Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters

Definitions

• the present invention relates to a polyester composition and a polyester fiber.
• Polyesters especially polyethylene terephthalate, are widely used in textile applications.
• the color development is improved by roughening the fiber surface in order to reduce the amount of surface reflection of light and improve the black color development.
• Patent Document 1 proposes a polyester composition in which the distance between particles is 0.2 to 0.7 ⁇ m and particles of 50 to 200 ⁇ m are present on the surface.
• Patent Document 2 proposes a polyester fiber containing 0.4 to 5% by weight of silica particles having an average primary particle size of 0.02 to 0.1 ⁇ m.
• Patent Document 3 describes a polyester composition containing 10 ppm to 75 ppm of a phosphorus compound, 1 to 20 ppm of a titanium compound, and 0.5 to 3.0% of silica particles having an average secondary particle size of 20 to 100 nm. Proposed.
• the fibers or compositions according to these documents are indefinite bodies in which particles are agglomerated, the silk-reeling property such as an increase in filter pressure during spinning cannot cope with the recent sophistication of fibers (fineness). There was a problem that the color development property, particularly the black color development property, was low.
• the present invention provides a polyester composition having excellent yarn-forming property and black color-developing property, and a polyester fiber having excellent black color-developing property.
• the problem of the present invention is solved by any of the following (1) to (3).
• (1) Contains 0.5 to 3.0% by weight of silica particles having an average primary particle size of 0.15 to 0.30 ⁇ m and a relative standard deviation of particle size of 0.40 or less, and polyester methoxy.
• Polyester fiber. (3) The polyester fiber according to (2) above, wherein the coefficient of friction of the running yarn is 0.35 or less for the yarn-pear-skin texture and 0.7 or less for the yarn-mirror surface.
• polyester composition of the present invention has both good yarn-making property and black color-developing property, it is possible to provide an optimum fiber especially for black formal use.
• the polyester composition of the present invention contains 0.5 to 3.0% by weight of silica particles having an average primary particle size of 0.15 to 0.30 ⁇ m and a relative standard deviation of particle size of 0.40 or less. Moreover, the methoxy group of the polyester is 10 ppm or less.
• the polyester composition of the present invention is a polyester whose main component is an aromatic dicarboxylic acid and a diol.
• aromatic dicarboxylic acid used in the present invention 95 mol% or more is preferably an aromatic dicarboxylic acid, and more preferably terephthalic acid is used.
• dicarboxylic acids may be contained as a copolymerization component within a range that does not impair the effects of the present invention.
• isophthalic acid isophthalic acid-5-sulfonate, naphthalene 2,6-dicarboxylic acid, bisphenoldicarboxylic acid, adipic acid, amber acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9- Known dicarboxylic acids such as nonandicarboxylic acid and 1,12-dodecanedicarboxylic acid can be mentioned.
• the diol used in the present invention it is preferable that 80 mol% or more is a linear alkylene glycol.
• the linear alkylene glycol include ethylene glycol, 1,3-propanediol, and 1,4-butanediol. These may be used alone or in combination of two or more.
• diols can be used in combination as a copolymerization component within a range that does not impair the effect of the present invention.
• diols include diethylene glycol, hexanediol, cyclohexanedimethanol, diethylene glycol bisphenol A ethylene oxide adduct, and polyethylene glycol.
• the polyester composition of the present invention may contain a matting agent such as titanium dioxide, fine particles such as aggregated alumina, an antioxidant such as a hindered phenol inducer, and other coloring pigments.
• a matting agent such as titanium dioxide, fine particles such as aggregated alumina, an antioxidant such as a hindered phenol inducer, and other coloring pigments.
• the polyester composition of the present invention contains silica particles as described above.
• the silica particles in the present invention are particles mainly composed of silicon oxide.
• the silica particles contained in the polyester composition of the present invention have an average primary particle size of 0.15 to 0.30 ⁇ m.
• the average primary particle size is larger than 0.30 ⁇ m, the surface of the fiber obtained from the polyester composition is not sufficiently roughened, and the color development property may be poor.
• the average primary particle size is less than 0.15 ⁇ m, the silica particles tend to aggregate, which may result in poor silk-reeling property.
• both color development and silk reeling property can be achieved, and when the average primary particle size is 0.15 to 0.20 ⁇ m, color development property and silk reeling property are better, which is preferable.
• the silica particles contained in the polyester composition of the present invention have the above-mentioned average primary particle size and the relative standard deviation of the particle size is 0.40 or less.
• the relative standard deviation is preferably 0.35 or less, more preferably 0.30 or less.
• the average primary particle size and relative standard deviation of the silica particles are determined by subjecting the surface of the polyester composition to a depth of 0.3 ⁇ m with a plasma reactor to expose the particles, and then using a scanning electron microscope to obtain 5000 particles. It can be obtained by processing more than one image with an image analyzer.
• the polyester composition of the present invention contains 0.5 to 3.0% by weight of silica particles. If the content of the silica particles is less than 0.5% by weight, the surface of the fiber obtained from the polyester composition may be insufficiently roughened and the color development property may be poor. If the content of the silica particles exceeds 3.0% by weight, the silica particles tend to aggregate, which may result in poor silk-reeling properties. When the content of the silica particles is in the above range, both color-developing property and silk-reeling property can be achieved, and when the content is 1.0 to 2.0% by weight, the color-developing property and silk-reeling property are more preferable.
• the method for producing silica particles used in the present invention is not particularly limited, but the wet method is preferably applied.
• Silica particles can be obtained by a hydrolysis method using, for example, sodium silicate or alkoxysilane as a starting material. From the viewpoint of dispersibility of silica particles and suppression of production of coarse particles, silica particles obtained using sodium silicate as a starting material are preferable.
• the polyester composition of the present invention can be produced by a conventionally known method, for example, by a direct polymerization method.
• the polyester composition of the present invention contains a polymer.
• the amount of methoxy groups in the polyester composition of the present invention is 10 ppm or less.
• the amount of methoxy groups in the polyester composition is 10 ppm or less, the color development property becomes good.
• the reason why the color development is good when the methoxy group of the polyester composition is 10 ppm or less is unknown, but when the number of methoxy groups is small, the amount of diethylene glycol (DEG) and the carboxyl terminal group (COOH terminal group) tends to increase. , It is presumed that the dye can be seated.
• DEG diethylene glycol
• COOH terminal group carboxyl terminal group
• the polyester composition As a method for producing polyester fibers from the polyester composition of the present invention, if necessary, the polyester composition is pre-dried in hot air or under reduced pressure, and is used in a spinning machine to be spun from a mouthpiece. At this time, in order to prevent deterioration of the polyester composition due to heat, the shorter the residence time of the polyester composition in the spinning machine is, the more preferable, and it is usually good to be within 20 minutes.
• the spinning temperature may be 250 to 300 ° C.
• the spun yarn is cooled and solidified by cold air, then oiled, and then picked up by a take-up roll that controls the spinning speed.
• the undrawn yarn taken up by the take-up roll is usually continuously drawn, but it may be taken up once and then drawn in another step.
• the spinning speed may be about 300 to 3000 m / min, preferably 500 to 2500 m / min.
• the obtained yarn is false-twisted while applying heat as necessary, and after obtaining a polyester processed yarn, a knitted fabric can be produced by using the processed yarn with a circular knitting machine.
• the number of silica particles on the fiber surface in which the distance between the centers of the adjacent silica particles is less than twice the average primary particle size is 4 or less per 10 ⁇ m 2. ..
• the distance between the centers of the fiber surface and the adjacent silica particles is less than twice the average primary particle size and the number of silica particles is 4 or less per 10 ⁇ m 2 , the spinning operability and black color development are good. Become.
• the silica particles are diluted with diol, which is a constituent of polyester, to 5% by weight or less to form a slurry. Then, between the end of the esterification reaction and the start of the polycondensation reaction, after adding the diol component so that the mol ratio of the aromatic dicarboxylic acid to the diol of the polyester composition after the addition of the silica particles is 2.2 or more, Add the slurry of silica particles.
• the polyester fiber of the present invention contains 0.5 to 3.0% by weight of silica particles having an average primary particle size of 0.15 to 0.30 ⁇ m and a relative standard deviation of particle size of 0.40 or less. Contains in the range.
• the average primary particle size is preferably 0.15 to 0.20 ⁇ m.
• the polyester fiber of the present invention preferably has a coefficient of friction of the running yarn of 0.35 or less for the yarn-pear-skin texture and 0.7 or less for the yarn-mirror surface because the guide wear when forming the yarn path is small.
• the fiber made of the polyester composition of the present invention can be subjected to a weight loss treatment by a known method.
• the weight loss treatment method include plasma treatment, laser treatment, and alkali weight loss treatment, but the alkali weight loss treatment is preferable from the viewpoint of the texture of the obtained fiber and dyeability.
• polyester fibers after removing the oil agent, the surface of the fibers was subjected to plasma low temperature ashing treatment in the same manner as in the polyester composition to expose the particles, and the fibers were treated with a scanning microscope and an image analyzer in the same manner as in the polyester composition.
• Silica particle content (% by weight) in the polyester composition 6 g of the polyester composition was melted and formed into a plate shape, the intensity was measured by fluorescent X-ray analysis using a fluorescent X-ray analyzer (PRIMUS II: manufactured by Rigaku Co., Ltd.), and a sample having a known content was prepared in advance. The metal content was defined as the silica particle content using a calibration curve. In the case of the polyester fiber, after removing the oil agent, the measurement was carried out by fluorescent X-ray analysis in the same manner as in the polyester composition.
• Friction coefficient The friction coefficient of the running yarn was measured by ⁇ METER manufactured by INTEC Inc. and calculated from the tension.
• Example 1 A slurry (calculated molar ratio 1.15) consisting of 300 parts by weight of terephthalic acid and 129 parts by weight of ethylene glycol was applied to an esterification reaction vessel equipped with a rectification column while maintaining the reaction vessel temperature at 240 to 245 ° C. over 3 hours. The reaction was carried out while continuously supplying water and distilling water from the upper stage of the distillation tower. The amount of water distilled off was 64 parts by weight, and the calculated esterification reaction rate of terephthalic acid was 98%. Of the obtained reactants, 43% (volume) was transferred to a polymerization reaction vessel while being filtered through a 10 micron filter.
• a silica particle consisting of 7.5 parts by weight of silica particles having a relative standard deviation of 0.30 and 142 parts by weight of ethylene glycol (concentration of silica particles of 5% by weight) is divided into three equal parts (volume) three times.
• the addition when the temperature in the system became 225 ° C. or lower, the addition was interrupted, and the process was kept on standby until the temperature in the system exceeded 225 ° C. After each addition, the mixture was waited until the temperature in the system reached 245 ° C. or higher (the mol ratio of aromatic dicarboxylic acid to diol was 3.0).
• the polymerization reaction tank was heated to 290 ° C. over 90 minutes and simultaneously depressurized to 60 Pa over 60 minutes, and the intrinsic viscosity of the polyester composition obtained in advance from the stirring load power was 0.66.
• the polycondensation reaction was carried out until This polyester composition was dried at 160 ° C. for 7 hours, spun at a spinning temperature of 290 ° C. and a spinning speed of 1500 m / min, and then stretched at a draw ratio of 2.81.
• the obtained polyester fiber has a methoxy group content of 5 ppm, a silica particle content of 1.5% by weight, an average primary particle size of 0.17 ⁇ m, and a relative standard deviation of the particle size of 0.30, between the centers of the silica particles.
• the number of particles whose distance was less than twice the average primary particle size was 0 per 10 ⁇ m 2.
• the spinning operability, the coefficient of friction of the yarn, and the black color development of the fiber were extremely good.
• Example 2 Polyester fibers were obtained in the same manner as in Example 1 except that the average primary particle size of the silica particles was 0.15 ⁇ m. The spinning operability, the coefficient of friction of the yarn, and the black color development were extremely good.
• Example 3 Polyester fibers were obtained in the same manner as in Example 1 except that the average primary particle size of the silica particles was 0.20 ⁇ m. The spinning operability, the coefficient of friction of the yarn, and the black color development were extremely good.
• Example 4 Polyester fibers were obtained in the same manner as in Example 1 except that the average primary particle size of the silica particles was 0.30 ⁇ m. The spinning operability and the coefficient of friction of the yarn were extremely good. The black color development was at a usable level.
• Example 5 Polyester fibers were obtained in the same manner as in Example 1 except that the relative standard deviation of the particle size of the silica particles was 0.40. The spinning operability, the coefficient of friction of the yarn, and the black color development were extremely good.
• Example 6 Polyester fibers were obtained in the same manner as in Example 1 except that the content of silica particles in the polyester fibers was 1.0% by weight. The spinning operability, the coefficient of friction of the yarn, and the black color development were extremely good.
• Example 7 Polyester fibers were obtained in the same manner as in Example 1 except that the content of silica particles in the polyester fibers was 2.0% by weight. The spinning operability, the coefficient of friction of the yarn, and the black color development were extremely good.
• Example 8 Polyester fibers were obtained in the same manner as in Example 1 except that the content of silica particles in the polyester fibers was 0.5% by weight. The spinning operability and black color development were extremely good. The yarn-mirror friction coefficient was at a usable level.
• Example 9 Polyester fibers were obtained in the same manner as in Example 1 except that the content of silica particles in the polyester fibers was set to 3.0% by weight. The black color development was extremely good. Spinning operability and yarn-mirror surface friction coefficient were at usable levels.
• Example 10 After the transesterification reaction of dimethyl terephthalate and ethylene glycol, the same silica particles as in Example 1 were added, and the polycondensation reaction was carried out in the same manner as in Example 1 to produce a polyester composition (B) (methoxy group amount: 20 ppm). did.
• a polyester fiber having a methoxy group content of 10 ppm was added to the polyester composition (60 parts by weight) produced in Example 1 by adding 30 parts by weight of the polyester composition (B), spinning and stretching in the same manner as in Example 1.
• Example 11 Polyester fibers were obtained in the same manner as in Example 1 except that the mol ratio of ethylene glycol and terephthalic acid at the time of adding silica particles was 2.2. The number of particles in which the distance between the centers of the silica particles in the obtained polyester fiber was less than twice the average primary particle size was 4 per 10 ⁇ m 2. Moreover, the spinning operability was excellent. The coefficient of friction between the thread and the satin finish and the black color development were at usable levels.
• Polyester fibers were obtained in the same manner as in Example 1 except that the average primary particle size of the silica particles was 0.12 ⁇ m. Many agglomeration of silica particles in the obtained polyester fiber was confirmed, and the dispersibility was poor and the spinning operability was poor.
• Polyester fibers were obtained in the same manner as in Example 1 except that the average primary particle size of the silica particles was 0.33 ⁇ m. The obtained polyester fiber was inferior in black color development.
• Polyester fibers were obtained in the same manner as in Example 1 except that the silica particles had a relative standard deviation of 0.44 particle size. The spinning operability and black color development of the obtained polyester fiber were poor.
• Polyester fibers were obtained in the same manner as in Example 1 except that the content of silica particles in the polyester fibers was set to 0.3% by weight. The obtained polyester fiber had poor black color development.
• Polyester fibers were obtained in the same manner as in Example 1 except that the content of silica particles in the polyester fibers was 3.3% by weight. The obtained polyester fiber had poor spinning operability.
• Example 7 Except that the concentration of the silica particles to be added was 7% by weight and 66 parts by weight of the diol was distilled off before the addition of the silica particles (the mol ratio of the aromatic dicarboxylic acid to the diol after the addition of the silica particles was 2.0).
• a polyester fiber was obtained in the same manner as in Example 1. The number of particles in which the distance between the centers of the silica particles on the surface of the obtained polyester fiber is less than twice the average primary particle size is 10 particles per 10 ⁇ m 2 , and both the spinning operability and the black color development property are poor. It was.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Artificial Filaments (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=74683813

Family Applications (1)

Country Status (4)

Citations (7)

Family Cites Families (4)

• 2020
  • 2020-08-26 JP JP2020545387A patent/JP7600685B2/ja active Active
  • 2020-08-26 WO PCT/JP2020/032203 patent/WO2021039848A1/ja not_active Ceased
  • 2020-08-26 CN CN202080060242.3A patent/CN114341264B/zh active Active
  • 2020-08-28 TW TW109129423A patent/TWI853078B/zh active

Patent Citations (7)

Also Published As

Similar Documents

Legal Events