WO2004060961A1 - ポリブチレンテレフタレート及びその製造方法ならびにその組成物およびフィルム - Google Patents

ポリブチレンテレフタレート及びその製造方法ならびにその組成物およびフィルム Download PDF

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WO2004060961A1
WO2004060961A1 PCT/JP2003/016471 JP0316471W WO2004060961A1 WO 2004060961 A1 WO2004060961 A1 WO 2004060961A1 JP 0316471 W JP0316471 W JP 0316471W WO 2004060961 A1 WO2004060961 A1 WO 2004060961A1
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WIPO (PCT)
Prior art keywords
weight
parts
polybutylene terephthalate
butanediol
pbt
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PCT/JP2003/016471
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English (en)
French (fr)
Japanese (ja)
Inventor
Masanori Yamamoto
Takahiro Uesaka
Hideyuki Fujino
Masahiro Adachi
Toshiyuki Tajiri
Hidekazu Shouji
Katsuhiko Sugiura
Shintarou Kishimoto
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Mitsubishi Chemical Corporation
Mitsubishi Engineering-Plastics Corporation
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Priority claimed from JP2003160711A external-priority patent/JP2004307794A/ja
Priority claimed from JP2003173487A external-priority patent/JP2005008736A/ja
Application filed by Mitsubishi Chemical Corporation, Mitsubishi Engineering-Plastics Corporation filed Critical Mitsubishi Chemical Corporation
Priority to AU2003289485A priority Critical patent/AU2003289485A1/en
Publication of WO2004060961A1 publication Critical patent/WO2004060961A1/ja

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    • 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • 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 polybutylene terephthalate, a method for producing the same, and a composition thereof.
  • the present invention relates to a color tone, hydrolysis resistance, and heat Yasuda
  • Polybutylene terephthalate excellent in qualitative properties, transparency, moldability and reduced in foreign matter, which can be suitably used for films, monofilaments, fibers, electric and electronic parts, automobile parts, etc. It relates to compositions and films. Background art
  • thermoplastic polyester resins Typical edges among thermoplastic polyester resins:
  • Certain polybutylene terephthalates have excellent moldability, mechanical properties, heat resistance, chemical resistance, fragrance retention, and other excellent physical and chemical properties. Widely used for injection molding products such as precision instrument parts. In recent years, it has been widely used in the fields of films, sheets, monofilaments, and fibers, taking advantage of its excellent properties.
  • polybutylene terephthalate also has a higher terminal lipoxyl group concentration, the higher the rate of hydrolysis reaction under moist heat, the lower the molecular weight due to hydrolysis, and consequently the mechanical properties. A major problem is that it causes a decrease.
  • the reaction for the continuous esterification of terephthalic acid and 1,4-butanediol is divided into two stages.In the first stage of the esterification reaction, only the organotin compound is added, and in the second stage of the esterification reaction.
  • a method has been proposed in which an organic titanium compound is added to reduce foreign substances and haze derived from the catalyst (for example, Japanese Patent Application Laid-Open No. 10-330468).
  • FIG. 1 is a diagram illustrating an example of an esterification reaction step or a transesterification reaction step employed in the present invention.
  • FIG. 2 is an explanatory diagram of another example of the esterification reaction step or transesterification reaction step employed in the present invention.
  • FIG. 3 is an explanatory diagram of another example of the esterification reaction step or transesterification reaction step employed in the present invention.
  • FIG. 4 is an explanatory diagram of another example of the esterification reaction step or transesterification reaction step employed in the present invention.
  • FIG. 5 is an explanatory diagram of another example of the esterification reaction step or transesterification reaction step employed in the present invention.
  • FIG. 6 is an explanatory diagram of an example of the polycondensation step employed in the present invention.
  • FIG. 7 is an explanatory diagram of another example of the polycondensation step employed in the present invention.
  • FIG. 8 is an explanatory diagram of another example of the polycondensation step employed in the present invention.
  • FIG. 9 is an explanatory diagram of another example of the polycondensation step employed in the present invention. Disclosure of the invention
  • the present invention has been made in view of the above circumstances, and has as its object to improve the color tone, hydrolysis resistance, heat stability, transparency, and moldability, and furthermore, to reduce the amount of foreign matter, to obtain a film or monofilament.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, if the esterification or transesterification reaction is performed under specific conditions, the use amount of the catalyst is increased because the efficiency of use of the catalyst is improved. It has been found that a novel polybutylene terephthalate can be obtained which can be remarkably reduced, and as a result, the content of the catalyst is remarkably low, thereby easily solving the above-mentioned problems. Also, esterification or esterification under certain conditions It has been found that by performing a steal exchange reaction, the conversion rate can be increased, foreign substances can be reduced, and side reactions can be suppressed.
  • the present invention has been completed based on the above findings, and the first gist of the present invention is to provide a polybutylene terephthalate characterized by containing titanium and having an amount of 33 ppm or less as a titanium atom. Be on the rate.
  • a second gist of the present invention is a polybutylene terephthalate having a step of performing an esterification reaction by continuously supplying terephthalic acid and 1,4-butanediol in the presence of a titanium catalyst in an esterification reaction tank.
  • the method for producing 1,4-butanediol at least a part of 1,4-butanediol is supplied to an esterification reactor independently of terephthalic acid, and 1,4-butanediol is supplied to an esterification reactor independently of terephthalic acid. 10% by weight or more of the titanium catalyst is supplied to the liquid phase of the reaction liquid, and 10% by weight or more of the titanium catalyst is supplied to the liquid phase of the reaction liquid independently of terephthalic acid. It is in the manufacturing method.
  • a third gist of the present invention is a polybutylene having a step of performing a transesterification reaction by continuously supplying a dialkyl terephthalate and 1,4-butanediol in a transesterification reaction tank in the presence of a titanium catalyst.
  • a portion of 1,4-butanediol is supplied to a transesterification reactor independently of dialkyl terephthalate, and supplied to a transesterification reactor independently of dialkyl terephthalate.
  • a polybutanediol wherein at least 10% by weight of monobutanediol is supplied to the reaction liquid phase, and at least 10% by weight of the titanium catalyst is supplied to the reaction liquid phase independently of terephthalic acid. It lies in the method of manufacturing butylene terephthalate.
  • the fourth gist of the present invention is a process of continuously performing an esterification reaction of terephthalic acid and an excess of 1,4-butanediol with respect to terephthalic acid in the presence of a titanium catalyst in an esterification reaction tank.
  • the method for producing polybutylene terephthalate having the following formula the molar ratio of terephthalic acid and 1,4-butanediol supplied to the esterification reactor per unit time (moles of 1,4-butanediol / terephthalic acid) (Molar number of acid) is controlled to be constant.
  • the fifth gist of the present invention is that, in a transesterification reaction tank, dialkyl terephthalate and an excess of 1,4-butanediol relative to dialkyl terephthalate are continuously esterified in the presence of a titanium catalyst.
  • the molar ratio of dialkyl terephthalate and 1,4-butanediol supplied to a transesterification reactor per unit time (1,4-butanediol (Moles / moles of terephthalic acid) is controlled to be constant.
  • the sixth gist of the present invention is that the polybutylene terephthalate according to the first gist, a phenolic antioxidant (B 1), a zeolite antioxidant (B 2), and a phosphorus antioxidant (B 3) And a heat-resistant polybutylene terephthalate composition comprising at least one antioxidant selected from the group consisting of:
  • a seventh aspect of the present invention is based on 100 parts by weight of the polybutylene terephthalate according to the first aspect, wherein a fatty acid residue having 12 to 36 carbon atoms and an alcohol residue having 1 to 36 carbon atoms are used.
  • a releasing agent selected from the group consisting of a fatty acid ester (C 1) and a paraffin wax and a polyethylene wax (C 2) (C) in an amount of 0.01 to 2 parts by weight. It is present in the butylene terephthalate composition.
  • the polybutylene terephthalate according to the first aspect in which the reinforcing filler (D) is contained in an amount of 0 to 200 parts by weight and the epoxy compound (E) is added in an amount of 100 to 100 parts by weight. 20 parts by weight of a hydrolysis-resistant polybutylene terephthalate composition.
  • the polybutylene terephthalate according to the first aspect has a weight ratio of 100 to 100 parts by weight, and the impact modifier (F) has a content of 0.5 to 40 parts by weight and a reinforcing filler (D). 0 to 200 parts by weight of an impact-resistant polybutylene terephthalate composition.
  • a brominated aromatic compound-based flame retardant (G) is used in an amount of 3 to 50 parts by weight, based on 100 parts by weight of the polybutylene terephthalate according to the first aspect.
  • a flame retardant polybutylene terephthalate composition comprising 1 to 30 parts by weight, an anti-dripping agent (I) 0 to 15 parts by weight and a reinforcing filler (D) 0 to 200 parts by weight. Exists.
  • the eleventh aspect of the present invention is based on a total of 100 parts by weight of 50 to 95 parts by weight of the polybutylene terephthalate according to the first aspect and 5 to 50 parts by weight of the polyphenylene ether resin (J).
  • Compatibilizer (K) 0.05 to 10 parts by weight, at least one compound selected from phosphate ester or phosphonitrile (L) 2 to 45 parts by weight, reinforcing filler (D) 0 to 200 parts by weight, an anti-dripping agent (I) 0 to 15 parts by weight, melamine cyanurate (M) 0 to 45 parts by weight and a metal borate (N) 0 to 50 parts by weight. It is a non-hazardous flame retardant polybutylene terephthalate composition.
  • the 12th gist of the present invention is that the polybutylene terephthalate according to the 1st gist is 100 parts by weight, the polycarbonate resin (O) is 5 to 100 parts by weight, and the organic phosphorus compound (P) is 0.01. 1 to 1 part by weight, a reinforcing filler (D) 0 to 200 parts by weight, and an impact modifier (F) 0 to 50 parts by weight in a polybutylene terephthalate composition.
  • a thirteenth aspect of the present invention resides in that 100 to 100 parts by weight of the polybutylene terephthalate according to the first aspect, 5 to 100 parts by weight of an aromatic polyester resin (Q) other than polybutylene terephthalate and reinforced filling Material (D)
  • the polybutylene terephthalate composition contains 0 to 200 parts by weight.
  • the polystyrene resin (R) is 5 to 100 parts by weight
  • the maleic anhydride-modified polystyrene resin (S) is 100 parts by weight of the polybutylene terephthalate according to the first aspect.
  • a polycarbonate resin (0) 0 to 40 parts by weight and a reinforcing filler (D) 0 to 200 parts by weight.
  • a fifteenth aspect of the present invention resides in a film comprising a polybutylene terephthalate containing titanium and having an amount of 33 ppm or less as a titanium atom.
  • the 16th gist of the present invention is that 1 to 99% by weight of polybutylene terephthalate and 1 to 99% by weight of polybutylene terephthalate containing titanium and having an amount of 33 ppm or less as a titanium atom (but not both). (Total amount of 100% by weight).
  • a seventeenth aspect of the present invention is to provide an aromatic polyester obtained by copolymerizing 1 to 99% by weight of polybutylene terephthalate containing titanium and having an amount of 33 ppm or less as a titanium atom and polytetramethylene glycol. 1 to 99% by weight (the total of both is 100% by weight).
  • the polybutylene terephthalate (hereinafter abbreviated as PBT) of the present invention has a structure in which terephthalic acid units and 1,4-butanediol units are ester-bonded, and 50 mol% or more of dicarboxylic acid units is terephthalic acid.
  • the proportion of terephthalic acid units in all dicarboxylic acid units is preferably at least 70 mol%, more preferably at least 80 mol%, particularly preferably at least 95 mol%, and
  • the proportion of 4-butanediol units is preferably at least 70 mol%, more preferably at least 80 mol%, particularly preferably at least 95 mol%. If the content of terephthalic acid units or 1,4-butanediol units is less than 50 mol%, the crystallization speed of PBT will decrease, leading to deterioration in moldability.
  • the dicarboxylic acid component other than terephthalic acid is not particularly limited.
  • phthalic acid isophthalic acid, 4,4 ′ diphenyldicarboxylic acid, 4, 4 ′ —Diphenyl ether dicarboxylic acid, 4, 4'-benzophenone dicarboxylic acid, 4, 4 'diphenoxyethane dicarboxylic acid, 4, 4' diphenyl sulfone dicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, etc.
  • Aromatic dicarboxylic acids 1,
  • Alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, and aliphatic dicarboxylic acids such as malonic acid, succinic acid, daltaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. I can do it.
  • These dicarboxylic acid components can be introduced into the polymer skeleton as a dicarboxylic acid or a dicarboxylic acid derivative such as dicarboxylic acid ester or dicarboxylic acid octalide as a raw material.
  • diol components other than 1,4-butanediol are not particularly limited, and include, for example, ethylene glycol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, Aliphatic diols such as polytetramethylene glycol, dibutylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,2-cyclohexanediol, Alicyclic diols such as 1,4-cyclohexanediol, 1,1-cyclohexane dimethylol, 1,4-cyclohexane dimethylol, xylylene glycol, 4,4'-dihydroxybiphenyl, 2,2- Bis (4-hydroxyphenyl) propane, bis (4-hydroxy And aromatic diols such as
  • hydroxycarboxylic acids such as lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-3-hydroxyethoxybenzoic acid, and alkoxycarboxylic acids
  • Monofunctional components such as acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butyl benzoic acid, benzoyl benzoic acid, etc., tricarboxylic acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid,
  • Trifunctional or higher polyfunctional components such as rimethylolethane, trimethylolpropane, glycerol, and pentaerythritol can be used as copolymer components. '
  • the PBT of the present invention is obtained by using a titanium catalyst as a catalyst in the esterification reaction (or transesterification reaction) between 1,4-butanediol and terephthalic acid (or dialkyl terephthalate).
  • titanium catalyst a titanium compound is usually used.
  • a titanium compound is usually used.
  • an inorganic titanium compound such as titanium oxide and titanium tetrachloride, a titanium alcohol such as tetramethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate; Titanium phenolate such as enil titanate and the like can be mentioned.
  • titanium phenolate such as enil titanate and the like can be mentioned.
  • tetraalkyl alkyl ether is preferred, and tetrabutyl titanate is more preferred.
  • tin may be used as a catalyst.
  • Tin is usually used as a tin compound, and specific examples thereof include dibutyltin oxide, methylphenyltin suloxide, tetraethyltin, hexethyl stannuloxide, cyclohexahexyldisuloxide, and the like.
  • magnesium compounds such as magnesium acetate, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium alkoxide, magnesium hydrogen phosphate, calcium acetate, calcium hydroxide, calcium carbonate, calcium oxide
  • antimony compounds such as antimony trioxide
  • germanium compounds such as germanium dioxide and germanium tetroxide
  • manganese compounds Using reaction compounds such as zinc compounds, zirconium compounds, cobalt compounds, orthophosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, phosphorus compounds such as esters and metal salts thereof, sodium hydroxide, sodium benzoate, etc. Is also good.
  • the above-mentioned catalyst and reaction aid may be added in portions, or may be added in the subsequent polycondensation reaction.
  • the PBT of the present invention is characterized by containing titanium and having an amount of 33 ppm or less as a titanium atom.
  • the above values are the weight ratio of atoms to PBT.
  • the lower limit of the above-mentioned titanium content is usually l ppm, preferably 3 ppm, more preferably 5 ppm, particularly preferably 8 ppm, and still more preferably 15 ppm.
  • the upper limit for the titanium content is preferably 30 ppm, more preferably 27 ppm. If the titanium content is more than 33 ppm, the color tone, hydrolysis resistance, transparency, moldability, etc. will deteriorate, and moreover, foreign matter tends to increase.If it is less than 1 ppm, the polymerizability will deteriorate. Sometimes.
  • a tin catalyst can be used together with a titanium catalyst.
  • tin catalysts have a lower catalytic activity than titanium catalysts, so it is necessary to increase the amount of tin catalyst compared to titanium catalysts.
  • too much tin catalyst can lead to color degradation and tin is toxic. Therefore, the amount of the tin catalyst used is usually 100 ppm or less, preferably 50 ppm or less, more preferably 20 ppm or less, and the most preferred embodiment is that no tin catalyst is used.
  • the content of titanium atoms, etc. can be determined using methods such as atomic emission, atomic absorption, and Induced Coupled Plasma (ICP) after recovering the metals in the polymer by wet ashing or other methods. Can be measured.
  • ICP Induced Coupled Plasma
  • the PBT of the present invention has an intrinsic viscosity of usually 0.60 to 2.00 dL / g, preferably 0.65 to 1.50 dLZg, and more preferably 0.75 to 1.30 dLZg. If the intrinsic viscosity is less than 0.60 dLZg, the mechanical strength of the molded product will be insufficient, and if it exceeds 2.00 dLZg, the melt viscosity will be high and the fluidity will deteriorate, and Shape properties tend to deteriorate.
  • the above intrinsic viscosity is a value measured at 30 ° C using a mixed solvent of phenolnotetrachloroethane (weight ratio 1/1).
  • the intrinsic viscosity of the plurality of PBTs to be used is preferably in the range of 0.60 to 2.00 dL / g, and the intrinsic viscosity of the composition is also in the above range.
  • the terminal lipoxyl group concentration of the PBT of the present invention is usually 0.1 to 35 / ie ciZg, preferably 1 to 25 ⁇ eqZg, more preferably 1 to 20 eqZg, and particularly preferably 1 to 15 eqZg. It is said. If the terminal carboxyl group concentration is too high, the hydrolysis resistance of PBT deteriorates.
  • the terminal lipoxyl group concentration be lower as the molecular weight becomes smaller and the molecular weight becomes lower and the molecular weight is more susceptible to the decrease in molecular weight due to hydrolysis. That is, it is recommended to satisfy the following equation (1-1). It is preferably Formula (1-2), more preferably (1-3), and particularly preferably Formula (1-4).
  • the concentration of lipoxyl group at the terminal end excluding the hydrolysis reaction is usually 1 to 30 eqZg, preferably l to 10 e. qL / g, more preferably 1 to 8 eq / g.
  • the concentration of lipoxyl group at the terminal end excluding the hydrolysis reaction is usually 1 to 30 eqZg, preferably l to 10 e. qL / g, more preferably 1 to 8 eq / g.
  • the lower the content of the catalytic substance, and the higher the molecular weight the smaller the increase in the terminal lipoxyl group concentration when heat is applied.
  • the temperature and time are specified because if the temperature is too low or the time is too short, the rate of increase in the terminal lipoxyl group concentration is too small, and if the temperature is too low or too short, the evaluation is too large. It is to be accurate. Another reason is that if the evaluation is performed at an extremely high temperature, side reactions other than the generation of a terminal lipoxyl group will occur at the same time, and the evaluation will be inaccurate. Under the heat treatment conditions, the decrease in the number average molecular weight due to a reaction other than the hydrolysis reaction caused by the water contained in the PBT can be ignored, and the increase in the terminal lipoxyl group concentration due to the hydrolysis reaction is the same as before and after the heat treatment.
  • AAV (d) is the amount of change in terminal lipoxyl group concentration due to the thermal decomposition reaction
  • ⁇ AV (t) is the total change in terminal lipoxyl group concentration before and after heat treatment
  • ⁇ (h) is the change in terminal lipoxyl group concentration due to hydrolysis reaction
  • ⁇ OH is the change in terminal hydroxyl group concentration before and after heat treatment.
  • the hydrolysis reaction is small, so that the water content of PBT used for the heat treatment is usually recommended to be 300 ppm or less.
  • the concentration of terminal hydroxyl groups before and after the heat treatment can be determined by NMR.
  • the terminal lipoxyl group concentration of PBT can be determined by dissolving PBT in an organic solvent and titrating it with an alkaline solution such as sodium hydroxide solution. Can be.
  • the terminal vinyl group concentration of the PBT of the present invention is usually 15 ⁇ eqZg or less, preferably 0.1 to 10 ⁇ eq_Zg, more preferably:! 88 zeq / g, particularly preferably 1-5 eci / g.
  • the terminal vinyl group concentration is too high, it causes deterioration of color tone and solid phase polymerization.
  • the vinyl group concentration tends to increase.
  • a methoxycarbonyl group derived from the raw material may remain, especially when dimethyl terephthalate is used as the raw material.
  • the methoxycarbonyl terminal generates methanol, formaldehyde, and formic acid by heat due to solid-state polymerization, kneading, molding, and the like, and these toxicity is a problem particularly when used for food.
  • Formic acid also damages metal forming equipment and vacuum equipment.
  • the concentration of the terminal methoxycarbonyl group in the present invention is generally 0.5 ⁇ e QZg or less, preferably 0.1 S / xe qZg or less, more preferably 0.2 ⁇ e Q / g or less, and particularly preferably 0.1 L or less. ⁇ e ciZg or less.
  • the cooling crystallization temperature of the PBT of the present invention is usually from 170 to 200, preferably from 172-195 ° C, and more preferably from 170 to 190 ° C.
  • the cooling crystallization temperature refers to a temperature lowering from a molten state of a resin using a differential scanning calorimeter. This is the temperature of the exothermic peak due to crystallization that appears when cooled at a rate of 20 ° C / min.
  • the cooling crystallization temperature corresponds to the crystallization speed. The higher the cooling crystallization temperature, the faster the crystallization speed, so that the cooling time during injection molding can be shortened and the productivity can be increased. If the crystallization temperature is low, crystallization takes a long time during injection molding, and the cooling time after injection molding must be extended, which tends to extend the molding cycle and reduce productivity.
  • the solution haze of the PBT of the present invention is not particularly limited, it is usually 10% or less as a solution haze when measuring 2.7 g of PBT dissolved in 20 mL of a phenol Z tetrachloroethane mixed solvent (3/2 by weight). It is preferably at most 5%, more preferably at most 3%, particularly preferably at most 1%. If the solution haze is high, the transparency tends to deteriorate and the amount of foreign substances tends to increase. Therefore, in applications where transparency is required, such as films, monofilaments and fibers, the commercial value is significantly reduced. Solution haze tends to increase with high catalyst content or high catalyst deactivation.
  • the foreign matter having a length of 5 zm or more contained in the PBT of the present invention is usually 60 particles / 10 g or less.
  • the number is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less.
  • Production methods of PBT are broadly classified into so-called direct polymerization methods using dicarboxylic acid as a main raw material and transesterification methods using dialkyl dialkyl sulfonate as a main raw material.
  • the former produces water during the initial esterification reaction, and the latter produces water during the initial transesterification reaction. There is a difference that alcohol is produced.
  • PBT production methods are broadly classified into a batch method and a continuous method based on the raw material supply or polymer delivery form.
  • the initial esterification reaction or transesterification reaction is performed in a continuous operation, and the subsequent polycondensation is performed in a batch operation, or conversely, the initial esterification reaction or transesterification reaction is performed in a batch operation and the subsequent polymerization is performed.
  • a direct polymerization method is preferred from the viewpoints of availability of raw materials, easy processing of distillate, height of raw material unit, and improvement effect of the present invention. Further, in the present invention, from the viewpoints of productivity and product quality stability and the improvement effect of the present invention, a method of continuously supplying raw materials and continuously performing an esterification reaction or a transesterification reaction is adopted. . In the present invention, a so-called continuous method in which a polycondensation reaction following an esterification reaction or a transesterification reaction is also continuously performed is preferable.
  • 1,4-butanediol is esterified independently of terephthalic acid (or dialkyl terephthalate) in an esterification reaction tank (or a transesterification reaction tank) in the presence of a titanium catalyst.
  • a step of continuously esterifying (or transesterifying) terephthalic acid (or dialkyl terephthalate) with 1,4-butanediol while supplying the mixture to the esterification reactor (or transesterification reactor) is preferably employed.
  • 1,4-butanediol supplied together with terephthalic acid or dialkyl terephthalate as a raw material slurry or solution is Separately, 1,4-butanediol is supplied to an esterification reactor or a transesterification reactor independently of terephthalic acid or dialkyl terephthalate.
  • 1,4-butanediol may be referred to as “separately supplied 1,4-butanediol”.
  • the “separately supplied 1,4-butanediol” composed of 1,4-butanediol collected by a condenser or the like may be referred to as “recycled 1,4-butanediol”. From the viewpoint of effective use of resources and simplicity of equipment, it is preferable to assign “recycled 1,4-butanediol” to “separate 1,4-butanediol”.
  • 1,4-butanediol distilled from an esterification reactor or a transesterification reactor contains components such as water, alcohol, tetrahydrofuran, and dihydrofuran in addition to the 1,4-butanediol component.
  • the 1,4-butanediol distilled out above should be separated and purified from components such as water, alcohol and tetrahydrofuran after being collected with a condenser or while collecting, and returned to the reaction tank. Is preferred.
  • the liquid phase of the reaction liquid refers to the liquid phase side of the gas-liquid interface in the esterification reaction tank or the transesterification reaction tank.
  • the proportion returned directly to the liquid phase of the reaction liquid is preferably at least 30% by weight, more preferably at least 50% by weight, particularly preferably at least 80% by weight, most preferably at least 90% by weight.
  • the temperature of the “separately supplied 1,4-butanediol” when returning to the reactor is usually 50 to 220 ° C., preferably 100 to 200 ° C. (: more preferably 150 to 200 ° C.). 0 to: L 90 ° C If the temperature of “separate feed 1,4-butanediol” is too high, the amount of tetrahydrofuran by-product tends to increase, and if it is too low, the heat load Increased Energy loss.
  • 10% by weight or more of the titanium catalyst used in the esterification reaction (or the transesterification reaction) is terephthalic acid ( Or dialkyl terephthalate) is preferably supplied directly to the liquid phase of the reaction liquid.
  • the liquid phase of the reaction liquid refers to the liquid phase side of the gas-liquid interface in the esterification reaction tank or the transesterification reaction tank, and the direct supply to the liquid phase of the reaction liquid means using a pipe or the like. This indicates that the catalyst is supplied directly to the liquid phase without passing through the gas phase of the reactor.
  • the proportion of the titanium catalyst added directly to the liquid phase of the reaction solution is preferably at least 30% by weight, more preferably at least 50% by weight, particularly preferably at least 80% by weight, most preferably at least 90% by weight. It is.
  • the above titanium catalyst can be supplied directly to the liquid phase of the reaction solution in the esterification reaction tank or transesterification reaction tank without dissolving or dissolving it in a solvent, etc.
  • a solvent such as 1,4-butanediol.
  • the concentration at this time is usually from 0.1 to 20% by weight, preferably from 0.05 to 10% by weight, more preferably from 0.08 to 8% by weight, as the concentration of the titanium catalyst with respect to the whole solution.
  • the water concentration in the solution is usually set to 0.5 to 1.0% by weight.
  • the temperature at the time of preparing the solution is usually 20 to 150 ° C, preferably 30 to 100 ° C, more preferably 40 to 80 ° C, from the viewpoint of preventing deactivation and aggregation. You. Also, the catalyst solution is preferably mixed with “separate supply 1,4-butanediol” via a pipe or the like and supplied to the esterification reaction tank or transesterification reaction tank from the viewpoints of deterioration prevention, precipitation prevention, and foreign matter control. .
  • An example of a continuous method employing a direct polymerization method is as follows. That is, the dicarboxylic acid component having terephthalic acid as a main component and the diol component having 1,4-butanediol as a main component are mixed in a raw material mixing tank to form a slurry, and a single or a plurality of esters are formed.
  • the esterification reaction is continuously performed usually for 5 to 10 hours, preferably 1 to 6 hours, and the obtained oligomer as an esterification reaction product is transferred to a polycondensation reaction tank,
  • a polycondensation reaction usually at a temperature of 210-280 ° C, preferably 220-265 ° C, usually no more than 27 kPa, preferably
  • the polycondensation reaction is carried out under a reduced pressure of 20 kPa or less, more preferably 13 kPa or less, and usually for 2 to 12 hours, preferably 3 to 10 hours under stirring.
  • the polymer obtained by the polycondensation reaction is usually transferred from the bottom of the polycondensation reaction tank to a polymer extraction die, extracted in a strand form, cut with a cutter with or after cooling with water, and pelletized. It is a granular material such as a chip.
  • the molar ratio between terephthalic acid and 1,4-butanediol preferably satisfies the following formula (III).
  • BM is the number of moles of 1,4-butanediol supplied from the outside to the esterification reactor per unit time
  • TM is the mole of terephthalic acid supplied from the outside to the esterification reactor per unit time.
  • An example of a continuous method employing the transesterification method is as follows. That is, in one or more transesterification reactors in the presence of a titanium catalyst, typically 110 ⁇ 260 ° C, preferably 140-245 ° C, more preferably 180-220 ° C, and usually 10-133 kPa, preferably 13-120 kPa, more preferably 60-101 kPa.
  • the ester exchange reaction is continuously performed under pressure, usually for 5 to 5 hours, preferably 1 to 3 hours, and the obtained transesterification reaction product is transferred to a polycondensation reaction tank as an oligomer.
  • a polycondensation reaction catalyst usually at a temperature of 210-280 ° C, preferably 220-265 ° C, usually no more than 27 kPa, preferably
  • the polycondensation reaction is carried out under a reduced pressure of 20 kPa or less, more preferably 13 kPa or less, and usually for 2 to 12 hours, preferably 3 to 10 hours under stirring.
  • the molar ratio of dialkyl terephthalate to 1,4-butanediol preferably satisfies the following formula (IV).
  • BM is the number of moles of 1,4-butanediol supplied externally to the transesterification reactor per unit time
  • DM is the dialkyl terephthalate supplied externally to the transesterification reactor per unit time. If the above BM / DM value is less than 1.1, the conversion and catalyst activity will decrease. If it exceeds 2.5, not only will the thermal efficiency decrease, but also By-products such as tetrahydrofuran tend to increase.
  • the value of BMZDM is preferably from 1.1 to; 1.8, more preferably from 1.2 to 1.5.
  • 1,4-butanediol supplied to the esterification (transesterification) reaction tank from the outside refers to 1,4-butanediol supplied together with terephthalic acid or dialkyl terephthalate as a raw material slurry or solution.
  • 1,4-butanediol which is supplied independently, and 1,4-butanediol used as a catalyst solvent, etc. It is.
  • the esterification reaction or transesterification reaction is preferably performed at a temperature equal to or higher than the boiling point of 1,4-butanediol to shorten the reaction time.
  • the boiling point of 1,4-butanediol depends on the pressure of the reaction, but it is 230 ° C at 110.lkPa (atmospheric pressure) and 205 ° C at 50 kPa.
  • the method of controlling the molar ratio of terephthalic acid or dialkyl terephthalate and 1,4-butanediol supplied to the reaction vessel per unit time to be constant is, for example, when terephthalic acid is used as a raw material.
  • the raw material slurry consisting of terephthalic acid and 1,4-butanediol is fixed at a certain molar ratio and supplied in a fixed amount. If the catalyst is composed of a 1,4-butanediol solution, its concentration And the supply amount is also constant, and at the same time, a certain amount of “separate supply 1,4-butanediol” is supplied to the esterification reaction tank.
  • the amount of 1,4-butanediol gas generated from the esterification reactor fluctuates greatly.
  • “separate 1,4-butanediol” is converted from “recycled 1,4-butanediol”
  • the 1,4-butanediol obtained by condensing it also fluctuates with a slight time delay from the above fluctuations in gas generation.
  • the supply amount of recirculated 1,4-butanediol supplied to the esterification reaction tank is controlled to be constant without changing, and terephthalic acid supplied to the esterification reaction tank is controlled.
  • the molar ratio of the raw material terephthalic acid or dialkyl terephthalate to 1,4-butanediol excluding “separately supplied 1,4-butanediol” is constant, for example, terephthalic acid and 1,4-butanediol
  • the supply amount is changed, that is, when the production amount is changed, the esterification reaction tank or ester is changed according to the change.
  • esterification reaction tank or the transesterification reaction tank known ones can be used, and any type such as a vertical stirring complete mixing tank, a vertical thermal convection type mixing tank, and a tower-type continuous reaction tank may be used.
  • a single tank or a plurality of tanks in which the same or different tanks are arranged in series may be used.
  • a reaction tank having a stirring device is preferable.
  • a type that rotates at high speed such as a turbine stirrer type high-speed rotary stirrer, a disk mill type stirrer, and a rotor mill type stirrer, is also used. You can do it.
  • the form of stirring is not particularly limited, and in addition to the usual stirring method in which the reaction solution in the reaction tank is directly stirred from the upper, lower, and lateral portions of the reaction tank, a part of the reaction solution is piped into the reactor. It is also possible to adopt a method in which the reaction solution is circulated by taking it out of the reactor and stirring with a line mixer or the like.
  • stirring blades can be selected, and specific examples include propeller blades, screw blades, turbine blades, fan turbine blades, disk turbine blades, faudler blades, full zone blades, and max blended blades. .
  • reaction vessels usually, a plurality of reaction vessels are used, preferably 2 to 5 reaction vessels are used, and the molecular weight is sequentially increased.
  • an initial esterification or transesterification reaction is followed by a polycondensation reaction.
  • a single reaction vessel or a plurality of reaction vessels may be used, but preferably, a plurality of reaction vessels are used.
  • the form of the reaction tank may be any type such as a vertical stirring complete mixing tank, a vertical thermal convection type mixing tank, a tower type continuous reaction tank, and the like, or a combination thereof. Among them, a reaction tank having a stirring device is preferable.
  • stirring device in addition to a normal type including a power unit, a bearing, a shaft, and a stirring blade, a high-speed rotary stirrer with a turbine stay, an overnight type, and a disk mill-type stirrer A type that rotates at high speed such as a rotor mill type stirrer can also be used.
  • the form of stirring is not particularly limited, and in addition to the usual stirring method in which the reaction solution in the reaction tank is directly stirred from the upper, lower, and lateral portions of the reaction tank, a part of the reaction solution is piped into the reactor. It is also possible to adopt a method in which the reaction solution is circulated by taking it out of the reactor and stirring it with a line mixer or the like. In particular, it is recommended that at least one of the polycondensation reactors be a horizontal reactor with a horizontal axis of rotation and excellent surface renewal and self-cleaning properties.
  • the rotation directions of the shafts are preferably in different directions, and more preferably, the rotation direction is such that the upper part is stretched and the lower part is involved in the polymer.
  • At least one reaction tank in at least one reaction tank, usually 1.3 kPa or less, preferably 0.5 kPa or less, more preferably 0.5 kPa or less. Under high vacuum below 3 kPa, typically 225-255.
  • the temperature is preferably 230 to 250 ° C, more preferably 233 to 245 ° C.
  • Solid-state polycondensation solid-state polymerization
  • the foreign matter derived from the catalyst is significantly reduced, so that the foreign matter does not need to be removed.
  • the quality is further improved. Is obtained.
  • a filter having the same opening as that used in a conventional PBT manufacturing facility it is possible to extend the life until replacement. If the life until replacement is set to be the same, a filter with a smaller opening can be installed.
  • the filter If the filter is installed too upstream in the manufacturing process, it will not be possible to remove foreign substances generated on the downstream side, and if the viscosity on the downstream side is high, the pressure loss at the filter will increase and the flow rate will be maintained. In order to achieve this, it is necessary to increase the size of the filter, to increase the size of the filter, and to increase the size of the filter and other equipment such as piping. Becomes inevitable. Therefore, the installation position of the filter depends on the intrinsic viscosity of PBT or its precursor. Usually, a position of 0.1 to 1.2 dL / g, preferably 0.2 to 1.2 OdLZg, and more preferably 0.5 to 0.9 dLZg is selected.
  • the filter medium constituting the filter may be any of a metal wind, a laminated metal mesh, a metal nonwoven fabric, a porous metal plate, and the like. From the viewpoint of filtration accuracy, a laminated metal mesh or a metal nonwoven fabric is preferable. Preferably, the opening is fixed by sintering.
  • the shape of the filter may be any type such as a basket type, a disk type, a leaf disk type, a tube type, a flat cylindrical evening, and a pleated cylindrical type. In order to prevent the operation of the plant from being affected, it is preferable to install a plurality of filters and use them by switching, or to install an auto screen changer or the like.
  • the absolute filtration accuracy of the filter is not particularly limited, it is generally 0.5 to 200 am, preferably 1 to 100 m, more preferably 5 to 50 m, and particularly preferably 10 to 30 xm. If the absolute filtration accuracy is too high, the effect of reducing foreign substances in the product will be lost, and if it is too low, productivity will decrease and the frequency of filter replacement will increase.
  • FIG. 1 is an explanatory view of an example of the esterification reaction step or transesterification reaction step employed in the present invention
  • FIGS. 2 to 5 are diagrams of another example of the esterification reaction step or ester exchange reaction step employed in the present invention
  • FIG. 6 is an explanatory view of an example of the polycondensation step employed in the present invention
  • FIGS. 7 to 9 are explanatory views of another example of the polycondensation step employed in the present invention.
  • terephthalic acid as a raw material is usually mixed with 1,4-butanediol in a raw material mixing tank (not shown) and supplied to the reaction tank (A) in a slurry form from a raw material supply line (1).
  • terephthalic acid dialkyl ester it is usually supplied to the reaction tank (A) without being mixed with 1,4-butanediol.
  • the titanium catalyst is preferably made into a solution of 1,4-butanediol in a catalyst preparation tank (not shown), and then supplied to the catalyst supply line (3).
  • recirculation 1, (4) An embodiment is shown in which a catalyst supply line (3) is connected to a butanediol recirculation line (2), and both are mixed and then supplied to the liquid phase portion of the reaction tank (A).
  • the gas distilled from the reaction tank (A) passes through the distillation line (5) and is separated into high-boiling components and low-boiling components in the rectification column (C).
  • the main component of the high-boiling component is 1,4-butyldiol
  • the main component of the low-boiling component is water and tetrahydrofuran for the direct polymerization method, and alcohol, tetrahydrofuran, and water for the transesterification method. It is.
  • the high-boiling components separated in the rectification column (C) are extracted from the extraction line (6), pass through the pump (D), and partly circulate from the recirculation line (2) to the reaction tank (A). And a part is returned from the circulation line (7) to the rectification column (C). The surplus is extracted outside through the extraction line (8).
  • the light-boiling components separated in the rectification column (C) are extracted from the gas extraction line (9), condensed in the condenser (G), passed through the condensate line (10), and stored in the tank (F). Is temporarily stored.
  • Part of the light-boiling components collected in the tank (F) is returned to the rectification column (C) via the extraction line (11), the pump (E) and the circulation line (12), and the remainder is It is extracted outside through the extraction line (13).
  • the condenser (G) is connected to an exhaust device (not shown) via a vent line (14).
  • the oligomer generated in the reaction tank (A) is extracted via the extraction pump (B) and the extraction line (4).
  • the catalyst supply line (3) is connected to the recirculation line (2), but both may be independent. Further, the raw material supply line (1) may be connected to the liquid phase of the reaction tank (A).
  • the process shown in Fig. 2 is different from the process shown in Fig. 1 in that the rectification tower (C) is equipped with a repoiler (H), and the supply line (15 ) Is provided.
  • the installation of the repoiler (H) facilitates the operation control of the rectification tower (C).
  • the process shown in Fig. 3 differs from the process shown in Fig. 1 in that a bypass line (16) branched from the circulation line (7) is connected to the gas phase of the reaction tank (A). You. Therefore, in the case of the process shown in FIG. 3, a part of the recirculated 1,4-butanediol returns to the reaction solution via the gas phase of the reaction tank (A).
  • the process shown in FIG. 4 is different from the process shown in FIG. 1 in that a flow control valve (J) and a flow control valve (K) are provided in the recirculation line (2) and the extraction line (8), respectively. Further, to detect the liquid level of the rectification tower (C) and adjust the opening of the flow control valve (K) based on the detection signal to adjust the liquid level of the rectification tower (C) to a constant level. In that a control device (L) is provided. The liquid level at the bottom of the rectification column (C) is
  • the temperature fluctuates slightly due to fluctuations in the temperature in (A), fluctuations in the amount of distilled gas divided by the composition of the distillate gas, fluctuations in the supply of raw materials, and fluctuations in the temperature of the rectification tower (C), the process shown in Fig.
  • the amount extracted from the extraction line (8) is adjusted, and the amount of recirculation from the recirculation line (2) is maintained constant .
  • the process shown in FIG. 5 is different from the process shown in FIG. 2 in that the recirculation line (2) and the extraction line (8) are provided with a flow control valve (J) and a flow control valve (K), respectively.
  • Withdrawal line (6) and circulation line (7) for high boiling component tanks respectively
  • a supply line (15) is provided at a position downstream of the reboiler (H) of the circulation line (7).
  • a control device (L) that detects the liquid level of (N) and adjusts the opening of the flow control valve (K) based on the detection signal to maintain the liquid level of the high boiling component tank (N) constant. ) Is provided.
  • the process shown in FIG. 5 has the same improvement effect as the process shown in FIG.
  • the process shown in Fig. 5 clarifies that a signal based on the liquid level fluctuation of the high boiling component tank (N) can be used as an input signal to the controller (L).
  • the oligomer supplied from the extraction line (4) shown in FIGS. 1 to 5 is polycondensed under reduced pressure in the first polycondensation reaction tank (a) to form a prepolymer, It is supplied to the second polycondensation reaction tank (d) via the extraction gear pump (c) and the extraction line (L1).
  • the polycondensation usually proceeds further at a lower pressure than in the first polycondensation reaction tank (a) to form a polymer.
  • the resulting polymer Is extracted from the die head (g) through the extraction gear pump (e) and the extraction line (L3) in the form of a molten strand, cooled with water, etc. And cut into pellets.
  • the symbol (L2) is the vent line of the first polycondensation reaction tank (a), and the symbol (L4) is the vent line of the second polycondensation reaction tank (d).
  • the process shown in FIG. 7 is different from the process shown in FIG. 6 in that a filter (f) is provided in the flow path of the extraction line (L3).
  • the process shown in FIG. 8 is different from the process shown in FIG. 6 in that a third polycondensation reaction tank (k) is provided after the second polycondensation reaction tank (d).
  • the third polycondensation reaction tank (k) is a horizontal reaction tank composed of a plurality of stirring blade blocks and equipped with a biaxial self-cleaning type stirring blade.
  • the polymer introduced from the second polycondensation reaction tank (d) to the third polycondensation reaction tank (k) through the extraction line (L3) is further subjected to polycondensation here, and then the extraction gear pump (M) and the melted strand from the die head (g) through the extraction line (L5), cooled with water, etc., cut with a rotary cutter (h), and pelletized.
  • the symbol (L 6) is the vent line of the third polycondensation reaction tank (k).
  • the process shown in Fig. 9 differs from the process shown in Fig. 8 in that a filter is installed in the middle of the extraction line (L3) between the second polycondensation reaction tank (d) and the third polycondensation reaction tank (k).
  • the difference is that (f) is equipped.
  • the PBT of the present invention includes 2,6-di-tert-butyl-4-octylphenol, pentaerythristyl-tetrakis [3- (3 ', 5'_t-butyl-4'-hydroxyphenyl) propionate] and the like.
  • Phenolic compounds such as dilauryl-1,3,3'-thiodipropionate, pen-erythrityl-tetrakis (3-lauryl thiodipropionate), triphenyl phosphite, tris (nonylphenyl) phosphite, tris ( Antioxidants, such as phosphorus compounds such as 2,4-Gt-butylphenylphosphite, paraffin wax,
  • Polyethylene wax, montanic acid or montanic acid Long-chain fatty acids such as esters, esters thereof, and release agents such as silicone oil may be added.
  • the PBT of the present invention may contain a reinforcing filler.
  • the reinforcing filler is not particularly limited, but examples thereof include inorganic fibers such as glass fiber, carbon fiber, silica-alumina fiber, zirconia fiber, boron fiber, boron nitride fiber, potassium silicon nitride potassium fiber, and metal fiber. And organic fibers such as fibers, aromatic polyamide fibers and fluororesin fibers. These reinforcing fillers can be used in combination of two or more. Among the above reinforcing fillers, inorganic fillers, particularly glass fibers, are preferably used.
  • the average fiber diameter is not particularly limited, but is usually l to 100 im, preferably 2 to 50 m, more preferably 3 to 30 / zm, and particularly preferably. Is 5-20 m.
  • the average fiber length is not particularly limited, but is usually 0.1 to 20 mm, preferably 1 to 10 mm.
  • the reinforcing filler is preferably used after surface treatment with a sizing agent or a surface treatment agent in order to improve interfacial adhesion with PBT.
  • the sizing agent or the surface treatment agent include functional compounds such as an epoxy compound, an acrylic compound, an isocyanate compound, a silane compound, and a titanate compound.
  • the reinforcing filler can be surface-treated in advance with a sizing agent or a surface treatment agent, or can be surface-treated by adding a sizing agent or a surface treatment agent when preparing a PBT composition.
  • the amount of the reinforcing filler to be added is usually 150 parts by weight or less, preferably 5 to 100 parts by weight, based on 100 parts by weight of the PBT resin.
  • the PBT of the present invention may contain other fillers together with the reinforcing filler.
  • Other fillers to be blended include, for example, plate-like inorganic fillers, ceramic beads, asbestos, wollastonite, talc, clay, my power, zeolite, power orient, potassium titanate, barium sulfate, titanium oxide, oxide Examples include silicon, aluminum oxide, and magnesium hydroxide.
  • plate-like inorganic filler examples thereof include glass flakes, mica, and metal foil. Among these, glass flake is preferably used.
  • a flame retardant can be added to the PBT of the present invention in order to impart flame retardancy.
  • the flame retardant is not particularly restricted but includes, for example, organic halogen compounds, antimony compounds, phosphorus compounds, other organic flame retardants, inorganic flame retardants and the like.
  • organic halogen compound include brominated polycarbonate, brominated oxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, poly (pentabromobenzyl acrylate), and the like.
  • the antimony compound include antimony trioxide, antimony pentoxide, and sodium antimonate.
  • Examples of the phosphorus compound include a phosphoric acid ester, polyphosphoric acid, ammonium polyphosphate, and red phosphorus.
  • Examples of other organic flame retardants include nitrogen compounds such as melamine and cyanuric acid.
  • Other inorganic flame retardants include, for example, aluminum hydroxide, magnesium hydroxide, silicon compounds, boron compounds and the like.
  • the PBT of the present invention may contain conventional additives and the like, if necessary.
  • additives are not particularly limited, and include, for example, stabilizers such as antioxidants and heat stabilizers, as well as lubricants, fillers, release agents, catalyst deactivators, nucleating agents, and crystallization accelerators. And the like. These additives can be added during or after the polymerization.
  • the crystal nucleating agent include talc, kaolin, boron nitride, and the like.
  • Examples of the above-mentioned filler include layered silicate, zeolite, silica, and the like.
  • ultraviolet absorbers, stabilizers such as weathering stabilizers, coloring agents such as dyes and pigments, antistatic agents, foaming agents, plasticizers, impact modifiers, etc. Can be blended.
  • the PBT of the present invention may include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polymethacrylate, ABS resin, polyacrylonitrile, polyamide, polyphenylene sulfide, polyethylene, if necessary.
  • Thermoplastic resins such as terephthalate, liquid crystal polyester, polyacetal, and polyphenylene oxide, and thermosetting resins such as phenolic resin, melamine resin, silicone resin, and epoxy resin can be blended. These thermoplastic resins and thermosetting resins can be used in combination of two or more.
  • the method of compounding the above-mentioned various additives and resins is not particularly limited, but it is preferable to use a single-screw or twin-screw extruder having equipment capable of devolatilizing from the vent opening as a kneader.
  • Each component, including additional components can be fed to the kneader at once or can be fed sequentially. Also, two or more components selected from each component, including additional components, can be mixed in advance.
  • the PBT of the present invention can be used as a general resin composition by an ordinary method in the resin field, and furthermore, the PBT of the present invention can be used in combination with a specific additive in various ways. It can be used as a specific polybutylene terephthalate composition having a function.
  • these resin compositions will be described.
  • the heat-resistant PBT composition of the present invention is a group consisting of the above-mentioned PBT (A), a phenolic antioxidant (B 1), a zeolite antioxidant (B 2) and a phosphorus antioxidant (B 3). It is characterized by containing one or more antioxidants selected from the group consisting of:
  • the phenolic antioxidant (B 1) used in the present invention means a phenolic antioxidant having a phenolic hydroxyl group.
  • the hindered phenolic antioxidant is a phenolic hydroxyl group to which a phenolic hydroxyl group is bonded.
  • the substituent having 4 or more carbon atoms may be bonded to a carbon atom of the aromatic ring by a carbon-carbon bond, or may be bonded via an atom other than carbon.
  • Specific examples of the phenolic antioxidant (B 1) used in the present invention include p-cyclohexylphenol, 31-t-butyl-4-methoxyphenol, 4,4′-isopropylidenediphenol, 1, 1-bis (4-hydro Non-hindered phenolic antioxidants, such as cyclohexane) cyclohexane, etc., 2-t-butyl-4-methoxyphenol, 2,6-di-t-butyl-p-cresol, 2,4,6-tri-t- Butylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, styrenated phenol, 2,5-di-t-butylhydroquinone, octadecyl-3- (3-, 3-di-t-butyl-4 Hydr
  • a hindered phenol-based antioxidant can be suitably used as a radical trapping agent because it tends to itself become a stable radical.
  • Hindered fenor The molecular weight of the toluene-based antioxidant is usually at least 200, preferably at least 500, and the upper limit is usually at most 300.
  • the zeotype antioxidant (B 2) used in the present invention means an antioxidant having no zirconium atom without a phenolic hydroxy group.
  • Specific examples of the zirconium-based antioxidants (B 2) include didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, and pen erythritol tetrakis (3-dodecylthiopropionate).
  • thiobis N-phenyl 3-naphthylamine
  • 2-mercaptobenzothiazole 2-mercaptobenzoimidazole
  • tetramethylthiuram monosulfide tetramethylthiuram disulphide
  • nickel dibutyldithiocarbamate nickel Isopropyl xanthate
  • trilauryl trithiophosphite and the like.
  • a thioether-based antioxidant having a thioether structure can be suitably used because it receives and reduces oxygen from an oxidized substance.
  • the molecular weight of the zirconium antioxidant is usually at least 200, preferably at least 500, and the upper limit is usually at least 300.
  • the phosphorus-based antioxidant (B 3) used in the present invention means a phosphorus-containing antioxidant having neither a phenolic hydroxyl group nor an iodine atom.
  • the phosphorus antioxidant (B 3) is preferably an antioxidant having a P (OR) 3 structure.
  • R is an alkyl group, an alkylene group, an aryl group, an arylene group, etc., three R may be the same or different, and two R may form a ring structure.
  • Such phosphorus-based antioxidants include triphenylphosphite, diphenyldecylphosphite, phenyldiisodecylphosphite, tri (nonylphenyl) phosphite, and bis (2,4-dibutylbutylphenyl) pen. Erythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pen and erythritol diphosphite.
  • the phenolic antioxidant (B 1) The content is usually 001 to 2 parts by weight, preferably 0.003 to 1 part by weight, based on 100 parts by weight of PBT. If the content of the phenolic antioxidant is less than 0.001 part by weight, the antioxidant effect may not be sufficiently exhibited, and if it exceeds 2 parts by weight, the oxidative heat stability may deteriorate, Decomposition of the resin may occur during kneading.
  • the zeolite-based antioxidant (B2) and the phosphorus- or phosphorus-based antioxidant (B3) improve the heat aging resistance of the resin composition, and improve the color tone, tensile strength and elongation. It has the effect of improving the retention such as degree.
  • the content of the zeolite antioxidant (B2) and the content of the phosphorus antioxidant (B3) are usually 0.001-1. 9 parts by weight, preferably 0.003 to 1 part by weight. If the content of each antioxidant is less than 0.001 parts by weight, the above effects may not be sufficiently exerted. If the content is more than 1.9 parts by weight, the oxidation heat stability may deteriorate, Decomposition of the resin may occur during melt-kneading.
  • the heat-resistant PBT composition of the present invention contains a phenolic antioxidant (B1), a zeolite antioxidant (B2), and / or a phosphorus-based antioxidant (B3)
  • the ratio of the zirconium antioxidant and / or the phosphorus antioxidant to 1 part by weight of the antioxidant is usually 2 to 5 parts by weight.
  • the ratio of the zirconium antioxidant and the Z or phosphorus antioxidant is less than 0.2 part by weight or more than 5 parts by weight, the effect of improving the heat aging resistance may be reduced.
  • the total content of the antioxidant is based on 100 parts by weight of PBT. Usually less than 2 parts by weight. If the total content of the antioxidants exceeds 2 parts by weight, the oxidative heat stability may be deteriorated, or the resin may be decomposed during melt-kneading.
  • the good releasable PBT composition of the present invention comprises a fatty acid residue having 12 to 36 carbon atoms and an alcohol residue having 1 to 36 carbon atoms with respect to 100 parts by weight of the PBT (A).
  • the fatty acid forming the fatty acid ester (C 1) used in the present invention must be a fatty acid ester comprising a fatty acid residue having 12 to 36 carbon atoms and an alcohol residue having 1 to 36 carbon atoms. And preferably a fatty acid ester comprising a fatty acid residue having 16 to 32 carbon atoms and an alcohol residue having 1 to 36 carbon atoms, and more preferably a fatty acid residue having 16 to 32 carbon atoms and 1 to carbon atoms. It is a fatty acid ester consisting of 20 alcohol residues.
  • fatty acids that form fatty acid esters (C 1) include lauric acid, myristic acid, palmitic acid, stearic acid, araquinic acid, behenic acid, lignoceric acid, serotinic acid, montanic acid, melisic acid, and raccelic acid.
  • lauric acid myristic acid, palmitic acid, stearic acid, araquinic acid, behenic acid, lignoceric acid, serotinic acid, montanic acid, melisic acid, and raccelic acid.
  • a monohydric alcohol, a dihydric alcohol and a trihydric or higher polyhydric alcohol can be used as the alcohol forming the fatty acid ester (C 1).
  • specific examples of such alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, lauryl alcohol, and stearyl alcohol.
  • Monohydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, and other dihydric alcohols, Trihydric alcohols such as serine and trimethylolpropane; and tetrahydric alcohols such as pentaerythritol and erythritol. Carbon number of alcohol residue If it exceeds 36, the effect of improving the releasability may not be sufficiently exhibited.
  • Examples of the method for producing the fatty acid ester (C 1) include a method in which a fatty acid and an alcohol are used as raw materials and esterification is performed in the presence of an acid catalyst such as sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, and the like.
  • an acid catalyst such as sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, and the like.
  • the alcohol forming the fatty acid ester is a high-boiling alcohol
  • a transesterification method can be employed between the lower alkyl ester of the fatty acid and the high-boiling alcohol.
  • fatty acid ester (C 1) examples include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl behenate, methyl montanate, isopropyl myristate, isopropyl palmitate, and laurin.
  • the molecular weight of (C 2) is usually 3 00-5000, preferably 500-3000. If the molecular weight is less than 300, it will easily evaporate from the vacuum vent during compounding, making it difficult to exert its effect, and wax will easily bleed out during molding, causing mold fouling. On the other hand, when the molecular weight exceeds 5,000, the effect as a release agent is reduced without bleeding out.
  • the content of the fatty acid ester (C1) is usually 0.01 to 2 parts by weight, preferably 0.1 to 1 part by weight based on 100 parts by weight of PBT. .
  • the content of the fatty acid ester (C1) is less than 0.01 parts by weight, the effect of improving the releasability (the effect of shortening the molding cycle) may not be sufficiently exhibited.
  • the effect of improving the releasability corresponding to the increase of the ester cannot be obtained, but rather the strength and the heat resistance may decrease.
  • the content of paraffin wax or polyethylene wax (C2) is usually from 01 to 2 parts by weight, preferably from 0.1 to 1 part by weight, based on 100 parts by weight of PBT. Department. If the content of paraffin wax or polyethylene wax (C2) is less than 0.01 parts by weight, the effect of improving releasability (the effect of shortening the molding cycle) may not be sufficiently exhibited, and if it exceeds 2 parts by weight. Does not provide the effect of improving the releasability corresponding to the increase in paraffin wax or polyethylene wax, but rather may lower the strength and heat resistance.
  • the hydrolysis-resistant PBT composition of the present invention contains 0.01 to 20 parts by weight of an epoxy compound (E) and 0 to 200 parts by weight of a reinforcing filler (D) based on 100 parts by weight of the above-mentioned PBT (A). It is characterized by doing.
  • the epoxy compound (E) used in the present invention may be monofunctional, difunctional, trifunctional or polyfunctional, or may be a mixture of two or more of these.
  • a bifunctional, trifunctional, or polyfunctional epoxy compound that is, a compound having two or more epoxy groups in one molecule is preferable.
  • Epoxy compound (E) is composed of alcohol, phenolic compound or carboxylic acid and Any of a glycidyl compound and an alicyclic epoxy compound obtained from the reaction with drin may be used.
  • epoxy compound (E) examples include methyldaricidyl ether, petylglycidylether, 2-ethylhexyldaricidyl ether, decylglycidylether, stearylglycidylether, phenyldaricidyl ether, butylphenyl Daricidyl ethers such as dalicidyl ether and arylglycidyl ether; neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, bisphenol A diglycidyl ether, etc.
  • Diglycidyl ethers fatty acid glycidyl esters such as daricidyl benzoate and sorbic acid dalycidyl ester; diglycidyl ester adipate; diglycidyl terephthalate Ester, diglycidyl esters such as orthophthalic acid diglycidyl ester le; 3, 4 _ epoxy cyclohexane Kishirumechiru 3, 4 etc. alicyclic diepoxy compounds such as hexyl Cal Po carboxylate and the like into single epoxycycloalkyl.
  • dalicidyl ether compounds obtained by the reaction of bisphenol A with epichlorohydrin, particularly bisphenol A diglycidyl ether, are preferred.
  • Examples of the type of the reinforcing filler (D) used in the present invention include glass fiber, carbon fiber, silica / alumina fiber, zirconia fiber, boron fiber, boron nitride fiber, potassium silicon titanate fiber, and metal.
  • Examples include inorganic fibers such as fibers, and organic fibers such as aromatic polyamide fibers and fluororesin fibers.
  • One of these reinforcing fillers may be used alone, or two or more of them may be used in combination. Of these, inorganic fillers are preferably used, and glass fiber is particularly preferably used.
  • the reinforcing filler (D) is an inorganic fiber or an organic fiber
  • its average fiber diameter is usually 1 to 100 m, preferably 2 to 50 m, more preferably 3 to 30 ⁇ m, and particularly preferably. 5 to 20 xm.
  • the average fiber length is usually 0.1 to 20. mm, preferably 1 to: I 0 mm.
  • the reinforcing filler (D) is preferably used after surface treatment with a sizing agent or a surface treatment agent in order to improve interfacial adhesion with PBT.
  • a sizing agent or a surface treatment agent include functional compounds such as an epoxy compound, an acrylic compound, an isocyanate compound, a silane compound, and a titanate compound.
  • the reinforcing filler (D) can be surface-treated in advance with a sizing agent or a surface treatment agent, and the surface treatment should be performed by adding a sizing agent or a surface treatment agent when preparing the PBT composition. Can also be.
  • glass fiber used in the present invention examples include various glass fibers such as E glass, C glass, A glass, S glass, and S-2 glass.
  • E-glass fiberglass which has a low alkali content and good electrical properties, is preferred.
  • the average fiber diameter of the glass fibers is usually 1 to 100 / m, preferably 2 to 50m, more preferably 3 to 30m, and particularly preferably 5 to 20 / im. Glass fibers with an average fiber diameter of less than 1 m are not easy to manufacture and may increase costs. Glass fibers having an average fiber diameter of more than 100 zm may decrease the tensile strength of the glass fibers.
  • the average fiber length of the glass fibers is usually from l to 20 mm, preferably from 1 to 10 mm. If the average fiber length is less than 0.1 mm, the reinforcing effect of the glass fiber may not be sufficiently exhibited.If the average fiber length exceeds 2 Omm, melt kneading with PBT or molding of the PBT composition May be difficult.
  • the glass fiber is preferably glass fiber that has been treated with a surface treatment agent.
  • a surface treatment agent By treating the surface of the glass fiber with the surface treatment agent, strong adhesion or bonding occurs at the interface between the PBT and the glass fiber, and the stress is transmitted from the PBT to the glass fiber, thereby exhibiting the reinforcing effect of the glass fiber.
  • Examples of the surface treatment agent to be used include, for example, chlorosilane-based compounds such as vinyltrichlorosilane and methylvinyldichlorosilane, vinyltrimethoxysilane, Vinyltriethoxysilane, biertriacetoxysilane, methacryloxy
  • Epoxysilane-based compounds such as ethyltrimethoxysilane and glycidoxypropyltrimethoxysilane, acryl-based compounds, isocyanate-based compounds, titanate-based compounds, and epoxy-based compounds.
  • the glass fiber is preferably a glass fiber that has been treated with a sizing agent.
  • a sizing agent By treating the glass fiber with a sizing agent, the workability of handling the glass fiber can be improved and the glass fiber can be prevented from being damaged.
  • the sizing agent used include resin emulsions such as vinyl acetate resin, ethylene-vinyl acetate copolymer, acrylic resin, epoxy resin, polyurethane resin, and polyester resin.
  • the content of the epoxy compound (E) is usually 0.01 to 20 parts by weight, preferably 0.03 to 10 parts by weight, based on 100 parts by weight of PBT.
  • the content of the epoxy compound (E) is less than 0.01 part by weight, there is almost no effect of improving the hydrolysis resistance, and when the content exceeds 20 parts by weight, other mechanical properties are degraded or the melting heat is stabilized. Or worse.
  • the content of the reinforcing filler (D) is usually 0 to 200 parts by weight, preferably 0 to 150 parts by weight, based on 100 parts by weight of PBT.
  • the content of the reinforcing filler (D) is more than 200 parts by weight, there is a possibility that melt-kneading and molding of the resin composition become difficult.
  • the impact-resistant PBT composition of the present invention comprises, based on 100 parts by weight of the above-mentioned PBT (A), 0.5 to 40 parts by weight of an impact resistance improving material (F) and 0 to 200 parts by weight of a reinforcing filler (D). Parts.
  • the impact modifier (F) used in the present invention is used to improve impact values such as Izod impact value, Charpy impact value, and surface impact value.
  • acrylic rubber is preferable.
  • Acrylic rubber is a rubber-like elastic material obtained by polymerization of acrylate or copolymerization based on acrylate, and a typical example is acrylate with a small amount of acrylate such as butyl acrylate.
  • a rubber-like polymer obtained by graft-polymerizing a graft-polymerizable monomer such as methyl methacrylate with a polymer obtained by polymerizing a cross-linkable monomer such as range acrylate is exemplified.
  • Examples of the acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, hexyl acrylate, and 2-ethyl hexyl acrylate in addition to butyl acrylate.
  • Examples of the crosslinkable monomer include, in addition to petylene diacrylate, esters of polyol and acrylic acid or methacrylic acid such as petylene dimethacrylate, trimethylolpropane trimethacrylate, divinylbenzene, vinyl acrylate, Vinyl conjugates such as vinyl methacrylate, aryl acrylate, aryl methacrylate, diaryl malate, diaryl fumarate, diaryl itaconate, monoaryl maleate, monoallyl fumarate, triaryl sinurate And allyl compounds. ⁇
  • graft polymerizable monomer examples include, in addition to methyl methacrylate, methacrylates such as ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate, styrene, and acrylonitrile.
  • methacrylates such as ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate, styrene, and acrylonitrile.
  • Can be A part of the graft polymerizable monomer may be used for producing a polymer by polymerizing the acrylate and the crosslinkable monomer, and may be copolymerized.
  • the content of the impact modifier (F) is usually 0.5 to 40 parts by weight, preferably 1 to 35 parts by weight, based on 100 parts by weight of PBT. Parts, more preferably 2 to 30 parts by weight. If the content of the impact modifier (F) is less than 5 parts by weight, no improvement in impact resistance ⁇ heat shock resistance is observed. If it exceeds 40 parts by weight, mechanical properties such as tensile strength and bending strength are significantly reduced.
  • the type and content of the reinforcing filler (D) are the same type and content as described in the above-mentioned hydrolysis-resistant PBT composition. .
  • the flame-retardant PBT composition of the present invention comprises 3 to 50 parts by weight of a brominated aromatic compound-based flame retardant (G) and 1 to 30 parts by weight of an antimony compound (H) based on 100 parts by weight of the PBT (A).
  • the anti-dripping agent (I) contains 0 to 15 parts by weight and the reinforcing filler (D) 0 to 200 parts by weight.
  • the brominated aromatic compound-based flame retardant (G) used in the present invention is an aromatic compound known as a brominated flame retardant used in a resin.
  • a brominated flame retardant used in a resin for example, an epoxy compound of tetrabromobisphenol A Oligomer, poly (pentabromobenzyl acrylate), polybromophenyl ether, brominated polystyrene, brominated epoxy, brominated imide, brominated polycarbonate, and the like.
  • Antimony compound used in the present invention as the (H), for example, include oxide antimony Ya antimonate salts, specific examples, antimony trioxide (Sb 2 ⁇ 3), antimony tetroxide (Sb 2 0 4) , antimony salts such as oxides or antimonate Natoriumu such antimony pentoxide (Sb 2 ⁇ 5).
  • the anti-dripping agent (I) used in the present invention refers to a compound having a property of preventing dripping of a resin during combustion, and specific examples thereof include silicone oil, silica, asbestos, fluororesin, and talc. Other examples include layered silicates such as my force. Particularly, from the viewpoint of the flame retardancy of the composition, preferred anti-dripping agents are fluorine-containing polymers or layered silicates.
  • fluororesin used as the anti-dripping agent (I) include polytetrafluoroethylene, tetrafluoroethylene perfluoro-mouth alkyl vinyl ether copolymer, And fluorinated polyolefins, such as tetrafluoroethylene Z ethylene copolymer, vinylidene fluoride, and polytetrafluoroethylene.
  • polytetrafluoroethylene, tetrafluoroethylene perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene Ethylene / ethylene copolymer is preferred, and polytetrafluoroethylene and tetrafluoroethylene / hexafluoropropylene copolymer are more preferred.
  • polytetrafluoroethylene those having a fibril-forming ability are preferable. That is, it is easily dispersed in a resin, and shows a tendency to form a fibrous material by combining polymers, and functions as an anti-dripping agent.
  • Polytetrafluoroethylene having the ability to form fibrils is classified into Type 3 according to the ASTM standard. For example, “Polyflon FA-500” or “F-201L” by Daikin Chemical Industries, Ltd., Asahi Glass Co., Ltd. ) Is commercially available as Teflon (R) 6 J from Mitsui. DuPont Fluorochemicals, Inc.
  • the melt viscosity of the fluororesin used as the anti-dripping agent (I) at 350 ° C. is usually 1.0 ⁇ 10 2 to 1.0 ⁇ 10 15 (Pa ⁇ s), preferably 1.0 ⁇ 10 3 11.0 ⁇ 10 14 (Pa ⁇ s), and more preferably 1.0 ⁇ 10 10 to 1.0 ⁇ 10 12 (Pa ⁇ s). If the melt viscosity is less than 1,0 X 10 2 (P a * s), the ability to prevent dripping during combustion is insufficient, and a composition larger than 1.0 X 10 15 (P a Has a markedly reduced fluidity.
  • a layered silicate as the anti-dripping agent (I) from the viewpoint of the fluidity of the resin composition of the present invention at the time of melting.
  • the layered silicate include a layered silicate, a modified layered silicate (a layered silicate in which a quaternary organic cation is inserted between layers), and a layered silicate having a reactive functional group or a modified layered silicate. From the viewpoint of the dispersibility of the layered silicate in the resin composition of the present invention and the ability to prevent dripping, a modified layered silicate, a layered silicate to which a reactive functional group is added, or a modified layered silicate is preferable.
  • the layered silicate or modified layered silicate to which the reactive functional group is added is preferably used.
  • a method of imparting a functional group a method of treating with a functionalizing reagent (silane coupling agent) is simple and preferable.
  • Examples of the functionalizing reagent include chlorosilanes having an epoxy group, chlorosilanes having a carbonyl group, chlorosilanes having a mercapto group, alkoxysilanes having an amino group, alkoxysilanes having an epoxy group, and the like. No.
  • chlorosilanes having an epoxy group such as 3-daricidyloxypropyldimethylchlorosilane, ⁇ - (3,4-epoxycyclohexyl) ethyldimethylchlorosilane, 3-daricidyloxypropyltrichlorosilane, Has an amino group such as 3-aminopropyltriethoxysilane, ⁇ — (2-aminoethyl) -1-3-aminopropyltrimethoxysilane, ⁇ — (2-aminoethyl) -3-aminopropylmethyldimethoxysilane
  • Epoxy groups such as alkoxysilanes, 3-daricidyloxypropylmethyljetoxysilane, 3-glycidyloxypropyl trimethoxysilane, r- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Alkoxysilanes having the following are
  • layered silicate used in the present invention include smectite-based clay minerals such as montmorillonite, hectorite, fluorine hectorite, savonite, suberite and subchinsite, Li-type fluorine teniolite, and Na-type fluorine teniolite.
  • swellable synthetic mica such as Na-type tetrasilicon fluoromica, Li-type tetrasilicon fluoromica, and the like, and any of natural products and synthetic products may be used.
  • smectite clay minerals such as montmorillonite and hectorite
  • swellable synthetic mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, and Na-type tetrasilicon fluorine mica are preferable.
  • the quaternary cation inserted between the layers of the modified layered silicate used in the present invention includes, for example, trimethyloctylammonium, trimethyldecylane Monium, trimethyl dodecyl ammonium,
  • Trimethylalkylammonium such as dimethyl, trimethylhexadecylammonium and trimethyloctadecylammonium, dimethyldioctylammonium methylditetraammonium, dimethyldihexadecylammonium, and dimethyl.
  • Silicone oil is also preferred as the dripping inhibitor (I).
  • the silicone oil is a compound having a dimethylpolysiloxane skeleton represented by the following general formula (1), and a terminal or a part or all of a side chain thereof is amino-modified, epoxy-modified, carboxyl-modified, or carbinol. Modified, methacryl-modified, mercapto-modified, phenol-modified, polyether-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester-modified, higher alkoxy-modified, and fluorine-modified may be functionalized.
  • the viscosity of the silicone oil used as the anti-dripping agent (I) at 25 ° C is usually 1000 to 30000 (cs), preferably 2000 to 25000 (cs), more preferably 3000 to 20000 (cs). .). If the viscosity is less than 1000 (c s.), The effect of preventing dripping during combustion is insufficient, and the flame retardancy is greatly reduced. If the viscosity is more than 30,000 (c s.), The composition is thickened due to the thickening effect. Has a markedly reduced fluidity.
  • the content of the brominated aromatic compound-based flame retardant (G) is usually 3 to 50 parts by weight, preferably 5 to 50 parts by weight based on 100 parts by weight of PBT. -40 parts by weight, more preferably 6-30 parts by weight.
  • the content of the brominated aromatic compound-based flame retardant (G) is less than 3 parts by weight, the flame-retardant effect is insufficient, and when it exceeds 50 parts by weight, the mechanical strength is reduced and the heat during melting is reduced. Stability tends to decrease.
  • the content of the antimony compound (H) is usually 1 to 30 parts by weight, preferably 2 to 25 parts by weight, more preferably 3 to 20 parts by weight with respect to 100 parts by weight of PBT. Department. If the content of the antimony compound (H) is less than 1 part by weight, a sufficient flame retardant effect cannot be obtained.If the content exceeds 30 parts by weight, the mechanical strength is reduced and the thermal stability during melting is reduced. easy.
  • the content of the anti-dripping agent (I) is usually 0 to 15 parts by weight based on 100 parts by weight of PBT. If the content of the anti-dripping agent (I) exceeds 15 parts by weight, the fluidity and mechanical properties may be reduced.
  • the type and content of the reinforcing filler (D) are the same type and content as described in the above-mentioned hydrolysis-resistant PBT composition.
  • the flame-retardant PBT composition of the present invention comprises a compatibilizer (K) based on a total of 100 to 50 parts by weight of the PBT (A) and 5 to 50 parts by weight of the polyolefin ether resin (J). ) 0.05 to 10 parts by weight, at least one compound selected from phosphate esters or phosphonitrile (L) 2 to 45 parts by weight, reinforcing filler (D) 0 to 200 parts by weight, anti-drip agent (I ) 0 to 15 parts by weight, melamine cyanurate (M) 0 to 45 parts by weight and metal borate (N) 0 to 50 parts by weight.
  • K compatibilizer
  • the polyphenylene ether resin (J) (hereinafter abbreviated as PPE) used in the present invention is a homopolymer or a copolymer having a structure represented by the following general formula (2).
  • R 1Q represents a hydrogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, or a hydrocarbonoxy group
  • R 11 represents a primary or secondary alkyl group
  • r represents an integer of 10 or more.
  • Examples of the primary alkyl group represented by R 1Q include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-amyl group, an n-hexyl group, an isoamyl group, a 2-methylbutyl group, Examples include a 2,3-dimethylbutyl group, a 2-, 3- or 4-methylpentyl group or a heptyl group.
  • Preferable examples of the secondary alkyl group include an isopropyl group, a sec-butyl group and a 1-ethylpropyl group.
  • Suitable homopolymers of PPE are, for example, those comprising 2,6-dimethyl-1,4-phenylene ether units.
  • a preferred copolymer is a random copolymer composed of a combination of the above units and 2,3,6-trimethylylene 1,4-phenylene ether units.
  • the intrinsic viscosity of the PPE (J) used in the present invention at 30 ° C measured in a black mouth form is usually 0.20 to 0.70 dL / g, preferably 0.25 to 0.70 dLZg, and Preferably it is 0.30 to 0.60 dL / g.
  • the intrinsic viscosity is less than 0.20 dLZg, the impact resistance of the composition is insufficient, and when it exceeds 0.80 dL // g, the gel component is large and the appearance of the molded article tends to deteriorate.
  • a compound having one or more functional groups A phosphite compound or the like can be used.
  • the compound having a functional group examples include an epoxy group-added PPE resin, a hydroxyalkylated PPE resin, a oxazoline-terminated PPE resin, a polyester in which a lipoxyl group end is modified with polystyrene, and an OH group end modified with polyethylene. Polyester and the like.
  • a phosphite or a polycarbonate resin is preferred from the viewpoints of hydrolysis resistance, crystallinity, mechanical properties, and flame retardancy of the composition of the present invention, and phosphite is preferred.
  • R 12 to R 14 each independently may contain an oxygen atom, a nitrogen atom, a sulfur atom, an alkyl group having 1 to 20 carbon atoms or a substitution or 6 to 30 carbon atoms. Represents an unsubstituted aryl group.
  • Specific examples of the general formula (3) include trioctyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triisooctyl phosphite, tris (nonylphenyl) phosphite, and tris
  • (2,4-Dinonylphenyl) phosphite tris (2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, tris (octylphenyl) phosphite, diphenylisooctylphosphite, diphenyl Examples include sodecyl phosphite, octyl diphenyl phosphite, dilauryl phenyl phosphite, diisodecyl phenyl phosphite, bis (nonylphenyl) phenyl phosphite, and diisooctyl phenyl phosphite.
  • u is 1 or 2
  • R 15 is the same or different and may contain an oxygen atom, a nitrogen atom or a sulfur atom, an alkyl group having 1 to 20 carbon atoms or a carbon number of 6 to And 30 represents a substituted or unsubstituted aryl group having 30.
  • R 16 represents an alkylene group having 1 to 20 carbon atoms or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms;
  • it represents an alkyltetrayl group having 4 to 18 carbon atoms.
  • R 15 examples include methyl, ethyl, propyl, octyl, isooctyl, isodecyl, decyl, stearyl, lauryl, phenyl, 21,3- or 4-methylphenyl, 2 , 4,1- or 2,6-dimethylphenyl, 2,3,6-trimethylphenyl, 2-, 3_ or 4-ethylphenyl, 2-, 4_ or 2-, 6-methylethyl, 2,3,6-triethylphenyl, 2-, 3- or 4-tert-butylphenyl, 2,4- or 2,6-ditert-butylphenyl, 2,6-di-tert-butyl _ 4 _Methylphenyl group, 2,6-ditert-butyl-4-ethylphenyl group, octylphenyl group, isooctylphenyl group, 2-, 3_ or 4-nonylphenyl group,
  • R 16 is a tetrayl group having a pentaerythrityl structure represented by the following general formula (5).
  • diisodecyl penyl erythritol diphosphite diaryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, diphenyl pentaerythritol diphosphite, and bisphenol erythritol diphosphite.
  • a compound in which u is 1 or 2 in the formula (4) is preferable.
  • R 16 is a compound represented by the general formula (5)
  • Compounds having a tetrayl group having a pentaerythrityl structure shown below are more preferable.
  • the composition of the present invention may contain a compound generated by the decomposition (hydrolysis, thermal decomposition, etc.) of these phosphite triesters.
  • polycarbonate resin used as the compatibilizer (K) in the present invention examples thereof include aromatic dihydroxy compounds or a thermoplastic aromatic polycarbonate polymer or copolymer which may be produced by reacting a small amount of the polyhydroxy compound with phosgene or a carbonic acid diester.
  • the aromatic polycarbonate resin is preferably a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and another aromatic dihydroxy resin. And a polycarbonate copolymer derived from the compound.
  • the molecular weight of the polycarbonate resin used as the compatibilizing agent (K) is usually 160000-1000 as the viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C using methylene chloride as a solvent. It is 30, 000, preferably 18, 000 to 23, 000.
  • a polycarbonate resin two or more types It is also possible to use a mixture of a lithium carbonate resin.
  • the phosphate ester compound (L) used in the present invention includes a wide range of phosphate esters. Specific examples thereof include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxetyl phosphate, triphenyl phosphate, tricresyl rephosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, and the like. Among them, a compound represented by the following general formula (6) is particularly preferable.
  • R 9 is p-phenyl Diene group, m-phenylene group, 4,4′-biphenylene group or a divalent group selected from the following.
  • ⁇ To 8 are preferably an alkyl group having 6 or less carbon atoms, more preferably an alkyl group having 2 or less carbon atoms, and particularly preferably a methyl group, from the viewpoint of improving the hydrolysis resistance of the composition of the present invention.
  • m is preferably 1 to 3, and more preferably 1.
  • R 9 is preferably a p-phenylene group. Or m-phenylene group, more preferably m-phenylene group.
  • a phospho: tolylic compound Rx Xl Di RlI having a group represented by the following general formula (7) is also suitably used.
  • X represents —0—, 1 S—, —NH— or a direct bond.
  • R 17 and R 18 represent an aryl group, an alkyl group, or a cycloalkyl group having 1 to 20 carbon atoms.
  • R 1 7-X-, R 18 - X- may be the same or different and n indicates to the 1 to 1 2 integer).
  • R 17 and R 18 include an optionally substituted alkyl group such as a methyl group, an ethyl group, a butyl group, a hexyl group and a benzyl group; and a cycloalkyl group such as a cyclohexyl group.
  • aryl groups such as an alkyl group, a phenyl group, and a naphthyl.
  • n is preferably from 3 to 10, more preferably 3 or 4.
  • the phosphonitrile compound of the general formula (7) may be a linear polymer or a cyclic polymer, but is preferably a cyclic polymer.
  • X is preferably 10- or -NH-, particularly preferably 10-.
  • phosphonitrile compound represented by the general formula (7) examples include hexaphenoxycyclotriphosphazene, hexa (hydroxyphenoxy) cyclotri phosphazene, octaphenoxycyclotetraphosphazene, and octa (hydroxyphenoxy) cyclo. Tetraphosphazene and the like.
  • Melamine cyanurate (M) used in the present invention is defined as It is a substantially equimolar reactant, and can be obtained, for example, by mixing an aqueous solution of sialic acid and an aqueous solution of melamine, reacting the mixture at a temperature of 90 to 100 ° C. with stirring, and filtering the resulting precipitate.
  • the particle size of melamine cyanurate is usually from 0.01 to 1000 m, preferably from 0.01 to 500 m. Some of the amino or hydroxyl groups of melamine cinurate may be substituted with other substituents.
  • the metal borate (N) used in the present invention is preferably one which is stable under the commonly used processing conditions and has no volatile components.
  • the metal borate (N) include alkali metal borate (eg, sodium tetraborate, potassium metaborate, etc.) and alkaline earth metal salts (eg, calcium borate, magnesium orthoborate, barium orthoborate, zinc borate, etc.) ) And the like.
  • the hydrated zinc borate, and preferably, 2 shall Zetaitaomikuron-3 [beta] 2 ⁇ 3 ⁇ 3. stable up to 5 Eta 2 is represented by 0 formula and 260 ° C or higher temperatures.
  • the content of polyphenylene ether (J) (PPE) is 95: 5 to 50:50, preferably 92: 8 to 50 by weight as PBT: PPE. 55:45, more preferably 90:10 to 60:40.
  • PPE polyphenylene ether
  • the ratio of PPE is less than 5, the flame retardancy and hydrolysis resistance of the composition become insufficient, and when it exceeds 50, the fluidity and chemical resistance of the composition are significantly reduced.
  • the content of the compatibilizer (K) is 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total of PBT and PPE.
  • the amount is 1 to 8 parts by weight, more preferably 0.3 to 5 parts by weight.
  • the content of (K) is less than 0.05 parts by weight, the physical properties of the composition, particularly the mechanical strength and flame retardance, are reduced. Surface appearance deteriorates.
  • the content of the phosphate ester or the phosphonium (L) is based on 100 parts by weight of the total of PBT and PPE. On the other hand, it is 2 to 45 parts by weight, preferably 3 to 40 parts by weight, more preferably 5 to 30 parts by weight. If the content of phosphate ester or phosphonium (L) exceeds 2 parts by weight, the flame retardancy of the composition will be insufficient, and if it exceeds 45 parts by weight, mechanical properties, hydrolysis resistance, molding Properties are significantly reduced.
  • the type and content of the reinforcing filler (D) are the same type and content as described in the above-mentioned hydrolysis-resistant PBT composition.
  • the type and content of the anti-dripping agent (I) are the same as those described in the flame-retardant PBT composition.
  • a layered silicate When a layered silicate is used as the anti-dripping agent (I) in the non-halogen flame-retardant PBT composition of the present invention, its content is usually 0 to 15 parts by weight based on 100 parts by weight of the total of PBT and PPE. Parts, preferably 0.3 to 12 parts by weight, more preferably 0.5 to 10 parts by weight. When the content of the layered silicate exceeds 15 parts by weight, the fluidity and mechanical properties are extremely reduced.
  • One type of layered silicate may be used, or two or more types may be used in combination.
  • silicone oil when silicone oil is used as the anti-dripping agent (I) in the non-halogen flame-retardant PBT composition of the present invention, its content is 0 to 15 parts by weight with respect to 100 parts by weight of PBT and PPE in total. , Preferably 0.005 to 8 parts by weight, more preferably 0 to 5.0 parts by weight. If the silicon oil content exceeds 15 parts by weight, the fluidity and mechanical properties will be significantly reduced.
  • the content of melamine cyanurate (M) is 0 to 45 parts by weight, preferably 3 to 40 parts by weight, based on 100 parts by weight of PBT and PPE in total. And more preferably 5 to 30 parts by weight.
  • the content of melamine (M) cyanurate exceeds 45 parts by weight, the toughness and ductility are reduced, and bleed-out and plate-out are caused.
  • a phosphate ester or phospho The ratio of at least one compound selected from nitriles (L) to melamine cynate (M) is usually 1: 9 to 9: 1, preferably 2: 8 to 8: 2, and more preferably 2.5. : 7.5 to 7.5: 2.5.
  • the content of the metal borate (N) is 0 to 50 parts by weight, preferably 2 to 45 parts by weight, based on 100 parts by weight of the total of PBT and PPE. More preferably, it is 3 to 40 parts by weight. If the content of the metal borate (N) exceeds 50 parts by weight, the mechanical properties tend to deteriorate.
  • the other functional PBT composition-1 of the present invention comprises 5 to 100 parts by weight of a polycarbonate resin (O) and 0.01 to 1 part by weight of an organic phosphorus compound (P) based on 100 parts by weight of the PBT (A).
  • This functional PBT composition 11 is excellent in dimensional stability, especially when it is formed into a molded product, in which the shrinkage and the warpage are reduced.
  • the polycarbonate resin (O) used in the present invention includes an aromatic dihydroxy compound or an optionally branched polycarbonate resin produced by reacting an aromatic dihydroxy compound or a small amount of a polyhydroxy compound with phosgene or a carbonic acid diester. Copolymers or copolymers are mentioned.
  • the amount is usually from 0.01 to 10 mol%, preferably from 0.1 to 2 mol%.
  • the aromatic polycarbonate resin is preferably a polycarbonate resin produced by reacting 2,2-bis (4-hydroxyphenyl) propane with phosgene or a carbonic acid diester, or 2,2-bis (4-hydroxyphenyl). Polycarbonate copolymers produced using propane and other aromatic dihydroxy compounds. Further, two or more kinds of polycarbonate resins may be mixed and used.
  • the molecular weight of the polycarbonate resin is usually 15,000 to 30,000, preferably 16,000 to 25, as the viscosity average molecular weight calculated from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent. , 000.
  • Examples of the organic phosphorus compound (P) used in the present invention include an organic phosphate compound, an organic phosphite compound, and an organic phosphonite compound. Of these, organic phosphate compounds are preferred. In particular, a long-chain alkyl acid phosphate compound represented by the following general formula (8) is preferable.
  • R represents an alkyl group having 8 to 30 carbon atoms, and n is 1 or 2.
  • R I represents n-octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, tridecyl
  • Examples include a sotridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an eicosyl group, and a triancotyl group.
  • a monoalkyl phosphate having n of 1, dialkyl acid phosphate having n of 2, or a mixture thereof is also used.
  • the content of the polycarbonate resin (O) is 5 to 100 parts by weight, preferably 7 to 90 parts by weight, more preferably 10 to 100 parts by weight with respect to 100 parts by weight of PBT. 80 parts by weight. If the content of the polycarbonate resin (O) is less than 5 parts by weight, the effect of reducing the shrinkage and warpage of the molded article is insufficient, and if it exceeds 100 parts by weight, the crystallization speed is slow and the melt viscosity is high and extremely high. In addition, the moldability deteriorates.
  • the content of the organic phosphorus compound (P) is usually 0.01 to 1 part by weight, preferably 0.05 to 0. 6 parts by weight, more preferably 0.1 to 0.4 part by weight.
  • the content of the organophosphorus compound (P) is less than 0.01 parts by weight, the effect of improving the heating stability and retention stability of the composition is reduced.
  • the content exceeds 1 part by weight the hydrolysis resistance is improved. Cause a decline.
  • the organic phosphorus compounds (P) may be used alone or in combination of two or more.
  • the type and content of the reinforcing filler (D) are the same type and content as described in the above-mentioned hydrolysis-resistant PBT composition. You.
  • the type of the impact modifier (F) the same type as described in the above impact-resistant PBT composition is used.
  • the content is 0 to 50 parts by weight, preferably 1 to 45 parts by weight, more preferably 2 to 40 parts by weight, based on 100 parts by weight of PBT.
  • the content of the impact modifier (F) exceeds 50 parts by weight, mechanical properties such as tensile strength and bending strength are significantly reduced.
  • the other functional PBT composition 1-2 of the present invention comprises 100 to 100 parts by weight of the above-mentioned PBT (A), and 5 to 100 parts by weight of an aromatic polyester resin (Q) other than PBT and reinforced.
  • the filler (D) is characterized by containing 0 to 200 parts by weight.
  • This functional PBT composition 12 is excellent in surface appearance (transparency) especially when it is formed into a molded article.
  • aromatic polyester (Q) other than PBT used in the present invention examples include polyalkylene terephthalate and polyalkylene naphthalate. Specific examples thereof include poly 1,4-cyclohexane dimethylene terephthalate.
  • PCT polyethylene terephthalate
  • PET polypropylene terephthalate
  • PEN polyethylene naphthalate
  • PPN polypropylene naphthalate
  • PBN polybutylene naphthalate
  • the polyethylene terephthalate as used herein is a polymer obtained by polycondensing terephthalic acid or an ester-forming derivative thereof with an alkylene glycol having 2 carbon atoms or an ester-forming derivative thereof.
  • a copolymer containing the above may be used.
  • dibasic acid components other than terephthalic acid and its lower alcohol esters include aliphatic acids such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, and succinic acid.
  • the Renokisaido adduct alcohols, glycerol, port of pentaerythritol Examples include a rehydroxy compound or an ester-forming derivative thereof.
  • the polypropylene terephthalate resin means a polymer or copolymer obtained by a polycondensation reaction using terephthalic acid or its ester-forming derivative and 1,3-propanediol as main components.
  • the polymer may be one in which part of terephthalic acid is replaced by another dicarboxylic acid or an ester-forming derivative thereof, and part of 1,3-propanediol is replaced by another diol and a no or triol. It may be replaced.
  • the ester-forming derivative an ester, particularly, dimethyl terephthalate is preferable.
  • the content of the aromatic polyester (Q) other than PBT is 5 to 100 parts by weight, preferably 100 to 100 parts by weight of PBT. It is 7 to 90 parts by weight, more preferably 10 to 70 parts by weight.
  • the content of the aromatic polyester (Q) other than PBT is less than 5 parts by weight, the surface appearance of the molded article is hardly improved, and when it exceeds 100 parts by weight, the molding cycle is increased. In addition, molding problems such as deterioration of mold release properties and deterioration of mechanical properties of molded products occur.
  • the type and content of the reinforcing filler (D) are the same type and content as described in the above-mentioned hydrolysis-resistant PBT composition. You. As a method for further improving the surface appearance (transparency), it is effective to add a catalyst that promotes a transesterification reaction.
  • the ester exchange promoting catalysts include oxides, hydroxides, and organic metals of metals belonging to Groups 1A, 2A, 2B, 4A, 4B, 5B, 7A, and 8 Among the metals, sodium, calcium, lithium zinc, cobalt, manganese and the like are preferable, and organic metal salts such as sodium stearate, calcium stearate and magnesium stearate are particularly preferable. .
  • the amount of addition is usually 0.001-1% by weight.
  • Another functional PBT composition 13 of the present invention comprises the PBT (A) 100 parts by weight 5 to 100 parts by weight of styrene resin (R), 0 to 40 parts by weight of maleic anhydride-modified polystyrene resin (S) or polycarbonate resin (0), and 0 to 200 parts by weight of reinforcing filler (D) It is characterized by doing.
  • This functional PBT composition 13 has excellent dimensional stability, especially when formed into a molded product, in which the shrinkage and the warpage are reduced.
  • the styrene-based resin (R) used in the present invention may be a rubber-modified styrene-based resin, and includes, for example, (1) a homo- or copolymer of an aromatic vinyl monomer, and (2) an aromatic vinyl monomer. At least one copolymer selected from a copolymer monomer (for example, a vinyl cyanide monomer) and a rubber component can be used. Styrene resins can be used alone or in combination of two or more.
  • Examples of the aromatic vinyl monomer include styrene, vinyltoluene, 0! -Methylstyrene and the like, and styrene is particularly preferred.
  • Examples of the vinyl cyanide monomer include unsaturated nitriles such as acrylonitrile and methacrylonitrile. These vinyl cyanide monomers can be used alone or in combination of two or more. The preferred vinyl cyanide monomer is acrylonitrile.
  • Examples of the rubber-modified styrene resin include an ABS resin and a HIPS resin.
  • the number average molecular weight of the styrene-based resin is usually 5X 10 4 ⁇ 20 0 X 1 0 4, preferably in the range of 1 X 1 0 4 ⁇ 100 X 10 4.
  • the number average molecular weight decreases the strength of the case of less than 0. 5X 10 4, 200 X 10 4 greater than the fluidity decreases.
  • the maleic anhydride-modified polystyrene resin (S) used in the present invention means a resin containing maleic anhydride in polystyrene.
  • a method of including maleic anhydride in polystyrene include a method of simply mechanically blending the two, and a method of copolymerizing a styrene monomer and maleic anhydride.
  • Examples of the latter copolymerization method include an emulsion polymerization method, a solution polymerization method, and a suspension polymerization method.
  • the content of maleic anhydride is usually 1 to 40% by weight, preferably 2 to 30% by weight. %, More preferably 3 to 20% by weight.
  • the content of the styrene-based resin (R) is 5 to 100 parts by weight, preferably 7 to 90 parts by weight, more preferably 100 parts by weight of PBT. Is from 10 to 80 parts by weight.
  • the content of the styrene-based resin (R) is less than 5 parts by weight, the effect of reducing the shrinkage and warpage of the molded product is insufficient, and when the content exceeds 100 parts by weight, the mechanical properties are significantly reduced. It is.
  • the maleic anhydride-modified polystyrene resin (S) or the polycarbonate resin (O) is used as a compatibilizer between PBT and a styrene-based resin containing no vinyl cyanide monomer such as HIPS. Function.
  • the content of these resins is 0 to 40 parts by weight, preferably 5 to 100 parts by weight per 100 parts by weight of PBT.
  • the type and content of the reinforcing filler (D) are the same type and content as described in the above-mentioned hydrolysis-resistant PBT resin.
  • the above-mentioned polycarbonate resin (O) the same type as described above for the water-resistant decomposition-resistant PBT resin is used.
  • a method for incorporating various additives into PBT a method in which additives are added by melt kneading is preferable.
  • a kneading method commonly used for thermoplastic resins can be applied.
  • each component including additional components, can be supplied to the kneader at once, or can be supplied sequentially.
  • two or more components selected from each component, including additional components can be mixed in advance.
  • a reinforcing filler such as glass fiber is added after the resin is melted in the middle of the extruder, thereby avoiding crushing and exhibiting high properties.
  • Add a liquid epoxy compound In the case of adding, the epoxy compound may be added by being pressed into the melt-kneaded PBT from the middle of the extruder.
  • the molding method of the PBT and its composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, molding methods such as injection molding, hollow molding, extrusion molding, and press molding are used. Can be applied.
  • the PBT of the present invention is excellent in color tone, hydrolysis resistance, thermal stability, transparency, and moldability, and thus is suitable for injection molded parts such as electric, electronic parts, and automobile parts. And excellent transparency and thermal stability, so the improvement effect is remarkable in applications such as films, monofilaments and fibers.
  • the film of the present invention is characterized by comprising PBT containing titanium and having an amount of 33 ppm or less as titanium atoms.
  • the PBT described above can be used as such a PBT.
  • the intrinsic viscosity of PBT for films is usually from 80 to 2.50 dLZg, preferably from 0.90 to 1.80 dLZg, more preferably from 1.00 to: L. 30 dLZg.
  • Other physical properties of PBT are the same as above.
  • the method for forming a PBT film in the present invention is not particularly limited, and is generally used for thermoplastic resins, that is, T-die casting, air-cooled inflation molding, and water-cooled blow molding injection.
  • a molding method, a polysinder roll method, or the like can be applied.
  • the PBT film of the present invention can be made into a composite film with another resin film.
  • Polyolefin resin low-density polyethylene: LDPE
  • high-density polyethylene: HDPE high-density polyethylene
  • an acid-modified or epoxy-modified resin is placed between the layers to form a three-layer, three-layer film. It is also possible.
  • PBTZ bonded Z polyamide a three-layer, three-layer film using polyamide instead of polyolefin resin to increase strength, and adhesive resin between PBT and polyamide, and polyamide and polyolefin, respectively.
  • a 6-layer film in which both polyamide and EVOH are arranged between PBT and polyolefin, and an adhesive resin is arranged between each layer
  • a 6-layer film (PBT / adhesive / EVOH / polyamide / adhesive / polyolefin) can also be used.
  • the co-extrusion method is generally used as a method of producing a composite film.After forming a PBT film, it is used to dry the laminate using an adhesive and then extruding, or another molten resin is put on the PBT film. Known methods such as extrusion lamination can also be used.
  • a coating agent or reactive adhesive such as an epoxy-based, urethane-based, titanate-based, or silicone-based resin is applied to the surface of a previously prepared film, or a known surface treatment such as corona discharge is applied. Can also be.
  • the thickness of the PBT film of the present invention (the thickness of the PBT film layer in the case of a composite film) is generally 5 to 200 m. In particular, in the case of a single-layer film, the thickness is usually 10 to 150 nm, preferably 20 to 100 xm.
  • PBT film layer usually 5-100 / im, preferably 10-80 m.
  • the overall thickness of the composite film is usually 20-300 ⁇ 111, preferably 50-200 / im.
  • the haze of a PBT film is affected by the film thickness and the molding conditions, and the haze increases as the film becomes thicker and as the cooling temperature after discharge increases. Accordingly, in the present invention, when a 50-zm PBT film is formed by the T-die casting method or the water-cooled inflation method, the haze of the film is preferably less than 2%.
  • the cooling temperature for obtaining such a film that is, the surface temperature of the first-stage cooling roll in the case of the casting method is 60 ° C or less, and the cooling water temperature in the case of the water-cooled inflation method is 70 ° C or less. is there.
  • the amount of the additive is determined when the crystallization temperature of the PBT resin composition is not higher than 20 (TC, and when the film is 50 m thick). It is preferable to adjust the haze not to exceed 2%.
  • the PBT of the present invention can be copolymerized or blended (alloyed) with other resins.
  • the PBT of the present invention can be easily controlled for crystallinity and transparency.
  • Suitable blend resins, especially for films include polyesters, polycarbonates, polyamides, polyphenylene ethers, polystyrene, polymethacrylic or polymethacrylic esters, polyacrylic or polyacrylic esters, and polyolefins.
  • the blended resin may be a PBT other than the PBT of the present invention.
  • PBT of the present invention having different compositions and molecular weights can be blended.
  • polyester is preferred from the viewpoint of compatibility and transparency, and aromatic polyester is particularly preferred.
  • aromatic polyesters the aromatic polyesters described in the above “Other functional PBT composition-1” are preferable.
  • the PBT of the present invention in which the residual catalyst is significantly reduced is used.
  • decomposition can be reduced.
  • the blending ratio (weight ratio) of the PBT of the present invention and another resin is not particularly limited, but is usually 99: 1 to 1:99, preferably 95: 5 to 5:95, and more preferably 90: 1. 10-: L 0: 90.
  • the PBT film of the present invention has the above-mentioned properties, it has a feature that the contents look beautiful, and in addition to a food packaging film, an industrial product packaging film, and a bag material for packaging these, It is suitable for use as a surface coating material film for producing design properties such as shrink film, and as a steel plate laminating film for building applications and food cans.
  • PBT was wet-decomposed with high-purity sulfuric acid and nitric acid for electronic industry, and measured using a high-resolution ICP (Induced Coupled Plasma) -MS (Mass Spectrometer) (manufactured by ThermoQuest).
  • ICP Induced Coupled Plasma
  • MS Mass Spectrometer
  • the temperature was raised from room temperature to 300 ° C at a temperature rising rate of 20 ° C / min, and then lowered to 80 ° C at a cooling rate of 20 ° C / min. Then, the temperature of the exothermic peak was defined as the cooling crystallization temperature. The higher the Tc, the faster the crystallization rate and the shorter the molding cycle.
  • the yellow index b value was calculated and evaluated. The lower the value, the less yellowish and the better the color tone.
  • the measurement was performed at 250 ° C and a load of 2.16 kg.
  • an automotive wire harness connector having a hinge portion was injection molded, and the bending property of the hinge portion was evaluated.
  • the hinge is bent to 90- at 10 ° C, the hinge The number of pieces containing cracks was measured. The measurement was performed on 40 connectors.
  • a 16-pole connector was continuously molded using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd .: Model SG-75 mm), and the shortest cooling time required to continuously mold 20 shots without leaving the molded product in the fixed mold was determined. .
  • the filling time was 1 second
  • the dwell time was 8 seconds
  • the cooling time after the dwell was set.
  • the cylinder temperature was set to 250 ° (:, the initial mold temperature was set to 45 ° C.
  • the shortest cooling time mentioned above means that if the cooling time is shortened, the molded product remains in the fixed mold. This is the shortest cooling time for stable continuous production.
  • PBT was produced in the following manner.
  • a slurry prepared at 60 ° C was prepared by mixing 1.80 moles of 1,4-butanediol with 1.00 moles of terephthalic acid.
  • From the feed line (1) to the reaction vessel (A) for esterification which has a screw-type stirrer filled with PBT oligomer with an esterification rate of 99% in advance, so as to be 41 kg, h. Supplied.
  • the bottom component of the rectification column (C) at 185 ° C was supplied from the recirculation line (2) at 17.2 kg / h, and tetrabutyl at 65 ° C was used as a catalyst from the catalyst supply line (3).
  • a 6.0% by weight solution of titanate in 1,4-butanediol was fed at 97 g / h (30 ppm based on theoretical polymer yield). The water content in this solution was 0.20% by weight.
  • the internal temperature of the reactor (A) is 230 ° C
  • the pressure is 78 kPa
  • the generated water, tetrahydrofuran and excess 1,4-butanediol are distilled from the distillation line (5), and rectification is performed.
  • the column (C) high-boiling components and low-boiling components were separated. After the system is stabilized, 98% by weight or more of the high boiling components at the bottom of the column are 1,4-butanediol, and the extraction line (8) is used so that the liquid level in the rectification column (C) is constant. Some of them were extracted to the outside. On the other hand, low-boiling components are extracted from the top of the tower in gaseous form.
  • the liquid was condensed in (G), and the liquid was extracted to the outside from the extraction line (13) so that the liquid level in the tank (F) became constant.
  • a certain amount of the oligomer produced in the reaction tank (A) is extracted from the extraction line (4) using the pump (B), and the average residence time of the liquid in the reaction tank (A) is 3.3 hr.
  • the liquid level was controlled.
  • the oligomer extracted from the extraction line 4 was continuously supplied to the first polycondensation reaction tank (a). After the system was stabilized, the esterification rate of the oligomer collected at the outlet of the reaction vessel (A) was 97.5%.
  • the internal temperature of the first polycondensation reaction tank (a) was 240 ° C and the pressure was 2.lkPa, and the liquid level was controlled so that the residence time was 120 minutes.
  • the initial polycondensation reaction was performed while extracting water, tetrahydrofuran, and 1,4-butanediol from the vent line (L2) connected to a pressure reducer (not shown).
  • the extracted reaction solution was continuously supplied to the second polycondensation reaction tank (d).
  • the internal temperature of the second polycondensation reaction tank (d) was 245 ° C, the pressure was 13 OPa, the liquid level was controlled so that the residence time was 90 minutes, and the vent connected to a pressure reducer (not shown)
  • the polycondensation reaction was further advanced while extracting water, tetrahydrofuran and 1,4-butanediol from the line (L4).
  • the obtained polymer was continuously extracted from the die head (g) in the form of a strand via the extraction line (L3) by the extraction gear pump (e), and cut by the rotary cutter (h). .
  • the intrinsic viscosity of the obtained polymer was 0.85 dLZg, and the terminal lipoxyl group concentration was 12.2 / ie Q / g.
  • Other analytical values are summarized in Table 1. PBT with little foreign matter, excellent color tone, good transparency and excellent thermal stability was obtained.
  • Example 1 was repeated, except that the polycondensation step shown in FIG. 7 was employed.
  • the filter (f) in the polycondensation step shown in Fig. 7 a pleated cylindrical filter made of metal nonwoven fabric and having an absolute filtration accuracy of 20 m was used. PBT with further reduced foreign matter than in Example 1 was obtained.
  • the analytical values are summarized in Table 1.
  • Example 1 the supply amount of tetrabutyl titanate was adjusted so that the Ti content in the polymer was as shown in Table 1, and the pressure in the second polycondensation reaction tank (d) was changed to 100 Pa. Was performed in the same manner as in Example 1. A PBT with less foreign matter, excellent color tone, good transparency and excellent thermal stability was obtained. The analytical values are summarized in Table 1.
  • Example 1 the supply amount of tetrabutyl titanate was adjusted so that the Ti content in the polymer was as shown in Table 1, and the temperature of the second polycondensation reaction tank (d) was changed to 250 ° C. Performed in the same manner as in Example 1. PBT with little foreign matter, excellent color tone, good transparency and excellent thermal stability was obtained. The analytical values are summarized in Table 1.
  • Example 1 Same as Example 1 except that the polycondensation step shown in FIG. 8 was employed in Example 1. I went to. At this time, the same conditions as in Example 1 were used up to the second polycondensation reaction tank (d). The internal temperature of the third polycondensation reaction tank (k) was 240 ° C, the pressure was 13 OPa, The time was 60 minutes. PBT with less foreign matter, excellent color tone, good transparency, excellent thermal stability, and a higher molecular weight than Example 1 was obtained. The analytical values are summarized in Table 1.
  • Example 6 was carried out in the same manner as in Example 6, except that the polycondensation step shown in FIG. 9 was employed.
  • the filter (f) in the polycondensation step shown in FIG. 9 a pleated cylindrical filter made of metal nonwoven fabric and having an absolute filtration accuracy of 20 m was used. PBT in which the amount of foreign substances was further reduced than in Example 6 was obtained.
  • the analytical values are summarized in Table 2.
  • Example 7 the same conditions as in Example 1 were performed up to the second polycondensation reaction tank (d).
  • the internal temperature of the third polycondensation reaction tank (k) was 245 ° C, the pressure was 13 OPa, and the The time was 70 minutes.
  • a higher viscosity PBT resin was obtained than in Example 7.
  • Example 1 the catalyst supply line (3) in the esterification step shown in Fig. 1 was connected to the raw material supply line (1), and the recirculation line (2) was located in the gas phase of the reaction tank (A). The procedure was carried out except that the supply amount of the 1,4-butanediol solution of tetrabutyl titanate was 194 g / h and the supply amount of the bottom component of the rectification column (C) was 17.1 kg. Performed as in Example 1. As shown in the table, haze and color tone deteriorated, and there were many foreign substances. Table 2 summarizes the analytical values. Comparative Example 2
  • reaction start time was a point when a predetermined temperature and a predetermined pressure were reached.
  • Example 1 the catalyst supply line (3) in the esterification step shown in Fig. 1 was connected to the raw material supply line (1), and the recirculation line (2) was located in the gas phase of the reaction tank (A).
  • the feed rate of the 1,4-butanediol solution of tetrabutyl titanate was 194 gZh, and the feed rate of the bottom component of the rectification column (C) was 17.1 kg.
  • the procedure was performed in the same manner as in Example 1 except that the polymerization step shown in FIG. 8 was employed.
  • Example 2 the same procedure as in Example 1 was performed up to the second polymerization reaction tank (d), the internal temperature of the third polymerization reaction tank (k) was 240 ° C, the pressure was 13 OPa, and the residence time was 60 minutes. .
  • the obtained PBT had many foreign substances and high haze and b-value.
  • the analytical values are summarized in Table 2.
  • Example 6-PBT 60 71 29 Melt mass flow rate g / 10min. 28 24 45 Tensile strength MPa 53 52 54 Tensile elongation at break 0/100 120 90 Mechanical properties Bending strength MPa 80 79 82 Flexural modulus MPa 2280 2200 2350 Impact strength KJ / m 4.0 4.4.3 3. 3 Before wet heat treatment 53 52 54 Tensile strength: MPa
  • Penyu erythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) probionate] (Ciba-Geigy, product name: Irgano xl 010)
  • Penyu erythritol tetrakis (3-dodecylthiopropionate) (Cipro Kasei Co., Ltd., trade name: SEENOX412 S)
  • Examples 17 to 18 and Comparative Examples 11 to 13 (Releasable PBT compositions) The following (1) and (2) were added to 100 parts by weight of each of the PBT obtained in Example 1, Comparative Example 1 and Comparative Example 2. The components were blended in the composition shown in Table 7, melt-kneaded at 260 ° C by a twin-screw extruder, extruded into strands and pelletized.
  • the molecular weight of the above-mentioned monmonic acid ester was measured by a melt viscosity method as follows. Fill the thermostatic oil bath with polyethylene glycol, adjust the atlantic viscometer to 135 ° C, hold the viscometer vertically, dilute the required amount of wax with decalin, and let the automatic viscometer flow the sample solution down. The number was measured and converted to the molecular weight.
  • ISO test pieces were formed from the above pellets, and the releasability was also evaluated. In addition, the resistance to water decomposition was evaluated. Table 7 shows the results.
  • Examples 19 to 20 and Comparative Examples 14 to 15 (Hydrolysis-resistant PBT composition) The following (1) and (2) were used for 100 parts by weight of each PBT pellet of Example 1, Comparative Example 1, and Comparative Example 2. ) was blended with the composition shown in Table 8 and pelletized in the same manner as in Example 9.
  • Brominated aromatic compound poly (pentabromobenzyl acrylate) (Buchi Mochem Far East Co., Ltd., trade name: PBBPA—FR1025)
  • PTFE Polytetrafluoroethylene
  • UL-94 test specimens (1/32 inch) were molded from the above pellets and tested for flammability according to UL-94.
  • UL-94 specimens were molded with an injection molding machine (Nippon Steel Works: Model J28SA) at a cylinder temperature of 270 ° (: 80 ° C). The pieces were molded, the hydrolysis resistance was evaluated, and the generated gas was measured from the pellets.
  • PBT with titanium atoms of 33 ppm or less brominated aromatic compound flame retardant (PBBPA), antimony compound (antimony trioxide), anti-drip agent (PTFE), reinforced filler
  • PBBPA brominated aromatic compound flame retardant
  • antimony compound antimony trioxide
  • PTFE anti-drip agent
  • reinforced filler By blending (glass fiber), it was possible to obtain a PBT composition having excellent hydrolysis resistance and flame retardancy and generating less gas.
  • Examples 25 to 27 and Comparative Examples 20 to 21 (Non-halogen flame-retardant PBT compositions) The following (1) to 100 parts by weight of each PBT of Example 1, Comparative Example 1, and Comparative Example 2 The component (7) was blended with the composition shown in Table 11, and pelletized in the same manner as in Example 10. 16471
  • PPE Polyphenylene ether
  • PC Polycarbonate resin
  • Zinc borate (Polux Japan Co., Ltd., trade name: FirebrakeZB)
  • UL-94 test pieces (1Z32 inch) were molded from the above pellets and tested for flammability according to UL-94.
  • UL-94 specimens were molded with an injection molding machine (Nippon Steel Works: Model J28SA) at a cylinder temperature of 270 ° (: 80 ° C). The test pieces were molded and evaluated for hydrolysis resistance. Table 11
  • PC Polycarbonate resin
  • Phosphorus compound octadecyl acid phosphate [Asahi Denka Kogyo Co., Ltd., trade name: AX-71 (mixture of monoalkyl and dialkyl)]
  • the cooling crystallization temperature of the pellet was measured by DSC. Further, ISO test pieces were prepared from the above pellets, and the tensile strength, the bending strength, the bending elastic modulus, and the Charpy impact value were measured. In addition, hydrolysis resistance was evaluated. The results are shown in Tables 14 and 15.
  • hydrolysis resistance is obtained by blending polyethylene terephthalate or polypropylene terephthalate and reinforced filler (glass fiber) with PBT having titanium atoms of 33 ppm or less.
  • a PBT composition having excellent crystallization temperature and high crystallization temperature was obtained.
  • Examples 35 to 39 and Comparative Examples 29 to 32 (Other Functional PBT Compositions 1 to 3) The following (1) was used for 100 parts by weight of each PBT pellet of Example 1, Comparative Example 1, and Comparative Example 2.
  • Components (4) to (4) were blended in the compositions shown in Tables 16 and 17, and pelletized in the same manner as in Example 10.
  • HI PS rubber (polybutadiene) content 8.8% by weight, average rubber particle diameter 1.8 m, number average molecular weight 92,000, weight average molecular weight 230,000, melt flow rate (temperature 200 ° C , Load 5Kg f) 1.8 g / 10 minutes rubber-modified polystyrene resin (A & M, product name: Dialex HT478)
  • PC Polycarbonate resin
  • ISO test pieces were prepared from the above pellets, and the tensile strength, bending strength, flexural modulus, and Charpy impact value were measured. In addition, hydrolysis resistance was evaluated. The results are shown in Tables 16 and 17. .
  • a S--43-43 Composition (parts by weight)
  • a single-layer film was obtained in the following manner.
  • a T-die with a width of 600 mm and a lip opening of 0.4 mm was attached to the tip of the extruder, and extruded into a curtain with a resin temperature of about 260 ° C and a discharge rate of 5 Kg / hr.
  • the extruded resin was continuously extruded onto a mirror-finished metal opening that rotates at a surface temperature of 60 ° (peripheral speed of about 3 mZ) and quenched to obtain a single-layer film.
  • the results are shown in Table 18.
  • a composite film was prepared in the following manner according to the coextrusion method.
  • the equipment used was a three-type, three-layer water-cooled multilayer blown film forming machine.
  • the extruder for the outer layer has a diameter of 40 ⁇
  • the extruders for the middle layer and the inner layer have a diameter of 40 ⁇
  • a composite film was produced in the following manner according to the dry lamination method. That is, first, a two-component dry laminating adhesive (manufactured by Toyo Moton Co., Ltd .: main agent (TM-51), hardener 5 (CA T-RT8)) was used for the above PBT film using Barco Ichiichi. (6/1 weight ratio mixture) was applied so as to have a dry weight of 5 g / m 2 and dried.
  • TM-51 main agent
  • CA T-RT8 hardener 5
  • films, monofilaments, fibers, electrical and electronic parts, automobile parts, etc. which are excellent in color tone, hydrolysis resistance, thermal stability, transparency, and formability, and have reduced foreign matter
  • the present invention provides PBT of stable quality that can be suitably used for the present invention, and the industrial value of the present invention is remarkable.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2003/016471 2002-12-27 2003-12-22 ポリブチレンテレフタレート及びその製造方法ならびにその組成物およびフィルム WO2004060961A1 (ja)

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AU2003289485A AU2003289485A1 (en) 2002-12-27 2003-12-22 Polybutylene terephthalate and method for production thereof, and composition comprising the same and film

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JP2002381124 2002-12-27
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JP2003160711A JP2004307794A (ja) 2003-02-18 2003-06-05 ポリブチレンテレフタレート及びその組成物
JP2003173487A JP2005008736A (ja) 2003-06-18 2003-06-18 ポリブチレンテレフタレートフィルム及び複合化フィルム
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110496575A (zh) * 2019-07-17 2019-11-26 江苏新东风化工科技有限公司 一种酯化生产后处理系统及其处理工艺
CN114621422A (zh) * 2021-04-07 2022-06-14 江苏睿安应用生物技术股份有限公司 一种连续快速生产聚酯产品的方法及其应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007026650A1 (ja) * 2005-08-29 2007-03-08 Mitsubishi Chemical Corporation ポリブチレンテレフタレート及びその製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0869141A1 (en) * 1997-03-31 1998-10-07 Toray Industries, Inc. Method for producing polybutylene terephthalate
JP2002080574A (ja) * 2000-09-05 2002-03-19 Toray Ind Inc ポリエステルの製造方法
JP2003012781A (ja) * 2001-04-24 2003-01-15 Mitsubishi Engineering Plastics Corp ポリブチレンテレフタレート樹脂及び成形品

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0869141A1 (en) * 1997-03-31 1998-10-07 Toray Industries, Inc. Method for producing polybutylene terephthalate
JP2002080574A (ja) * 2000-09-05 2002-03-19 Toray Ind Inc ポリエステルの製造方法
JP2003012781A (ja) * 2001-04-24 2003-01-15 Mitsubishi Engineering Plastics Corp ポリブチレンテレフタレート樹脂及び成形品

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110496575A (zh) * 2019-07-17 2019-11-26 江苏新东风化工科技有限公司 一种酯化生产后处理系统及其处理工艺
CN114621422A (zh) * 2021-04-07 2022-06-14 江苏睿安应用生物技术股份有限公司 一种连续快速生产聚酯产品的方法及其应用
CN114621422B (zh) * 2021-04-07 2024-02-13 广州德恒致远科技有限公司 一种连续快速生产聚酯产品的方法及其应用

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