염착성이 우수한 난연섬유용 난연성 폴리에스테르 수지, 이의 제조방법 및 이를 포함하는 심색성이 우수한 난연섬유

In the present invention " Represented in the formula,R₁ Is independently a hydrogen atom, methyl or ethyl and, a is 1 - 3 are disclosed " represented as when a process is provided for, when a is 3, a plurality of R¹ , I.e. R¹ And the dog 3 substituents, these plurality of R¹ Such as plating film is same or different, R¹ Each of the both hydrogen atoms, may be methyl or ethyl, or R¹ As each of the others, R¹ One of theHydrogen atom, the other anti-and the other one is ethyl meaning that the viscoelastic materials are disclosed. And, the content a substituent represented in interpreting as an example, other forms of similar substituted airway will be interpreted in the same way.

Less than a material used for the detailed of the SFC.

The flame retardant polyester resin phthalic and aliphatic diol followed oligomeric; compound formula 1; and compounds of formula 2; polymer polymerizing a mixture comprising a flame retardant polyester resin, dye, dye or the like as well as exhaustion with excellent, (and/or brilliant company) brilliant fiber working temperature deviation is lowered so as to face consisting of a recovery line are brilliant fiber are disclosed.

In the present invention, the phthalic acid is terephthalic acid and isophthalic acid (terephthalic acid) (isophthlic acid) can be at least one selected from 1 comprising, preferably terephthalic acid can be used.

And, in that the aliphatic diol of Korean aliphatic diol 2 - 20 carbon atoms, preferably ethylene glycol, percutaneous, propylene glycol, butylene glycol, trimethyl glycol, tetramethylene glycol, pen hit methyl glycol, hexamethylene glycol, [heyp[heyp] The other methyl [leyn[leyn] the recall which will grow, preparation of methylene glycol, it plays but the methyl [leyn[leyn] the glycol, car methyl [leyn[leyn] glycol, fortune car methyl [leyn[leyn] glycol, selected from at least one of boron and tri car methyl [leyn[leyn] glycolcar methyl [leyn[leyn] glycol 1 species or 2, more preferably ethylene glycol, percutaneous, propylene glycol and butylene glycol by weight of at least one species selected from 1 or 2 can be.

And, the oligomer comprises a phthalic acid and the aliphatic diol 1:1. 20 - 1. 50 molar ratio, preferably 1:1. 25 - 1. 40 molar ratio, more preferably 1:1. 25 - 1. 35 can be prepared by the reaction of esterification using molar ratio, the, an aliphatic diol molar ratio 1. 2 is below the resultant polyester resin can be, aliphatic diol 1. 5 molar ratio to exceed the cost due to the use of unreacted aliphatic diol and receiving higher pressures when operating in meeting the problem are disclosed.

In the present invention, it acts as a flame-retardant polyester resin compound formula 1 increase, relative to the weight of the entire mixture is used in an amount thereof before a polymerization reaction, so that the 5,000 - 7,000 ppm (P content of reference), preferably so that the 5,200 - 6,500 ppm (P content of reference), more preferably 5,500 - 6,300 ppm (P content of reference) input such that the antenna disclosed. The, injection quantity by the following formula 1 to 5,000 ppm (P content of reference) may not ensure sufficient flame retardancy is below and, allowing an excess of P exceeds 7,000 ppm (P content of reference) during polymerization and deterioration of the heat resistance and viscosity lowering the terminal reactive polymer chip can increase a count. In the final product due to freezing apparatus and method which can be object-knit and woven by plural pass through the step of which the range can be used now.

[Formula 1]

In formula 1, R¹ Is - OH, - COOH, - CH₂ COOH, - CH₂ CH₂ COOH, - CH₂ CH₂ CH₂ COOH or - CH₂ CH₂ CH₂ CH₂ COOH and, preferably the R¹ The - CH₂ COOH, - CH₂ CH₂ COOH, or - CH₂ CH₂ CH₂ COOH are disclosed.

In the present invention, compounds of formula 2 dyes in ion, in particular cation (cation) silica in dye exhaustion performance exerted ferric ion through bonds to serve as, the phthalic acid 1 mole is used in an amount and for non-3. 0 - 5. 0 molar ratio, preferably 3. 225 - 4. 515 molar ratio, more preferably 3. 5 - 4. 2 molar ratio used now. The, compounds of formula 2 formed at 3. 0 molar ratio is below sufficient exhaustion pyruvates which can be put over the apex, the amount of the 5. 0 exceeds a limiting oxygen index of polyester resin too many molar ratio and the amount of oxide layer is formed, the problem brilliant fiber lower mechanical properties thereof can.

[Formula 2]

In the formula 2, the R¹ And R² Are independently alkyl 1 - 10 carbon atoms, alkylene 2 - 5 carbon atoms, a cycloalkyl or phenyl group and of 5 - 6 carbon atoms, preferably R¹ And R² 1 - 5 carbon atoms are independently alkyl, alkylene or phenyl group and 2 - 3 carbon atoms, more preferably R¹ And R² 1 - 3 alkyl carbon atoms independently are disclosed.

And, the formula 2 compound is preferably represented by formula 2 - 1 can be compounds.

[Formula 2 - 1]

In the formula 2 - 1, the R¹ And R² 1 - 5 carbon atoms are independently alkyl, alkylene or phenyl group and 2 - 3 carbon atoms, preferably R¹ And R² Are independently 1 - 3 carbon atoms and alkyl, more preferably R¹ And R² Are independently alkyl 1 - 2 carbon atoms are disclosed.

Also, flame retardant polyester resin phthalic, an aliphatic diol, copolymer of formula 1 and formula 2 compound having a compound represented by formula 3 in addition to the metal catalyst, magnesium acetate (Mg acetate), germanium (Ge acetate) acetate, zinc acetate (Zn acetate) 1 a catalyst including at least one selected from, preferably further includes a metal catalyst can be a group represented by the formula 3. And, use of the metal catalyst, based on the total weight of the metal catalyst has a mixture that is used in an amount of 100 - 500 ppm, preferably 150 - 400 ppm so that the use of a good ancestry.

[Formula 3]

In the formula 3, R² Is hydrogen atom, alkyl of 1 - 5 carbon atoms, cycloalkyl of 5 - 6 carbon atoms, alkoxy group or phenyl group and 1 - 2 carbon atoms, preferably hydrogen atom, alkyl or cycloalkyl of 1 - 5 carbon atoms and 5 - 6 carbon atoms, more preferably 1 - 2 alkyl carbon atoms are disclosed.

Also, the flame retardant polyester resin thermal stabilizers, an antifoaming agent, antioxidant, lubricant, light stabilizer, hydrolysis stabilizers, mold release agent, pigment, antistatic agent, conductivity imparting agent, EMI shields, magnetic transportation to, mineral filler, cross-linking agent, antibacterial agent, processing aid, metal inert agent, hundred million subject of a speech, fluorine-based dropping agent, my rubbing system, my attrition system, and coupling and the like selected from 1 species or 2 can be followed by at least one further additive manufacturing.

In the present invention, can be a general use in the art using the ten stabilizersten stabilizers, preferably tree methyl gun [su[su] pay [thu[thu] (trimethylphosphate), tree [thil[thil] Gun [su[su] pay [thu[thu] (Triethyl phosphate), tree butyl gun [su[su] pay [thu[thu] (Tributyl phosphate), tributoxyethyl phosphate (Tributoxyethyl phosphate), tree [khu[khu] thread phosphate (Tricresyl phosphate), a triaryl phosphate ISO pro the [ley[ley] which will bloom mote [tu[tu] (Triaryl phosphate isopropylated), hydroquinone bis - (diphenyl phosphate) (Hydroquinone bis - (diphenyl phosphate)) by weight of at least one species selected from 1 or 2 can be.

Phthalic polyester resin of the present invention aliphatic diol described prior followed in producing oligomer; the oligomer, the formula 1 compound represented by formula 2 by mixing compounds and producing a mixture; said mixture and producing polymers by polymerization reaction; and by making including process can.

Also, removing unreacted monomer and oligomer, i.e. polymers can be further comprises a solid state polymerization process.

A manufacturing method of the present invention, the phthalic acid, an aliphatic diol, type of formula 1 and formula 2 compound compound, as a material for the aforementioned amount are the same as described.

And, when the polymerization represented by the chemical formula 3 metal catalyst, thermal stabilizers, an antifoaming agent, antioxidant, lubricant, light stabilizer, hydrolysis stabilizers, mold release agent, pigment, antistatic agent, conductivity imparting agent, EMI shields, magnetic transportation to, mineral filler, cross-linking agent, antibacterial agent, processing aid, metal inert agent, hundred million subject of a speech, fluorine-based dropping agent, my rubbing system, my attrition system, and at least one coupling agent selected from adding 1 is performed may be filled.

Also, oligomer of the esterification reaction comprises in producing 230 °C - 250 °C, water (dehydration) occurring during dehydrating reaction is performed while in now. The, 230 °C esterification reaction temperature is below output from reactants can be, exceeds the temperature in the range of 250 °C generates carrying out an esterification reaction product can be the antenna disclosed.

And, the step of manufacturing a 270 °C - 290 °C and 1 (polymerization) polymerization of the polymer. 5 torr or less is performed under a condition of, preferably 270 °C - 280 °C and 1. 5 torr or less under a condition of, more preferably 275 °C - 280 °C and 1. 5 torr can conditions below. The, reaction temperature is below 270 °C cylinder or oligomer polymerization stage in the surface unit molecular weight reaction participating rates in main process in which the reaction yield attaching vacuum steps, 290 °C exceeds the heat resistance or flame retardant polyester resin formed by a reactive flame retardant unique generating pinholes due to lack lowering and hydrocarbon is electrode layer can be in the temperature range within which the brown color of carrying out now.

The intrinsic viscosity (IV) is prepared by the process of the present invention polyester resin 0. 500 - 0. With 750 dl/g may be, intrinsic viscosity (IV) is preferably 0. 550 - 0. With 700 dl/g can be, like in the form of injection for the production of intrinsic viscosity in the range of which is coated brilliant fiber have WIPO.

Using flame retardant polyester resin of the present invention previously described below in such manner producing the brilliant fiber in mammals are also described, the brilliant fiber flame retardant polyester resin shape; the flame retardant polyester resin in drying the 110 °C - 130 °C 3 - 5 hours; and emitting the dried flame retardant polyester resin; producing process including brilliant fiber can be performed.

The flame retardant polyester resin excellent in said polyester described previous shape are the same.

And, in the existing drying in the drying 130 °C - 150 °C is eliminating, the invention relates to a polyester resin produced by using components having certain and composition ratio using bar, can lower the processing temperature, drying can be performed in 110 °C - 130 °C, preferably under small 110 °C - 120 °C can be performing.

Also, in step 270 °C - 300 °C of radiation is the radiation temperature and R5 represents 4,000 mpm - 5,000 mpm can be performing radiation, preferably radiation temperature 270 °C - 290 °C in performing radiation and R5 represents 4,000 mpm - 5,000 mpm disapproval. The, radiation temperature is below 270 °C polymer alignment (alignment) is risen by lacking a miss in shoessalt half (dyeing is normally amount) and there may be a, 300 °C heat decomposition company due to a high temperature exceeds the current generated by the conjugate fiber can be disclosed. And, there is a lack in shoes polymer alignment (alignment) is below 4,000 mpm radial velocity is a miss by salt half (dyeing is normally amount) is risen and there could, trimmed material can be generated by lowering productivity. 5,000 mpm as expected in the shoes variation of properties and reduced elongation exceeds by invitation generation and then pass through the step on an upper face of large volumes of process problem thereof can problem.

Also, in according to the invention, the radiation can be carried out using a general use in the art yarn, preferably to reduce reflected light for improving the sharpness and modified cross section using radiation brilliant fibercore chromatic characteristic yarn is performed now. The shaped yarn is triangular, star, such as yarn can be in the form of a hollow yarn using modified cross section.

The amplifier amplifies the flame-retardant polyester resin and produced by the manufacturing method of the present invention based on measured using CIE 1976 standard brilliant fibercolorimetryprofit rate APHA color (color yield), the melt viscosity of 0.1 K/S value (K/S Value) 10 - 16, preferably 13 - 16 can be characterized.

Also, 70 - 80 de brilliant fiber when yarns of the present invention, strength 3. 0 - 4. 0 g/de and, elongation at 20% - 40%, preferably 25% - 35% elongation excellent mechanical properties as unembossed thereof can.

Also, when measured on the basis of the present invention call brilliant fiber KS-a M ISO 4589 - 1, a limiting oxygen index (LOI) is 28% - 38%, preferably 33% - 38% is capable of having a disclosed.

Or less, which utilizes the present invention more specifically describe be incorporated less than 1000. However, limiting the scope of this invention to embodiments has the, this will be interpreted for aiding understanding of the present invention.

[Embodiments]

Embodiments 1: flame retardant polyester resin

1:1 diester phthalic acid and ethylene glycol. 3 molar ratio after mixing, 240 °C while removing water generated in carrying out an esterification reaction oligomers prepared.

Then an oligomer compound having a formula 1 - 1, the polymer represented by formula 2 - 1 compound having a metal catalyst is charged and stirring was by 3 steps. The, compounds of formula 1 when the P content 5,800 ppm based on the total weight of the mixture so that the reference input, the phthalic acid diester compound having a formula 2 - 1 1 4 mol. 0 molar ratio to his input. And, the metal catalyst has a mixture of 300 ppm based on the total weight that was input.

Then the mixture is 278 °C - 280 °C and 1. 5 torr or less polymers by polymerization reaction under a condition of producing flame retardant polyester resin with a reinforcing agent.

Of producing a flame-retardant polyester resin (IV) have an inherent viscosity of right hemp clothwith (Ubbelohde) viscometer measuring, for table 1 have shown to result.

[Formula 1 - 1]

In the formula 1 - 1, R¹ The - CH₂ CH₂ COOH are disclosed.

[Formula 2 - 1]

In the formula 2 - 1, the R¹ And R² Are all methyl group disclosed.

[Formula 3]

In the formula 3, R² Is methyl group disclosed.

Embodiments 2

The embodiments in the same flame retardant polyester resin and is 1, the compounds of formula 1 - 2 instead of compound formula 1 - 1 using flame retardant polyester resin with a reinforcing agent.

[Formula 1 - 2]

In the chemical formula 1 - 2, R¹ The - CH₂ CH₂ CH₂ COOH are disclosed.

Embodiments 3

The embodiments in the same flame retardant polyester resin and is 1, the compounds of formula 2 - 1 compound having a formula 2 - 2 instead of using flame retardant polyester resin with a reinforcing agent.

[Formula 2 - 2]

In the formula 2 - 2, the R¹ And R² Both ethyl is are disclosed.

Embodiments 4

The example 1 and the same flame retardant polyester resin is, 6,300 ppm based on the total weight of the mixture compound the formula 1 - 1 when the reference input so that the P content, phthalic acid diester compounds represented by the formula 2 - 1 1 mol 4. 51 to molar ratio is put in the flame retardant polyester resin with a reinforcing agent.

Embodiments 5

The example 1 and the same flame retardant polyester resin is, 6,300 ppm based on the total weight of the mixture compound the formula 1 - 1 when the reference input so that the P content, phthalic acid diester compounds represented by the formula 2 - 1 1 mol 3. 25 molar ratio to throwing a flame retardant polyester resin with a reinforcing agent.

Comparison example 1

The example 1 and the same flame retardant polyester resin is, based on the total weight of the formula 1 - 1 compound having a P content so that the mixture is put in the reference 8,000 ppm, flame retardant polyester resin with a reinforcing agent.

Comparison example 2

The example 1 and the same flame retardant polyester resin is, phthalic acid diester compounds represented by the formula 2 - 1 1 mol 6. 0 to molar ratio is put in the flame retardant polyester resin with a reinforcing agent.

Comparison example 3

The example 1 and the same flame retardant polyester resin is, phthalic acid diester compounds represented by the formula 2 - 1 2 1 mol. 3 molar ratio to throwing a flame retardant polyester resin with a reinforcing agent.

Manufacturing example 1: brilliant fiber manufacturing

The flame-retardant polyester resin made in embodiments 1 4 120 °C effective in time, through radiation (star) in island brilliant fiber 75de also manufactured in production with modified cross section.

And, the radiation 280 °C and 1. 2 - 1. 3 torr 104e in radial velocity of 4,500 mpm by dielectrophoresis.

Manufacturing example 2 - Manufacturing example 5 and Non attainments artists 1 - Non attainments artists 3

In the same example 1 and said brilliant fiber being separated, the embodiments 2 - 5 and comparison example 1 embodiments of flame retardant polyester resin instead of using the same conditions 1 - 3 each flame retardant polyester resin prepared by performing radiation in the brilliant fiber to, manufacturing example 2 - 5 and non-artists attainments each 1 - 3 implementation.

Non attainments artists 4

In the same example 1 and said brilliant fiber being separated, the embodiments of flame retardant polyester resin instead flame retardant polyester resin (except the chemical yarn ESFRON [ley[ley]) 1 using brilliant fiber prepared.

Experiment example 1: brilliant fiber measuring properties

(1) measuring flame retardant

Method UL 94 provided AVH chambers are utilized to KS M 3305, polyester fiber flame retardant were measured.

(2) strength, elongation measurement

Fiber steel, using measurements of automatic tension tester (Textechno yarn) elongation speed of 50 cm/m, 50 cm by applying gripping distance were measured. Strength and elongation when the formed fiber is cut until the lifting force constant deniers (g/de) dividing the load suffering from stretching a strength, elongation percentage (%) indicating a value in an extended length to the first length was defined.

(3) limiting oxygen index measuring

Limiting oxygen index (LOI) determined the KS-a M ISO 4589 - 1 based on the call.

(4) cup salt time(S)

Fire measuring method based on cup salt time (KS K 0585:2008) were measured. Wherein, when evaluating the degree 5 seconds (fire) is exposed to fire cup salt time garden behind as the time elapsed after the removal material presses when going out, bio garden, if 3 seconds pass are disclosed.

(5) color obtained rate measurement (ColorYield)

CIE 1976 method based on profit rate APHA color were measured.

The results of experiments of example 1 - 5 example 2 the table manufacturing solution heat brilliant fiber strength, and elongation as well as limiting oxygen index is high, flame retardant were confirmed. Also, 10 - 16 K/S profit rate APHA color value having bar, excellent core chromatic characteristic can be confirmed, the unselected bit line is very good when compared to the attainments 4, using the same to exhaustion of flame retardant polyester resin of the present invention having excellent excellent brilliant fibercore chromatic characteristic S. and imidazole-based.

And, compounds represented by formula 1 in the case of very good system for non beyond the 7,000 ppm attainments 1, as compared to manufacturing example 1, lower strength yarn of the control unit.

Also, the molar ratio of the compound represented by formula 2 2 5 in the case of at least system for non artists attainments, manufacturing as compared to example 1, the problem limiting oxygen index and strength rather lower. And, the molar ratio of the compound represented by formula 2 3 3 in the case of less than system for non artists attainments, the APHA color profit rate K/S value 13, as compared to manufacturing example 1 result which might be made, through, that a comparison example 3 polyester resin is employed for the waste exhaustion have, as a result using the same result brilliant fibercore chromatic characteristic falls has been prepared.

The embodiments and experiments incorporated as well as the flame-retardant polyester resin excellent exhaustion, even amount of 10 low processing temperatures, made using the same brilliant fiber flame retardant, core chromatic characteristic mechanical properties were to 1:1 by weight. This, such as through a curtain may be expect higher flame retardant product are disclosed.