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
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
  • C08G63/183—Terephthalic acids
• • 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
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
• • 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
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

• the present invention relates to a polyester composition having excellent long-term continuous spinnability and excellent polymer dischargeability during repeated polymerization.
• Polyethylene fibers and polypropylene fibers which are one type of polyolefin fibers, have a light weight and chemical resistance, but have a drawback that they are difficult to dye because they have no polar functional groups. Therefore, it is not suitable for clothing use, and at present it is limited to interior uses such as tile carpets, household rugs, car mats, and other material uses such as ropes, curing nets, filter cloths, narrow tapes, braids, and upholstery. Used in certain applications.
• Patent Document 1 discloses a polyester obtained by copolymerizing cyclohexanedimethanol
• Patent Document 2 discloses a dyeable amorphous polymer obtained by blending a polyester obtained by copolymerizing isophthalic acid and cyclohexanedimethanol with polyolefin as a dyeable amorphous polymer.
• Polyolefin fibers have been proposed.
• Patent Document 3 proposes a dyeable polyolefin fiber using a copolymerized polyester obtained by copolymerizing cyclohexanedicarboxylic acid as a dyeable polymer. This document describes that by controlling the dispersion diameter of the copolymerized polyester blended with the polyolefin to a specific range, a dyeable polyolefin fiber exhibiting higher color developability can be obtained.
• Patent Document 3 Although the method described in Patent Document 3 is excellent in that the coloring property is improved, the pack pressure increases when spinning is continuously performed for a long time, and it is necessary to change the pack during the spinning. Therefore, there was a problem that productivity was insufficient.
• An object of the present invention is to provide a polyester composition to be blended with a polyolefin, which can solve the above-mentioned problems of the prior art and can obtain a dyeable polyolefin composition having excellent coloring properties and excellent long-term continuous spinnability. Is to do.
• the polyester composition when the polyester composition is repeatedly polycondensed two or more times using the same polycondensation apparatus, the oxidatively degraded polyester composition adhering to the vicinity of the discharge port of the polycondensation apparatus is mixed into the discharged polyester composition, This causes an increase in pack pressure during long-term continuous spinning.
• a copolymerized polyester obtained by copolymerizing ethylene glycol with a dicarboxylic acid component containing terephthalic acid and / or an ester-forming derivative thereof, cyclohexanedicarboxylic acid and / or an ester-forming derivative thereof, and the following (I) A polyester composition characterized by satisfying the following.
• the polyester composition contains 1 to 35 mmol / kg of a phenol residue.
• the polyolefin composition blended with the polyester composition of the present invention can provide a dyeable polyolefin fiber with high productivity while suppressing an increase in pack pressure during long-term spinning.
• the polyester composition of the present invention is a polyester composition containing terephthalic acid and / or an ester-forming derivative thereof, cyclohexanedicarboxylic acid and / or an ester-forming derivative thereof, and ethylene glycol as main raw materials.
• examples of terephthalic acid and / or its ester-forming derivative include terephthalic acid, dimethyl terephthalate and diethyl terephthalate, and any one of these may be used alone, or two or more thereof may be used. You may use together.
• examples of the cyclohexanedicarboxylic acid include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives of cyclohexanedicarboxylic acid such as 1,2 cyclohexanedicarboxylic acid.
• 1,4-cyclohexanedicarboxylic acid can be suitably employed from the viewpoint of heat resistance and mechanical properties.
• the polyester composition of the present invention contains a phenol residue in an amount of 1 mmol / kg or more and 35 mmol / kg or less.
• the polyester composition contains 1 mmol / kg or more of phenol residues
• an oxidized product of the polyester composition is generated near the discharge port of the polycondensation apparatus. This makes it possible to suppress the increase in pack pressure during long-term continuous spinning of the dyeable polyolefin fiber and the occurrence of thick discharge at the time of polycondensation discharge of the polyester composition.
• the phenol residue is more preferably at least 3 mmol / kg, particularly preferably at least 5 mmol / kg. Further, by setting the phenol residue to 35 mmol / kg or less, it is possible to suppress gelation generated when an excessive amount of a phenolic antioxidant is added. It is possible to suppress the rise in pressure and the occurrence of thick discharge at the time of discharging polycondensation of the polyester composition.
• the phenol residue content is more preferably 30 mmol / kg or less, particularly preferably 25 mmol / kg or less. The measurement of the phenol residue will be described in Examples described later.
• the majority of the phenol residues contained in the polyester composition of the present invention are derived from phenolic antioxidants added during the polycondensation reaction of the polyester composition.
• the amount of phenol residues excluding those derived from phenolic antioxidants is extremely small.
• the phenolic antioxidant in the present invention is a radical chain reaction inhibitor having a phenol structure, and may be used alone or in combination of two or more.
• pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenol) propionate) (for example, Irganox 1010 manufactured by BASF), 2,4,6-tris (3 ′, 5′-) Di-t-butyl-4'-hydroxybenzyl) mesitylene (for example, Adekastab AO-330 manufactured by ADEKA), 3,9-bis [1,1-dimethyl-2- [ ⁇ - (3-t-butyl-4- Hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5,5] -undecane (eg, Sumitomo Chemical Sumilizer GA-80, ADEKA Adekastab AO-80
• Cyanox 1790 has a high oxidative decomposition inhibiting effect, it can be suitably employed.
• pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenol) propionate) eg, Irganox 1010 manufactured by BASF
• 3,9-bis [1,1-dimethyl-2- [ ⁇ - (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5,5] -undecane for example, Sumiremo Chemical Sumilizer GA-80 and ADK STAB AO-80 manufactured by ADEKA are less likely to be scattered even at the polycondensation temperature of the polyester composition and can be used particularly preferably.
• the polyester composition of the present invention can suppress an increase in pack pressure during long-term continuous spinning of dyeable polyolefin fibers by setting the filtration pressure difference ⁇ P to 2.0 MPa or less.
• ⁇ P is more preferably 1.8 MPa or less, and particularly preferably 1.6 MPa or less.
• the filtration pressure difference ⁇ P is such that a polyester composition dried to a water content of less than 500 ppm is passed through a polyester composition temperature of 240 ° C., a discharge rate of 10 g / min, and a filter area of 24.5 ⁇ with a filter opening of 5 ⁇ m sintered fiber filter for 4 hours.
• the difference between the filtration pressure after 4 hours and the filtration pressure after 1 hour (the filtration pressure after 4 hours-1 the filtration pressure after 1 hour) when flowing.
• the polyester composition is prepared before the polycondensation reaction starts. Dispersion of the phenolic antioxidant in the polyester composition before the start of the discharge may be mentioned.
• a method of dispersing the phenolic antioxidant in the polyester composition before the start of the discharge a method of adding a phenolic antioxidant in an optional process shown in a method for producing a polyester composition described later is exemplified. Among them, it is preferable to add the phenolic antioxidant before the start of the polycondensation reaction of the low polymer of the polyester composition from the viewpoint of improving the dispersibility of the phenolic antioxidant and increasing the efficiency of the antioxidant ability.
• the polyester composition of the present invention preferably has a heat of fusion ( ⁇ Hm) of 0.1 J / g or more and 30 J / g or less.
• ⁇ Hm heat of fusion
• ⁇ Hm is more preferably 1 J / g or more, and particularly preferably 5 J / g or more.
• the refractive index of the polyester composition decreases and approaches the refractive index of the polyolefin, so that the color developability of the fiber using the dyeable polyolefin composition can be improved.
• the dye absorption rate is high, and the color developability is good. Therefore, it is more preferably 29 J / g or less, and particularly preferably 27 J / g or less.
• the ⁇ Hm of the polyester composition can be measured by the following method.
• the composition pellets are vacuum dried in a vacuum oven at 130 ° C. for 12 hours.
• Approximately 5 mg of the polymer after vacuum drying was weighed, and the temperature was raised from 0 ° C. to 280 ° C. at a rate of 16 ° C./min, using a differential scanning calorimeter (DSC) model Q2000 manufactured by TA Instruments. Perform the DSC measurement with a program that holds for 5 minutes.
• the heat of fusion ( ⁇ Hm) is calculated from the melting peak observed during the heating process. When a plurality of melting peaks are observed, the sum of continuous heats of fusion including the top of the highest melting peak is defined as ⁇ Hm.
• the method for adjusting the ⁇ Hm of the polyester composition of the present invention to the above range is not particularly limited.
• the blending amount of cyclohexanedicarboxylic acid is 35 parts by weight or more and 90 parts by weight with respect to 100 parts by weight of terephthalic acid as a raw material.
• the following adjustment methods are available.
• the polyester composition of the present invention preferably has an intrinsic viscosity (IV) of 0.60 or more and 0.70 or less.
• IV intrinsic viscosity
• the amount of the polyester composition deposited can be reduced.
• IV is more preferably 0.61 or more, and particularly preferably 0.62 or more.
• the IV is preferably 0.69 or less, particularly preferably 0.68 or less.
• the polyester composition of the present invention is usually produced by any one of the following processes (1) to (3). That is, (1) a process of using a terephthalic acid, cyclohexanedicarboxylic acid and ethylene glycol as raw materials to obtain a low polymer by a direct esterification reaction and further obtain a high molecular weight polyester composition by a subsequent polycondensation reaction.
• a low-polymer polyethylene terephthalate is obtained by a transesterification reaction.
• terephthalic acid, cyclohexanedicarboxylic acid, and ethylene glycol are added, a low polymer is obtained by an esterification reaction, and a high molecular weight polyester composition is obtained by a subsequent polycondensation reaction.
• the reaction temperature is preferably 250 ° C. or less and the pressure is preferably 1.2 ⁇ 100,000 Pa or more in order to suppress the by-product of diethylene glycol.
• the lower the reaction temperature is 290 ° C. and the lower the pressure, the shorter the polymerization time, which is preferable.
• the reaction temperature is preferably 230 ° C. or less, and the pressure is preferably atmospheric pressure or more.
• the pressure is preferably atmospheric pressure or more.
• the esterification reaction proceeds without a catalyst, but the transesterification reaction uses a compound such as magnesium, manganese, calcium, cobalt, lithium, or titanium as a catalyst. You may.
• a titanium compound, an aluminum compound, a tin compound, an antimony compound, a germanium compound and the like are used. These metal compounds may be hydrates.
• magnesium compound used in this case examples include magnesium oxide, magnesium hydroxide, magnesium alkoxide, magnesium acetate, magnesium carbonate and the like.
• manganese compound examples include manganese chloride, manganese bromide, manganese nitrate, manganese carbonate, manganese acetylacetonate, and manganese acetate.
• the calcium compound examples include calcium oxide, calcium hydroxide, calcium alkoxide, calcium acetate, calcium carbonate and the like.
• cobalt compound examples include cobalt chloride, cobalt nitrate, cobalt carbonate, cobalt acetylacetonate, cobalt naphthenate, and cobalt acetate.
• lithium compound examples include lithium oxide, lithium hydroxide, lithium alkoxide, lithium acetate, lithium carbonate and the like.
• titanium compound examples include titanium complexes, titanium alkoxides such as tetra-i-propyl titanate, tetra-n-butyl titanate and tetra-n-butyl titanate tetramer, titanium oxides obtained by hydrolysis of titanium alkoxides, titanium acetylacetonate And the like.
• a titanium complex using a polycarboxylic acid and / or a hydroxycarboxylic acid and / or a polyhydric alcohol as a chelating agent is preferable from the viewpoint of the thermal stability of the polymer, the color tone, and the amount of deposits around the base.
• the chelating agent for the titanium compound include lactic acid, citric acid, mannitol, and tripentaerythritol.
• Examples of the aluminum compound include aluminum carboxylate, aluminum alkoxide, aluminum chelate compound, and basic aluminum compound. Specific examples include aluminum acetate, aluminum hydroxide, aluminum carbonate, aluminum ethoxide, aluminum isopropoxide, and aluminum acetyl. Examples include acetonate and basic aluminum acetate.
• Tin compounds include monobutyltin oxide, tin acetate, tin octylate, tin alkoxide and the like.
• Antimony compounds include antimony alkoxide, antimony glycolate and antimony trioxide.
• germanium compound examples include germanium alkoxide and germanium oxide.
• the polyester composition of the present invention preferably contains a phosphorus compound as a stabilizer.
• a phosphorus compound as a stabilizer.
• phosphoric acid, trimethyl phosphate, ethyl diethylphosphonoacetate and the like are preferable, and 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10- 3 such as tetraoxa-3,9-diphosphaspiro [5,5] undecane (PEP-36: manufactured by Asahi Denka) or tris (2,4-di-tert-butylphenyl) phosphite (IRGAFOS168: manufactured by BASF) Phosphorus compounds are more preferred from the viewpoint of improving color tone and heat resistance.
• an antioxidant an ultraviolet absorber, a flame retardant, a fluorescent whitening agent, a matting agent, a plasticizer or an antifoaming agent or other additives may be added as required.
• the polyester composition of the present invention can be produced by batch polymerization or semi-continuous polymerization.
• the dyeable polyolefin composition obtained by blending the polyester composition of the present invention is a polymer alloy composition having a sea-island structure in which the polyolefin is a sea component and the polyester composition is an island component.
• the polyester composition of the present invention in a polyolefin as a dyeable polymer in an island, it is possible to impart color development to the polyolefin.
• the polymer capable of dyeing the island component is exposed on the surface in the polymer alloy composition.
• the above-mentioned polymer alloy composition means that the island component is present in a discontinuously dispersed state.
• the island component is discontinuous, for example, in the case of a fiber made of a polymer alloy composition, the island component has an appropriate length in the fiber axis direction, and a cross section perpendicular to the fiber axis, that is, the fiber The shape of the sea-island structure in the cross section is different.
• the island components are discontinuously dispersed, since the island components are spindle-shaped, the coloring efficiency by the light transmitted to the island components is improved, the sharpness is improved, and deep coloring is obtained.
• fibers made of the polymer alloy composition blended with the polyester composition of the present invention include core-sheath conjugate fibers in which one island is formed continuously and in the same shape in the fiber axis direction, and a plurality of islands are formed in the fiber axis direction. It is essentially different from sea-island composite fibers formed continuously and in the same shape.
• a polymer alloy composition can be obtained, for example, by melt-kneading a polyolefin, the polyester composition of the present invention and a compatibilizer.
• the raw materials used are as follows. 1.
• Dimethyl terephthalate manufactured by SK Chemical Company
• Terephthalic acid High-purity terephthalic acid manufactured by Mitsui Chemicals, Inc.
• 1,4-cyclohexanedicarboxylic acid manufactured by Shin Nippon Rika Co., Ltd.
• Ethylene glycol manufactured by Mitsubishi Chemical Corporation 5.
• IRGANOX1010 manufactured by BASF 6.
• ADK STAB PEP-8 manufactured by ADEKA Sumilizer TP-D: manufactured by Sumitomo Chemical Co., Ltd.
• the physical properties in the examples were measured by the methods described below.
• Phenol residue content 0.01 g of the polyester composition was decomposed at 4O 0 C with 4 mL of 10% methanolic hydrochloric acid. After cooling, 1 mL of methanolic hydrochloric acid was added, and the precipitate was filtered. The filtrate was measured by high performance liquid chromatography (LC-20A, manufactured by Shimadzu Corporation), and the content of phenol residues contained in the polyester compositions of the following Examples and Comparative Examples was calculated.
• LC-20A high performance liquid chromatography
• the standard solution for high performance liquid chromatography is IRGANOX1010, methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 3- (3,5-di-tert-butyl-4-hydroxy-4-hydroxyphenyl).
• (Phenyl) propionic acid was prepared by dissolving each in a chloroform / acetonitrile solvent to prepare a calibration curve.
• the measurement conditions are as follows. Column bath: 50 ° C Eluent: A. 0.1 vol% formic acid aqueous solution; Acetonitrile program: 0.0 minutes ⁇ 10.0 minutes B25% ⁇ 100% 10.0 minutes ⁇ 20 minutes B100% Flow rate: 0.8 mL / min Sample injection volume: 20 ⁇ l Detection wavelength: 260-280 nm.
• Intrinsic viscosity The obtained polyester composition was dissolved in an o-chlorophenol solvent to prepare solutions having concentrations of 0.5 g / dL, 0.2 g / dL, and 0.1 g / dL. Thereafter, the relative viscosity ( ⁇ r) at 25 ° C. of the obtained solution having the concentration C was measured by an Ubbelohde viscometer, and ( ⁇ r-1) / C was plotted against C. The intrinsic viscosity was determined by extrapolating the obtained results to a concentration of 0.
• IV intrinsic viscosity
• FIG. Filtration pressure difference ⁇ P The filtration pressure difference ⁇ P was measured using a Fuji Melt Spinning Tester (MST-C400) manufactured by Fuji Filter.
• MST-C400 Fuji Melt Spinning Tester
• the polyester composition dried to a water content of less than 500 ppm was flowed at a polyester composition temperature of 240 ° C. through a sintered fiber filter having a filter area of 24.5 ⁇ and a filter opening of 5 ⁇ m at a discharge rate of 10 g / min for 4 hours
• the difference between the filtration pressure after 4 hours and the filtration pressure after 1 hour was defined as the filtration pressure difference ⁇ P.
• FIG. Melt viscosity ratio
• the polyester composition dried to a water content of less than 500 ppm was measured in a nitrogen atmosphere at 290 ° C. using Capillograph 1B (manufactured by Toyo Seiki Seisaku-sho, Ltd.) according to JIS 7199: 1999.
• the capillary die used had an inner diameter of 1 mm and a length of 40 mm.
• L. Fiber color tone after dyeing (L * value) Using the fiber obtained in the example or the comparative example as a sample, about 2 g of tubular knitting was prepared using a circular knitting machine NCR-BL (3 inch and a half (8.9 cm), 27 gauge) manufactured by Eiko Sangyo. In an aqueous solution containing 1.5 g / L of sodium carbonate and 0.5 g / L of surfactant Granup US-20 manufactured by Meisei Chemical Co., Ltd., scoured at 80 ° C. for 20 minutes, washed with running water for 30 minutes, and dried with hot air at 60 ° C. Dried in the machine for 60 minutes. The scoured knitted fabric after scouring was dry-heat set at 135 ° C.
• the knitted tube was placed in an aqueous solution containing 2 g / L of sodium hydroxide, 2 g / L of sodium dithionite, and 0.5 g / L of surfactant Granup US-20 manufactured by Meisei Chemical Co., Ltd., at a bath ratio of 1: 100. After reducing and washing at 80 ° C. for 20 minutes, it was washed with running water for 30 minutes and dried in a 60 ° C. hot air drier for 60 minutes. The tubular knit after the reduction washing was dry-heat set at 135 ° C. for 1 minute, and a finishing set was performed.
• the L * value was measured using a spectrophotometer CM-3700d manufactured by Minolta, using a D65 light source, a viewing angle of 10 °, and optical conditions of SCE (specular reflection light removal method). The measurement was performed three times for one sample, and the average value was defined as L * value.
• Example 1 Transesterification reaction
• 100 kg of dimethyl terephthalate and 56 kg of ethylene glycol were melted at 150 ° C. under a nitrogen atmosphere, and the temperature was raised to 230 ° C. over 3 hours with stirring, Methanol was distilled off and transesterification was performed to obtain bis (hydroxyethyl) terephthalate.
• the reaction system After reaching a predetermined stirring torque, the reaction system was purged with nitrogen and returned to normal pressure to stop the polycondensation reaction, and retention before discharge was carried out for 30 minutes. After the retention before discharge, the liquid was discharged in a strand shape, cooled, and immediately cut. The time from the start of the pressure reduction to the arrival of the predetermined stirring torque was 2 hours and 00 minutes.
• the obtained pellets were vacuum-dried at 95 ° C. for 12 hours, then supplied to an extruder-type melt spinning machine to be melted, and then spun at a spinning temperature of 250 ° C. and a discharge rate of 31.5 g / min (a discharge hole diameter of 0.18 mm, (A discharge hole length of 0.23 mm, 36 holes, and a round hole) to obtain a spun yarn.
• the spun yarn is cooled by a cooling air having a wind temperature of 20 ° C. and a wind speed of 25 m / min, and an oil agent is applied and converged by a lubricating device and taken up by a first godet roller rotating at 3000 m / min.
• the obtained undrawn yarn is drawn under the conditions of a first hot roller temperature of 90 ° C., a second hot roller temperature of 130 ° C., a draw ratio of 2.1 times, and a draw speed of 500 m / min to obtain a dyeable polyolefin fiber of 50 dtex-36f. Obtained.
• Table 1 shows the fiber properties, fabric properties, and the amount of the composition deposited and deposited on the first and second hot rollers during stretching of the obtained dyeable polyolefin fiber.
• Examples 2 to 15 [Comparative Examples 1 to 4]
• Dyeable polyolefin fibers were obtained in the same manner as in Example 1, except that the raw materials and the intrinsic viscosity IV of the polyester composition were changed as shown in Tables 1 and 2.
• Tables 1 and 2 show the fiber properties, cloth properties, and the amount of the composition deposited and deposited on the first and second hot rollers during stretching of the obtained dyeable polyolefin fiber.
• the dyeable polyolefin composition containing the polyester composition of the present invention has excellent long-term continuous spinnability, and has a vivid and deep coloring property, and is preferably used as a fiber or a fiber structure. it can.

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• 2019
  • 2019-08-20 CN CN201980051978.1A patent/CN112543790B/zh active Active
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