the results of evaluation of flame retardancy by a combustion test. As a result, there was no drip, the number of times of flame contact was 5, and the flame retardancy was excellent.

Example 3
A silicone compound having a branched structure of T units as a silicone compound, a terminal group is a hydroxyl group, a phenyl group content of 50 mol% with respect to a side chain organic group of the silicone compound, and a weight average molecular weight of about 2000 silicone compound is used. A drawn yarn was obtained in the same manner as in Example 1 except that.

  The results are shown in Table 1. Both the undrawn yarn and the drawn yarn had almost the same physical properties as Comparative Example 1, that is, regular polyester, and had good mechanical properties.

  Table 2 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was about 240 nm, the maximum dispersion diameter was 280 nm, and the dispersion characteristics were excellent.

  In addition, Table 2 shows the results of evaluation of flame retardancy by a combustion test. As a result, there was no drip, the number of times of flame contact was 4, and the flame retardancy was excellent.

Example 4
A silicone compound having a T-unit branched structure as a silicone compound, an end group being an ethoxy group, and a phenyl group content of 100 mol% with respect to a side chain organic group of the silicone compound, and a weight average molecular weight of about 2000 A drawn yarn was obtained in the same manner as in Example 1 except that was used.

  The results are shown in Table 1. Both the undrawn yarn and the drawn yarn had almost the same physical properties as Comparative Example 1, that is, regular polyester, and had good mechanical properties.

  Table 2 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was 18 nm, the maximum dispersion diameter was 26 nm, and the dispersion characteristics were excellent.

  In addition, Table 2 shows the results of evaluation of flame retardancy by a combustion test. As a result, there was no drip, the number of times of flame contact was 5, and the flame retardancy was excellent.

Example 5
Silicone compound having a T-unit branched structure as a silicone compound, an end group being an ethoxy group, a phenyl group content of 80 mol% with respect to a side chain organic group of the silicone compound, and a weight average molecular weight of about 2000 A drawn yarn was obtained in the same manner as in Example 1 except that the compound was used.

  The results are shown in Table 1. Both the undrawn yarn and the drawn yarn had almost the same physical properties as Comparative Example 1, that is, regular polyester, and had good mechanical properties.

  Table 2 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was 180 nm, the maximum dispersion diameter was 200 nm, and the dispersion characteristics were excellent.

  In addition, Table 2 shows the results of evaluation of flame retardancy by a combustion test. As a result, there was no drip, the number of times of flame contact was 5, and the flame retardancy was excellent.

Example 6
Silicone compound having a T-unit branched structure as a silicone compound, an end group being an ethoxy group, a phenyl group content of 50 mol% with respect to a side chain organic group of the silicone compound, and a weight average molecular weight of about 2000 A drawn yarn was obtained in the same manner as in Example 1 except that the compound was used.

  The results are shown in Table 1. Both the undrawn yarn and the drawn yarn had almost the same physical properties as Comparative Example 1, that is, regular polyester, and had good mechanical properties.

  Table 2 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was 320 nm, the maximum dispersion diameter was 410 nm, and the dispersion characteristics were excellent.

  In addition, Table 2 shows the results of evaluation of flame retardancy by a combustion test. As a result, there was no drip, the number of times of flame contact was 4, and the flame retardancy was excellent.

Example 7
Silicone compound having a branched structure of T units as a silicone compound, a terminal group being a hydroxyl group, a phenyl group content of 100 mol% with respect to a side chain organic group of the silicone compound, and a weight average molecular weight of about 4000 A drawn yarn was obtained in the same manner as in Example 1 except that was used.

  The results are shown in Table 1. Both the undrawn yarn and the drawn yarn had almost the same physical properties as Comparative Example 1, that is, regular polyester, and had good mechanical properties.

  Table 2 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was 16 nm, the maximum dispersion diameter was 25 nm, and the dispersion characteristics were excellent.

  In addition, Table 2 shows the results of evaluation of flame retardancy by a combustion test. As a result, there was no drip, the number of times of flame contact was 5, and the flame retardancy was excellent.

Example 8
Silicone compound having a branched structure of T units as a silicone compound, a terminal group being a hydroxyl group, a phenyl group content of 80 mol% with respect to a side chain organic group of the silicone compound, and a weight average molecular weight of about 4000 A drawn yarn was obtained in the same manner as in Example 1 except that was used.

  The results are shown in Table 1. Both the undrawn yarn and the drawn yarn had almost the same physical properties as Comparative Example 1, that is, regular polyester, and had good mechanical properties.

  Table 2 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was 200 nm, the maximum dispersion diameter was 280 nm, and it had excellent dispersion characteristics.

  In addition, Table 2 shows the results of evaluation of flame retardancy by a combustion test. As a result, there was no drip, the number of times of flame contact was 5, and the flame retardancy was excellent.

Example 9
Silicone compound having a branched structure of T units as a silicone compound, a terminal group being a hydroxyl group, a phenyl group content of 50 mol% with respect to a side chain organic group of the silicone compound, and a weight average molecular weight of about 4000 A drawn yarn was obtained in the same manner as in Example 1 except that was used.

  The results are shown in Table 1. Both the undrawn yarn and the drawn yarn had almost the same physical properties as Comparative Example 1, that is, regular polyester, and had good mechanical properties.

  Table 2 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was 380 nm, the maximum dispersion diameter was 490 nm, and it had excellent dispersion characteristics.

  In addition, Table 2 shows the results of evaluation of flame retardancy by a combustion test. As a result, there was no drip, the number of times of flame contact was 4, and the flame retardancy was excellent.

Example 10
Silicone compound having a T-unit branched structure as a silicone compound, an end group being an ethoxy group, a phenyl group content of 100 mol% with respect to a side chain organic group of the silicone compound, and a weight average molecular weight of about 4000 A drawn yarn was obtained in the same manner as in Example 1 except that the compound was used.

  The results are shown in Table 1. Both the undrawn yarn and the drawn yarn had almost the same physical properties as Comparative Example 1, that is, regular polyester, and had good mechanical properties.

  Table 2 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was 29 nm, the maximum dispersion diameter was 39 nm, and the dispersion characteristics were excellent.

  In addition, Table 2 shows the results of evaluation of flame retardancy by a combustion test. As a result, there was no drip, the number of times of flame contact was 5, and the flame retardancy was excellent.

Example 11
Silicone compound having a T-unit branched structure as a silicone compound, an end group being an ethoxy group, a phenyl group content of 80 mol% with respect to a side chain organic group of the silicone compound, and a weight average molecular weight of about 4000 A drawn yarn was obtained in the same manner as in Example 1 except that the compound was used.

  The results are shown in Table 1. Both the undrawn yarn and the drawn yarn had almost the same physical properties as Comparative Example 1, that is, regular polyester, and had good mechanical properties.

  Table 2 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was 240 nm, the maximum dispersion diameter was 350 nm, and the dispersion characteristics were excellent.

  In addition, Table 2 shows the results of evaluation of flame retardancy by a combustion test. As a result, there was no drip, the number of times of flame contact was 4, and the flame retardancy was excellent.

Example 12
Silicone compound having a T-unit branched structure as a silicone compound, an end group being an ethoxy group, a phenyl group content of 50 mol% with respect to a side chain organic group of the silicone compound, and a weight average molecular weight of about 4000 A drawn yarn was obtained in the same manner as in Example 1 except that the compound was used.

  The results are shown in Table 1. Both the undrawn yarn and the drawn yarn had almost the same physical properties as Comparative Example 1, that is, regular polyester, and had good mechanical properties.

  Table 2 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was 410 nm, the maximum dispersion diameter was 580 nm, and the dispersion characteristics were excellent.

  In addition, Table 2 shows the results of evaluation of flame retardancy by a combustion test. As a result, there was no drip, the number of times of flame contact was 4, and the flame retardancy was excellent.

Example 13
A silicone compound having a branched structure of D unit as a silicone compound, a terminal group is a hydroxyl group, and a phenyl group content is 100 mol% with respect to a side chain organic group of the silicone compound, and a weight average molecular weight is about 2000. A drawn yarn was obtained in the same manner as in Example 1 except that it was used.

  The results are shown in Table 1. Both the undrawn yarn and the drawn yarn had almost the same physical properties as Comparative Example 1, that is, regular polyester, and had good mechanical properties.

  Table 2 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was about 14 nm, the maximum dispersion diameter was 32 nm, and the dispersion characteristics were excellent.

  In addition, Table 2 shows the results of evaluation of flame retardancy by a combustion test. As a result, there was no drip, the number of times of flame contact was 4, and the flame retardancy was excellent.

Example 14
A silicone compound having a branched structure of D units as a silicone compound, a terminal group being a hydroxyl group, a phenyl group content of 80 mol% with respect to a side chain organic group of the silicone compound, and a weight average molecular weight of about 2000. A drawn yarn was obtained in the same manner as in Example 1 except that it was used.

  The results are shown in Table 1. The yarn physical properties were almost the same as in Comparative Example 1, that is, regular polyester, and had good mechanical properties.

  Table 2 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was about 500 nm, the maximum dispersion diameter was 610 nm, and the dispersion characteristics were excellent.

  In addition, Table 2 shows the results of evaluation of flame retardancy by a combustion test. As a result, the number of drip was 1 and the number of flame contact was 4 and had excellent flame retardancy.

Examples 15-28
Polybutylene terephthalate having an IV of 0.63 is used as the polyester polymer, kneading temperature, spinning temperature is 265 ° C., spinning speed is 1500 m / min, the nozzle diameter is 0.23 mm-24H, the stretching temperature is 80 ° C., and the stretching ratio is 2. A drawn yarn was obtained in the same manner as in Example 1 except that the silicone compound of Examples 1 to 14 was used as the silicone compound.

  The results are shown in Table 3. Both the undrawn yarn and the drawn yarn had almost the same physical properties as Comparative Example 4, that is, regular polybutylene terephthalate, and had good mechanical properties.

  Table 4 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was in the range of 29 nm to 490 nm in Examples 15 to 28, the maximum dispersion diameter was in the range of 50 to 640 nm, and had excellent dispersion characteristics.

  In addition, Table 4 shows the results of evaluation of flame retardancy by a combustion test. As a result, the number of times of drip was in the range of 0 to 2 times, and the number of times of flame contact was 4 times in the example with the smallest number of flame contact.

Examples 29-42
Polypropylene terephthalate with an IV of 0.62 is used as the polyester polymer, the kneading temperature, the spinning temperature is 265 ° C., the spinning speed is 2000 m / min, the nozzle diameter is 0.30 mm-24H, the stretching temperature is 80 ° C., and the stretching ratio is 2.1 times. A modified yarn was obtained in the same manner as in Example 1 except that the silicone compound of Examples 1 to 14 was used as the silicone compound.

  The results are shown in Table 5. Both the undrawn yarn and the drawn yarn had almost the same physical properties as those of Comparative Example 7, that is, regular polypropylene terephthalate, and had good mechanical properties.

  Table 6 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was in the range of 90 to 510 nm in Examples 29 to 42, the maximum dispersion diameter was in the range of 170 to 650 nm, and had excellent dispersion characteristics.

  In addition, Table 6 shows the results of evaluation of flame retardancy by a combustion test. As a result, the number of times of drip was in the range of 0 to 2 times, and the number of times of flame contact was 4 times in the example with the smallest number of flame contact.

Examples 43-56
L-lactide was mixed with 150 ppm of tin octylate, polymerized in a reaction vessel equipped with a stirrer in a nitrogen atmosphere at 192 ° C. for 10 minutes, further chipped with a twin screw extruder, and then in a nitrogen atmosphere at 140 ° C. After obtaining a poly-L-lactic acid polymer having a weight average molecular weight of 151,000 as a polyester polymer by solid-phase polymerization at 210.degree. C., the kneading temperature is 210.degree. C., the drying temperature is 100.degree. C. for 12 hours, the spinning temperature is 210.degree. The speed was changed to 3000 m / min, the cap diameter of 0.30 mm-18H, the stretching temperature of 90 ° C., and the stretching ratio of 1.6 times (no spinning), and the silicone compounds of Examples 1 to 14 were used as silicone compounds. Except for the above, a drawn yarn was obtained in the same manner as in Example 1.

  The results are shown in Table 7. The yarn physical properties of the undrawn yarn and drawn yarn were almost the same as those of Comparative Example 10, that is, regular polylactic acid, and had good mechanical properties.

  Table 8 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was in the range of 190 to 580 nm in Examples 43 to 56, the maximum dispersion diameter was 250 to 680 nm, and had excellent dispersion characteristics.

  In addition, Table 8 shows the results of evaluation of flame retardancy by a combustion test. As a result, the drip was not in all the examples, and the number of times of flame contact was 4 in the example with the smallest number of flame contact, and had excellent flame retardancy.

Comparative Example 1
A drawn yarn was obtained in the same manner as in Example 1 using only a polyethylene terephthalate chip without using a silicone compound and kneading.

  The results are shown in Table 1.

  In addition, Table 2 shows the results of evaluation of flame retardancy by a combustion test. As a result, the number of drip was 10 and the number of flame contact was 1 and the flame retardancy was low.

Comparative Example 2
Silicone compound having a D-unit branched structure, a terminal group is a methyl group, and a weight-average molecular weight of about 10,000 is 0 mol% with respect to the side chain organic group of the silicone compound. Although an attempt was made to obtain a drawn yarn in the same manner as in Example 1 except that was used, the physical properties of the undrawn yarn were greatly deteriorated and could not be drawn. The results are shown in Table 1.

  Table 2 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was 8000 nm, the maximum dispersion diameter was 9800 nm, and the dispersion state was very poor.

  In addition, Table 2 shows the results of evaluation of flame retardancy by a combustion test. As a result, the number of drip was 5 times and the number of flame contact was 2 times, which was improved as compared with Comparative Example 1. However, compared with Examples 1 to 14, the drip suppression effect and flame retardancy were low. It was.

Comparative Example 3
Silicone compound having a T-unit branched structure, a terminal group being a methyl group, and a phenyl group content of 0 mol% with respect to the side chain organic group of the silicone compound, a weight-average molecular weight of 2000 A stretched yarn was obtained in the same manner as in Example 1 except that was used, but the physical properties of the unstretched yarn were greatly deteriorated and could not be stretched. The results are shown in Table 1.

  Table 2 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameter of the silicone compound was 5000 nm, the maximum dispersion diameter was 6800 nm, and the dispersion state was very poor.

  In addition, Table 2 shows the results of evaluation of flame retardancy by a combustion test. As a result, the number of drip was 4 times and the number of flame contact was 2 times, which was improved as compared with Comparative Example 1, but the flame retardancy was low as compared with Examples 1-14.

Comparative Example 4
A drawn yarn was obtained in the same manner as in Example 15 using only a polybutylene terephthalate chip without using a silicone compound and without kneading.

  The results are shown in Table 3.

  In addition, Table 4 shows the results of evaluation of flame retardancy by a combustion test. As a result, the number of drip was 12 and the number of flame contact was 1 and the flame retardancy was low.

Comparative Examples 5 and 6
Using the silicone compounds of Comparative Examples 2 and 3, respectively, an attempt was made to obtain a drawn yarn in the same manner as in Example 15. However, the undrawn yarn had a large decrease in yarn properties and could not be drawn.

  The results are shown in Table 3.

  Table 4 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameters of the silicone compounds were 8500 nm and 4500 nm, respectively, the maximum dispersion diameters were 10100 nm and 5500 nm, respectively, and the dispersion state was very bad.

  In addition, Table 4 shows the results of evaluation of flame retardancy by a combustion test. As a result, the drip times were 7 times and 5 times, respectively, and the flame contact times were 2 times and 2 times, respectively, which were improved as compared with Comparative Example 4, but were incombustible characteristics when compared with Examples 15 to 28. Was low.

Comparative Example 7
A drawn yarn was obtained in the same manner as in Example 29 using only a polypropylene terephthalate chip without using a silicone compound and kneading.

  The results are shown in Table 5.

  In addition, Table 6 shows the results of evaluation of flame retardancy by a combustion test. As a result, the number of drip was 13 times, the number of flame contact was 2 times, and the flame retardancy was low.

Comparative Examples 8 and 9
Using the silicone compounds of Comparative Examples 2 and 3, respectively, an attempt was made to obtain a drawn yarn in the same manner as in Example 29. However, the decrease in the physical properties of the undrawn yarn was so great that it could not be drawn.

  The results are shown in Table 5.

  Table 6 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameters of the silicone compounds were 8900 nm and 7800 nm, respectively, and the maximum dispersion diameters were 10900 nm and 8900 nm, respectively, and the dispersion state was very poor.

  In addition, Table 6 shows the results of evaluation of flame retardancy by a combustion test. As a result, the drip times were 6 times and 6 times, respectively, and the flame contact times were 2 times and 2 times, respectively, which were improved as compared with Comparative Example 7, but compared with Examples 29 to 42, flame retardancy characteristics Was low.

Comparative Example 10
A drawn yarn was obtained in the same manner as in Example 43 using only a polylactic acid chip without using a silicone compound and kneading.

  The results are shown in Table 7.

  In addition, Table 8 shows the results of evaluation of flame retardancy by a combustion test. As a result, the number of drip was 15 times, the number of flame contact was 2 times, and the flame retardancy was low.

Comparative Examples 11 and 12
Using each of the silicone compounds of Comparative Examples 2 and 3, an attempt was made to obtain a drawn yarn in the same manner as in Example 43, but the decrease in the yarn physical properties of the undrawn yarn was so great that the drawing could not be performed.

  The results are shown in Table 7.

  Table 8 shows the results of measuring the dispersion diameter of the silicone compound. The average dispersion diameters of the silicone compounds were 10900 nm and 9800 nm, respectively, the maximum dispersion diameters were 11200 nm and 10700 nm, respectively, and the dispersion state was very poor.

  In addition, Table 8 shows the results of evaluation of flame retardancy by a combustion test. As a result, the drip times were 7 times and 6 times, respectively, and the flame contact times were 2 times and 2 times, respectively, which were improved as compared with Comparative Example 10, but compared with Examples 43 to 56, flame retardancy characteristics Was low.

It is an example of the transmission electron microscope (TEM) photograph which shows the shape of the fiber of the single fiber cross section which comprises the polyester-type fiber structure of this invention.

Explanation of symbols

X: Maximum horizontal diameter of silicone compound Y: Maximum vertical diameter of silicone compound

Claims (3)

A fiber structure comprising a polyester fiber, wherein the fiber structure contains a silicone compound, and the average dispersion diameter of the silicone compound is in the range of 0.1 nm to 1000 nm. Structure. The polyester fiber structure according to claim 1, wherein the silicone compound contains a phenyl group. The polyester fiber structure according to claim 1 or 2, wherein the silicone compound is a silicone resin.