KR20000066633A - Manufacturing of Nonflammable Polyester Fiber - Google Patents

Abstract

PURPOSE: A process for preparing a retardant polyester fiber by introducing specified phosphorous compounds and manganese salts in the process of polycondensation is provided which produces polyester fibers having excellent spinning workability, flame retardancy and UV stability. CONSTITUTION: In the process of manufacturing polyester fibers from at least one dicarboxylic acid or its ester forming derivatives, at least one glycol or its ester forming derivatives, a compound of formula (II) as a flame retardant, manganese salts and phosphorous compound of formula (III) as an UV stabilizer are polycondensed. In formula, R4 and R5 are H or the same or different radical having C2-4 ω-hydroxy, m is an integer of C1-5, R6 is H or C1-3 alkyl.

Description

Manufacturing Method of Flame Retardant Polyester Fiber {Manufacturing of Nonflammable Polyester Fiber}

The present invention relates to a method for preparing a polyester having excellent flame retardancy, and more particularly, by copolymerizing a novel reactive flame retardant to a polyester composed of glycol and polycarboxylic acid, excellent flame retardancy without lowering the inherent physical properties of polyester. It relates to a method for producing a polyester fiber having excellent stability against ultraviolet (UV).

In general, polyester, especially polyethylene terephthalate (hereinafter, PET) has excellent mechanical properties, good chemical resistance such as chemical resistance, and is widely used in fibers, films, and engineering plastics. However, such a conventional polyester has a disadvantage that it is easy to burn, and in the case of various molded articles including fibers, flame retardancy is urgently required in view of fire prevention.

In general, a method of manufacturing a flame retardant polyester fiber includes a method of treating a flame retardant on the surface of the first fiber, a method of spinning by adding a flame retardant material at the time of spinning, and a method of adding and copolymerizing a flame retardant material at the time of polymerization. The first method is advantageous in terms of manufacturing cost, but there is a problem in durability, the second method has a problem that the radioactivity is lowered and the physical properties of the yarn is also lowered. The third method is advantageous in terms of durability of flame retardancy, and has an advantage of being similar to a general polyester manufacturing process. A bromine (Br) flame retardant and a phosphorus (P) flame retardant are mainly used.

Inventions using bromine-based flame retardants include Japanese Patent Laid-Open No. 62-6912, Japanese Patent Laid-Open No. 53-46398, Japanese Patent Laid-Open No. 51-28894, and bromine compounds are susceptible to thermal decomposition at high temperatures. In order to obtain a large amount of flame retardant must be added as a result, there is a problem that the color of the polymer is degraded, light resistance is lowered, toxic gases are generated during combustion.

In addition, inventions using phosphorus-based flame retardants include U.S. Pat.Nos. 3,941,752, 5,399,428, 5,180,793, and Japanese Patent Application Laid-Open No. 50-56488. Since it is bonded to a chain, or back bone), there is a problem in that physical properties are deteriorated due to hydrolysis during the post-processing of polyester fibers, in particular during dyeing.

In Japanese Patent Laid-Open No. 52-47891, a flame retardant polyester was prepared by adding a phosphorus flame retardant represented by the following formula (I) at any stage of an ester exchange reaction and a polycondensation reaction. However, this method delays the polycondensation reaction time, deteriorates the color of the polymer and decreases the viscosity, which causes problems such as trimming during spinning. In addition, the present invention has a disadvantage in that the cost increases when compared to the polymerization method of terephthalic acid (hereinafter referred to as TPA) when dimethyl terephthalate (hereinafter referred to as DMT) is used as a raw material for PET polymerization.

next

Wherein R ¹ and R ² are the same or different groups and are each selected from a halogen atom, a hydrocarbon group of 1 to 10 carbon atoms, and a monovalent ester forming functional group, R ³ is a monovalent ester forming functional group, and A is a divalent or 3 Is an organic residue, and l and m are each an integer of 0 to 4, and n is 1 or 2.)

The present invention solves the problems caused by using a bromine or phosphorus flame retardant as described above, while producing a flame-retardant polyester by the TPA method, focusing on the fact that the manganese phosphate is effective in improving the UV stability specific phosphorus and manganese By introducing hepatitis during the polycondensation reaction, a technical problem is provided to provide a method for producing flame retardant polyester fiber having excellent spinning workability, flame retardancy and UV stability.

Hereinafter, the present invention will be described in detail.

The dicarboxylic acid or ester forming derivative thereof used to prepare the flame retardant polyester of the present invention includes terephthalic acid, isophthalic acid, biphenyl dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dica Aromatic dicarboxylic acids, such as a carboxylic acid, these ester formation derivatives, alicyclic dicarboxylic acids, such as 1, 4- cyclohexane dicarboxylic acid, alkanedicarboxylic acid of C2-C6, etc. can be used. .

Among these, in order not to significantly reduce the economics and the properties of the flame retardant polyester, it is preferable to make the mole ratio of terephthalic acid to the total dicarboxylic acid of 70% or more. If it is less than 70 mol%, the melting point or glass transition temperature is lowered, causing moldability problems, or when using some expensive copolymer monomer, the manufacturing cost is too high. As the glycol component, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane Alkanediols, such as diols, Alicyclic diols, such as 1, 4- cyclohexanediol and 1, 4- cyclohexane dimethanol, Aromatic diols, such as bisphenol A and bisphenol S, Ethylene oxide or propylene oxide addition product of aromatic diol, etc. to be. In order to express proper physical properties of the polymer, it is preferable that the molar ratio of ethylene glycol in the total polymer glycol component is 70% or more. If lower than this, a molding problem occurs.

The content of the polymer represented by the following general formula (II) used as a flame retardant is preferably 500 to 50,000 ppm, more preferably 1,000 to 20,000 ppm, based on the phosphorus atom. If the content of phosphorus atom is less than 500ppm, the desired flame retardant effect cannot be expected, and if it exceeds 50,000ppm, there is also a problem that it is difficult to increase the degree of polymerization of the produced polyester, and the crystallinity is so low that it is difficult to produce a fiber or film. Problems arise and are undesirable.

next

(In formula, R <^4> and R <^5> is the same or another radical group which has a hydrogen atom or the C2-C4 ω-hydroxy group, and m is an integer of 1-5.)

In addition, the content of manganese salt used as a UV stabilizer is preferably in the range of 0.1 to 500ppm and more preferably in the range of 0.2 to 200ppm based on the manganese atoms in the polymer. If it is smaller than 0.1 ppm, it is difficult to obtain the desired UV stability, and if it exceeds 500 ppm, problems of dispersibility occur, which causes problems such as an increase in pack pressure during spinning. In addition, the content of the phosphorus-based material represented by the following general formula (III) is in the range of 0.1 to 500ppm content of the number of people in the polymer. More preferably, the range of 0.2-200 ppm is good. The content of the phosphorus-based material may be added as long as the reaction with manganese salt is not a problem, but if it exceeds 500 ppm, the activity of the catalyst is lowered, making it difficult to prepare a desired flame retardant polyester.

next

(R ⁶ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

The flame retardant represented by the general formula (II) is added at any position of the esterification reaction or the polycondensation reaction, but when the terminal is a carboxylic acid, it is preferable to add the flame retardant at the beginning of the esterification reaction. In addition, the manganese salt and the material represented by the formula (III) can be added at any stage, but is preferably added during the polycondensation reaction.

In the following examples, the intrinsic viscosity of the flame retardant polyester was dissolved in a 6: 4 weight ratio solution of phenol and 1,1,2,2, -tetrachloroethane and measured at 20 ° C., and the melting point and the glass transition temperature were measured by differential scanning. Obtained by an analytical system (Differential Scanning Calorimetry, Perkin Elmer DSC 7). Phosphorus content in the polymer was analyzed using a wet method and the color was measured using an automatic colorimetric colorimeter. In addition, the UV stability was evaluated as the ultimate viscosity retention rate by measuring the intrinsic viscosity after the polymer was formed into a film by hot press (Hot press) and irradiated with UV lamp for 20 hours. In addition, flame retardant is flammable after spinning, made into knitted fabric, and after refining, weight loss, and dyeing, the value of limit oxygen index (Lol, KS M 3032, B-1) and the flame retardant evaluation method for medical fibers are evaluated by 45 ° gradient method (KS K O580). Evaluated.

Example 1

8000 parts of terephthalic acid, 3342 parts of ethylene glycol, 4 parts of antimony trioxide as a catalyst and a substance represented by the general formula (II), p is 1, and R ⁴ and R ⁵ are both hydrogen, 9, 10-dihydro. -9-oxa-10-(2,3-dicarboxypropyl)-10-phosphapenatrene-10-oxide (9, 10-dihydro-9-oxa-10-(2,3-dicarboxypropyl)-1O- 642 parts of phosphaphenathrene-1O-oxide) (hereinafter referred to as flame retardant A) was added and subjected to esterification as in the normal PET esterification reaction, and after the effluent of theoretical amount was released (97% of esterification reaction), manganese salt 11ppm acetate based on manganese atoms, 15ppm phosphoric acid based on the number of people, 40 parts titanium dioxide as a quencher, and polycondensation in the same manner as the conventional PET polycondensation method. A polymer of dl / g was obtained.

The obtained polymer was dried, spun and fired to prepare a twisted yarn of 75 denier / 24 filaments, which was then knitted into an interlock structure to be subjected to post-processing.

Example 2

Except for adding trimethyl phosphate as a phosphorus-based material represented by the general formula (III) was carried out in the same manner as in Example 1 and the results are shown in Table 1.

Example 3

After adding 8650 parts of terephthalic acid, 3700 parts of ethylene glycol, and 4 parts of antimony trioxide as a catalyst, it was esterified as in the normal PET esterification reaction and after the effluent of theoretical amount was discharged (97% of esterification reaction), The substance represented by (II) includes 9, 10-dihydroxy-9-oxa-10- (2,3-di- (hydroxy) in which p is 1 and R ⁴ and R ⁵ are 2-hydroxy ethylene groups. Ethoxy) carbonylpropyl) -10-phosphaphenanthrene-10-oxide) (9,10-dihydroxy-9-oxa-10- (2,3-di- (hydroxyethoxy) carbonylpropyl) -10-phosphaphenanthrene-10 -1380 parts of oxide (hereafter referred to as flame retardant B) (65 wt% EG solution for actual products), 11 ppm of manganese acetate as the manganese atom as the manganese salt, and phosphoric acid as a phosphorous substance represented by general formula (III) 15ppm as standard, 40 parts of titanium dioxide as a quencher is added to the normal PET Finally obtaining a polymer of intrinsic viscosity 0.643di / g were combined condensation polymerization like.

The obtained polymer was dried, spun and fired to prepare a twisted yarn of 75 denier / 24 filaments, which was then knitted into an interlock structure to be subjected to post-processing. The results are shown in Table 1 below.

Example 4

Except for adding trimethyl phosphate as a phosphorus-based material represented by the general formula (III) was carried out in the same manner as in Example 1 and the results are shown in Table 1.

Comparative Example 1

After adding 8680 parts of terephthalic acid, 3400 parts of ethylene glycol, and 4 parts of antimony trioxide as a catalyst, it was esterified as in the normal PET esterification reaction, and after the effluent of theoretical amount flowed out (97% of esterification reaction), 40 parts of titanium dioxide was added and polycondensed in the same manner as in the conventional PET polycondensation to finally obtain a polymer having an ultimate viscosity of 0.640 di / g.

The obtained polymer was dried, spun and fired to prepare a twisted yarn of 75 denier / 24 filaments, which was then knitted into an interlock structure to be subjected to post-processing. The results are shown in Table 1 below.

Comparative Example 2

Except for the addition of manganese salt and phosphoric acid was carried out in the same manner as in Example 3 and the results are shown in Table 1.

<Table 1>

* LOl: limit oxygen index

Ultimate viscosity after UV irradiation

* UV Stability =--------------100

Extreme viscosity before UV irradiation

Since the present invention does not increase the pack pressure during spinning, the spinning workability is good, and the produced flame retardant polyester yarn is excellent in color and flame retardancy, and also excellent in UV resistance.

Claims (3)

In preparing polyester fibers from at least one or more dicarboxylic acids or ester forming derivatives thereof and at least one or more glycol blacks thereof, the compound of formula (II) is used as a flame retardant as a UV stabilizer. A method of producing a flame retardant polyester fiber, characterized in that polycondensation by adding a manganese salt and a phosphorus compound of the general formula (III). next (In formula (II), R ⁴ and R ⁵ are the same or different radicals having a hydrogen atom or a ω-hydroxy group having 2 to 4 carbon atoms, and m is an integer having 1 to 5 carbon atoms.) next (In formula (III), R ⁶ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) The method for producing a flame retardant polyester fiber according to claim 1, wherein the content of phosphorus in the polyester polymer is 500 to 50,000 ppm. The content of manganese salt is 0.1 to 500 ppm based on the manganese atoms in the polymer, and the content of phosphorus compound represented by the general formula (III) is such that the content of the phosphorus to the polymer is 0.1 to 500 ppm. Method for producing a flame retardant polyester fiber to the.