CN100434452C - Polybutylene terephthalate and method for production thereof, and composition comprising the same and film - Google Patents

Polybutylene terephthalate and method for production thereof, and composition comprising the same and film Download PDF

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CN100434452C
CN100434452C CNB2003801099122A CN200380109912A CN100434452C CN 100434452 C CN100434452 C CN 100434452C CN B2003801099122 A CNB2003801099122 A CN B2003801099122A CN 200380109912 A CN200380109912 A CN 200380109912A CN 100434452 C CN100434452 C CN 100434452C
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polybutylene terephthalate
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pbt
weight
film
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CN1753930A (en
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山本正规
上坂贵洋
藤野秀之
足立政弘
田尻敏之
庄司英和
杉浦克彦
岸本伸太郎
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Mitsubishi Chemical Corp
Mitsubishi Rayon Co Ltd
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Mitsubishi Kasei Corp
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Abstract

A polybutylene terephthalate (PBT) which contains titanium and has a titanium content of 33 ppm or less; and a composition comprising the polybutylene terephthalate. In a preferred embodiment, the polybutylene terephthalate exhibits a crystallization temperature in the course of the decrease of temperature of 170 to 190 DEG C, has a concentration of a terminal vinyl group of 0.1 to 10 mueq/g, exhibits a haze of its specific solution of 10 % or less, exhibits an increase of the concentration of a terminal carboxyl group of 0.1 to 30 mueq/g after being heat-treated under specific conditions, and contains foreign particles having a size of 5 mum or larger in an amount of 50 pieces/10 g-polymer or less. The PBT and a composition comprising the PBT are excellent in color tone, hydrolysis resistance, heat stability, transparency and processability, and is reduced in the content of foreign matter, and thus can be suitably used for a film, a monofilament, a fiber, an electric or electronic part, an automobile part or the like.

Description

Polybutylene terephthalate and manufacture method thereof with and composition and film
Technical field
The present invention relates to polybutylene terephthalate and manufacture method thereof and composition and film.In detail, the present invention relates to tone, hydrolytic resistance, thermostability, the transparency, have excellent formability, and, can reduce foreign matter, applicable to the polybutylene terephthalate of film, monofilament, fiber, electrical and electronic parts, trolley part etc. and manufacture method thereof with and composition and film.
Background technology
The polybutylene terephthalate of the engineering plastics of conduct representative in thermoplastic polyester, process complexity, mechanical properties, thermotolerance, resistance, fragrance protectiveness, other excellent physics, chemistry owing to be shaped, be used in the injection molded article of trolley part, electrical and electronic parts, precision machinery parts etc. widely.In recent years, effectively utilize its excellent character, also be widely used in fields such as film, sheet, monofilament, fibers and come.
We know, in general, its end carboxy concentration of polyester is high more, hydrolytic resistance is poor more (for example, on December 22nd, 1989, the 192nd～193 page of Nikkan Kogyo Shimbun distribution " saturated polyester resin handbook "), in polybutylene terephthalate, the end carboxy concentration height, hydrolysis reaction speed under damp and hot also becomes greatly, because the molecular weight that causes of hydrolysis reduces and then cause the serious problems such as reduction of mechanical properties etc.
In addition,, when moulding, cause the rising of end carboxy concentration once more because common melt-shaping is to carry out at the fusing point of polybutylene terephthalate or more than the fusing point, in the goods after becoming shaping, the problem that has hydrolytic resistance to worsen more.
In order to solve the above problems, in a single day the polybutylene terephthalate that melt polymerization is obtained solidifies, make it again to carry out solid state polymerization at its fusing point or the temperature below the fusing point, thus the method (for example, the spy opens flat 9-316183 communique) that terminal carboxyl concentration is reduced., as described above, in original polybutylene terephthalate, though by solid state polymerization terminal carboxyl concentration is reduced, when moulding, causes the rising of end carboxy concentration once more, in the goods after becoming shaping, the problem that has the effect that makes solid state polymerization to diminish.
On the other hand, particularly in purposes such as film, sheet, monofilament, fiber since commodity value be subjected to a great extent foreign matter, blushing, painted etc. about, so require the reduction or the improvement of these problems consumingly.Foreign matter in polybutylene terephthalate or blushing are considered to except the general resin deterioration thing that is called as focal spot or the burnt material of mouthful mould, and the inactivation material or the condensed matter of the metallic compound that adds as catalyzer also are its reasons.
Therefore, proposed terephthalic acid and 1,4-butyleneglycol successive esterification is divided into 2 stages, in the esterification in the 1st stage, only be added with machine tin compound, in the esterification in the 2nd stage, add organic titanic compound, thereby reduce from the foreign matter of catalyzer or the method for blushing (for example, the spy opens flat 10-330468 communique).
, because the metal concentration height in the polybutylene terephthalate that finally obtains, the reduction effect of foreign matter or blushing is limited, because these metallic compounds cause producing the problem (with reference to patent documentation 4) of the deterioration or the stable on heating deterioration of polymkeric substance tone.In addition, the rising of the end carboxy concentration during above-mentioned fusion, because metallic compound is accelerated as catalyzer, the result also has the shortcoming that causes hydrolytic resistance to worsen.
The simple declaration of accompanying drawing
Fig. 1 is the explanatory view of an example of the esterification operation that adopts in the present invention or transesterification reaction operation.
Fig. 2 is the esterification operation of employing in the present invention or another routine explanatory view of transesterification reaction operation.
Fig. 3 is the esterification operation of employing in the present invention or another routine explanatory view of transesterification reaction operation.
Fig. 4 is the esterification operation of employing in the present invention or another routine explanatory view of transesterification reaction operation.
Fig. 5 is the esterification operation of employing in the present invention or another routine explanatory view of transesterification reaction operation.
Fig. 6 is the explanatory view of an example of the polycondensation step that adopts in the present invention.
Fig. 7 is another routine explanatory view of the polycondensation step that adopts in the present invention.
Fig. 8 is another routine explanatory view of the polycondensation step that adopts in the present invention.
Fig. 9 is another routine explanatory view of the polycondensation step that adopts in the present invention.
Summary of the invention
The present invention makes in view of above-mentioned truth, its purpose is to provide a kind of tone, hydrolytic resistance, thermostability, the transparency, has excellent formability, and the foreign matter minimizing, applicable to the polybutylene terephthalate and the manufacture method thereof of film, monofilament, fiber, electrical and electronic parts, trolley part etc. and contain this polybutylene terephthalate, and have the polybutylene terephthalate composition and the film of various functions.
Present inventors, carried out deep research for solving above-mentioned problem, found that, if carry out esterification or transesterification reaction under given conditions, can improve the utilising efficiency of catalyzer, the usage quantity of catalyzer is significantly reduced, its result, obtain the novel polybutylene terephthalate that the catalyzer amount obviously reduces, thus, can easily solve above-mentioned problem.Also find in addition, by carrying out esterification or transesterification reaction under given conditions, can improve transformation efficiency, reduce foreign matter, suppress side reaction.
The present invention is based on above-mentioned idea and finishes, and its 1st main points is a kind of polybutylene terephthalate, it is characterized in that this polybutylene terephthalate contains titanium, and is 33ppm or below the 33ppm in its content of titanium atom.
The 2nd main points of the present invention are a kind of manufacture method of polybutylene terephthalate, it is characterized in that, in the esterification groove, in the presence of titanium catalyst, have and supply with terephthalic acid and 1 continuously, the 4-butyleneglycol carries out in the manufacture method of polybutylene terephthalate of process of esterification, with 1, at least a portion of 4-butyleneglycol does not supply to the esterification groove independently with terephthalic acid, and this part 1 of esterification groove will be supplied to independently, 10 weight % in the 4-butyleneglycol or offer the liquid phase part of reaction solution more than the 10 weight % are with 10 weight % of titanium catalyst or do not supply to the liquid phase part of reaction solution more than the 10 weight % independently with terephthalic acid.
The 3rd main points of the present invention are a kind of manufacture method of polybutylene terephthalate, it is characterized in that, in the transesterification reaction groove, in the presence of titanium catalyst, have and supply with dimethyl terephthalate ester and 1 continuously, the 4-butyleneglycol carries out in the manufacture method of polybutylene terephthalate of process of transesterification reaction, with 1, at least a portion of 4-butyleneglycol does not supply to the transesterification reaction groove independently with dimethyl terephthalate ester, and this part 1 of transesterification reaction groove will be supplied to independently, 10 weight % in the 4-butyleneglycol or offer the liquid phase part of reaction solution more than the 10 weight % are with 10 weight % of titanium catalyst or do not supply to the liquid phase part of reaction solution more than the 10 weight % independently with terephthalic acid.
The 4th main points of the present invention are a kind of manufacture method of polybutylene terephthalate, it is characterized in that, in the esterification groove, in the presence of titanium catalyst, have and supply with terephthalic acid continuously and with respect to 1 of terephthaldehyde's excessive acid, the 4-butyleneglycol carries out in the manufacture method of polybutylene terephthalate of process of esterification, the control time per unit is supplied in the terephthalic acid and 1 of esterification groove, it is certain that the mol ratio of 4-butyleneglycol (1, the mole number of the mole number/terephthalic acid of 4-butyleneglycol) keeps.
The 5th main points of the present invention are a kind of manufacture method of polybutylene terephthalate, it is characterized in that, in the transesterification reaction groove, in the presence of titanium catalyst, have supply with continuously dimethyl terephthalate ester and with respect to dimethyl terephthalate ester excessive 1, the 4-butyleneglycol carries out in the manufacture method of polybutylene terephthalate of process of transesterification reaction, the control time per unit is supplied in the dimethyl terephthalate ester and 1 of transesterification reaction groove, it is certain that the mol ratio of 4-butyleneglycol (1, the mole number of the mole number/terephthalic acid of 4-butyleneglycol) keeps.
The 6th main points of the present invention are a kind of heat resistant poly butylene terephthalate composition, it is characterized in that, contain and be selected from the polybutylene terephthalate that the 1st main points mention and be selected from the oxidation inhibitor more than a kind or a kind in phenolic antioxidant (B1), sulfur type antioxidant (B2) and the Phosphorus oxidation inhibitor (B3).
The 7th main points of the present invention are a kind of polybutylene terephthalate composition of good release property, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts that the 1st main points are mentioned, contain the fatty acid ester (C1) of the pure residue that is selected from the fatty acid residue that contains carbonatoms 12～36 and carbonatoms 1～36 and releasing agent (C) 0.01～2 weight part of paraffin and polyethylene wax (C2).
The 8th main points of the present invention are a kind of hydrolytic resistance polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts that the 1st main points are mentioned, contain and strengthen weighting agent (D) 0～200 weight part and epoxy compounds (E) 0.01～20 weight part.
The 9th main points of the present invention are a kind of shock-resistance polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts that the 1st main points are mentioned, contain shock-resistant improvement material (F) 0.5～40 weight part and strengthen weighting agent (D) 0～200 weight part.
The 10th main points of the present invention are a kind of flame retardance poly butylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts that the 1st main points are mentioned, contain bromo aromatics based flame retardant (G) 3～50 weight parts, antimony compounds (H) 1～30 weight part, dripping inhibitor (I) 0～15 weight part and strengthen weighting agent (D) 0～200 weight part.
The 11st main points of the present invention are a kind of non-halogen fire retardant polybutylene terephthalate composition, it is characterized in that, polybutylene terephthalate 50～95 weight parts of mentioning with respect to the 1st main points and total 100 weight parts of polyphenylene oxide resin (J) 5～50 weight parts contain solubilizing agent (K) 0.05～10 weight part, be selected from least a kind compound (L) 2～45 weight parts of phosphoric acid ester or phosphonitrile, strengthen weighting agent (D) 0～200 weight part, dripping inhibitor (I) 0～15 weight part, melamine cyanurate (M) 0～45 weight part and borate metal salt (N) 0～50 weight part.
The 12nd main points of the present invention are a kind of polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts that the 1st main points are mentioned, contain polycarbonate resin (O) 5～100 weight parts, organo phosphorous compounds (P) 0.01～1 weight part, strengthen weighting agent (D) 0～200 weight part and shock-resistant modifying agent (F) 0～50 weight part.
The 13rd main points of the present invention are a kind of polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts that the 1st main points are mentioned, contain polybutylene terephthalate aromatic polyester-based resin (Q) 5～100 weight parts and reinforcement packing material (D) 0～200 weight part in addition.
The 14th main points of the present invention are a kind of polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts that the 1st main points are mentioned, contain styrene resin (R) 5～100 weight parts, maleic anhydride modified polystyrene resin (S) or polycarbonate resin (O) 0～40 weight part, strengthen packing material (D) 0～200 weight part.
The 15th main points of the present invention are a kind of film, it is characterized in that, this film contains polybutylene terephthalate, and described polybutylene terephthalate contains titanium and is 33ppm or below the 33ppm in its content of titanium atom.
The 16th main points of the present invention are a kind of film, it is characterized in that, this film contains polybutylene terephthalate 1～99 weight % and polyethylene terephthalate 1～99 weight % (still, both add up to 100 weight %), described polybutylene terephthalate contains titanium and is 33ppm or below the 33ppm in its content of titanium atom.
The 17th main points of the present invention are a kind of film, it is characterized in that, this film contain polybutylene terephthalate 1～99 weight % and copolymerization polytetramethylene glycol aromatic polyester 1～99 weight % (still, both add up to 100 weight %), described polybutylene terephthalate contains titanium and is 33ppm or below the 33ppm in its content of titanium atom.
The preferred plan that carries out an invention
＜polybutylene terephthalate 〉
Below, the present invention is described in detail.Said polybutylene terephthalate of the present invention (below, brief note is PBT), be meant and have terephthalic acid units and 1,4-butyleneglycol unit ester linkage structure, 50 moles of % of dicarboxylic acid units or 50 moles of % are above to be made of terephthalic acid units, 50 moles of % or 50 moles of % of diol component are above by 1, the polymer that 4-butyleneglycol unit constitutes.The ratio of the terephthalic acid units in whole dicarboxylic acid units, preferred 70 moles of % or 70 moles are more than the %, be more preferably 80 moles of % or 80 moles more than the %, preferred especially 95 moles of % or 95 moles are more than the %, whole 1 in diol units, the unitary ratio of 4-butyleneglycol, preferred 70 moles of % or 70 moles are more than the %, be more preferably 80 moles of % or 80 moles more than the %, preferred especially 95 moles of % or 95 moles are more than the %.Terephthalic acid units or 1,4-butyleneglycol unit than 50 moles of % after a little while, the crystallization speed of PBT reduces, and causes the deterioration of plasticity.
In the present invention, have no particular limits for the dicarboxylic acid composition beyond the terephthalic acid, can enumerate, for example, phthalic acid, m-phthalic acid, 4,4 '-diphenyl dicarboxylic acid, 4,4 '-phenyl ether dicarboxylic acid, 4,4 '-benzophenone dicarboxylic acid, 4,4 '-biphenoxyl ethane dicarboxylic acid, 4,4 '-sulfobenzide dicarboxylic acid, 2, aromatic dicarboxylic acids such as 6-naphthalic acid, 1, the 2-cyclohexane dicarboxylic acid, 1, the 3-cyclohexane dicarboxylic acid, 1, ester ring type dicarboxylic acid such as 4-cyclohexane dicarboxylic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, aliphatic dicarboxylic acids such as sebacic acid etc.These dicarboxylic acid compositions, can be used as dicarboxylic acid or with dicarboxylic acid derivatives such as dicarboxylic ester, dicarboxylic acid carboxylic acid halides as raw material, import in the polymer backbone.
In the present invention, to 1, diol component beyond the 4-butyleneglycol has no particular limits, can enumerate, for example, ethylene glycol, Diethylene Glycol, polyoxyethylene glycol, 1, the 2-propylene glycol, 1, ammediol, polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1, the 5-pentanediol, neopentyl glycol, 1, the 6-hexylene glycol, 1, aliphatic diols such as 8-ethohexadiol, 1, the 2-cyclohexanediol, 1, the 4-cyclohexanediol, 1, the 1-hydroxymethyl-cyclohexane, 1, ester ring type glycol such as 4-hydroxymethyl-cyclohexane, the xylylene glycol, 4,4 '-dihydroxybiphenyl, 2, two (4-hydroxyphenyl) propane of 2-, aromatic diols such as two (4-hydroxyphenyl) sulfone etc.
In the present invention, trifunctionals such as simple function composition, tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, trihydroxybenzoic acid, trimethylolethane, TriMethylolPropane(TMP), glycerine, tetramethylolmethane such as lactic acid, oxyacetic acid, m-Salicylic acid, P-hydroxybenzoic acid, 6-hydroxyl-2-naphthoic acid, right-hydroxycarboxylic acids such as beta-hydroxy ethoxybenzoic acid, alkoxyl group carboxylic acid, stearyl alcohol, phenylcarbinol, stearic acid, phenylformic acid, p t butylbenzoic acid, benzoylbenzoic acid or the multifunctional one-tenth more than the trifunctional can also be graded and use as copolymer composition.
PBT of the present invention is 1, when the esterification (or transesterification reaction) of 4-butyleneglycol and terephthalic acid (or terephthalic acid dialkyl), uses titanium catalyst and obtains as catalyzer.
Can use common titanium compound as titanium catalyst, as its concrete example, can enumerate titanium phenolate things such as titanium alcoholate, tetraphenyl titanic acid ester such as inorganic titanium compounds such as titanium oxide, titanium tetrachloride, metatitanic acid tetramethyl ester, titanium isopropylate, tetrabutyl titanate etc.Wherein, preferred tetralkyl titanate, this wherein, preferred tetrabutyl titanate.
Except titanium, tin also can be used as catalyzer and uses.Tin uses as tin compound usually, as its concrete example, can enumerate dibutyl tin oxide, oxidation methyl phenyltin, tin tetraethyl, oxidation triethyltin, oxidation ring six hexyls two tin, bis oxide dodecyl tin, stannic ethyl hydroxide, hydroxide triphenyltin, acetate triisobutyl tin, dibutyltin diacetate, two lauric acid tin diphenyls, trichlorine Monobutyltin, tributyltin chloride, butyl disulfide tin, oxidation butylhydroxy tin, stannoacetic acid, ethyl stannonic acid, butyl stannonic acid etc.
In addition, except titanium, can also use calcium cpds such as magnesium compounds such as magnesium acetate, magnesium hydroxide, magnesiumcarbonate, magnesium oxide, magnesium alkoxide, secondary magnesium phosphate, calcium acetate, calcium hydroxide, lime carbonate, calcium oxide, pure calcium, secondary calcium phosphate, and germanium compounds such as antimony compounds, germanium dioxide, four germanium oxides such as ANTIMONY TRIOXIDE SB 203 99.8 PCT, manganic compound, zn cpds, zirconium compounds, cobalt compound, ortho-phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, Tripyrophosphoric acid, their ester or reaction promoters such as phosphorus compound, sodium hydroxide, Sodium Benzoate such as metal-salt.
When above-mentioned catalyzer or reaction promoter, esterification (or transesterification reaction) they are a plurality of reactive tank, can portion-wise addition, in addition, also can append in the successive polycondensation stage.
PBT of the present invention is characterized in that, contains titanium and is 33ppm or below the 33ppm in its content of titanium atom.Above-mentioned value is the weight ratio with respect to the atom of PBT.In the present invention, the lower limit of above-mentioned titanium content is generally 1ppm, and preferred 3ppm is more preferably 5ppm, preferred especially 8ppm, very preferred 15ppm.The upper limit of titanium content, preferred 30ppm is more preferably 27ppm.The content of titanium than 33ppm for a long time, deteriorations such as tone, hydrolytic resistance, the transparency, plasticity, and, the tendency that also has foreign matter to increase, than 1ppm after a little while, polymerizability worsens sometimes.
In the present invention, can use tin catalyst with titanium catalyst.Usually and since tin catalyst compare catalysis with titanium catalyst can be low, so compare the more addition of needs with titanium catalyst., if the usage quantity of tin catalyst too much will cause the deterioration of tone, and tin also has toxicity.Therefore, the usage quantity of tin catalyst is generally 100ppm or below the 100ppm, and preferred 50ppm or below the 50ppm is more preferably 20ppm or below the 20ppm, best scheme is not use tin catalyst.After the amount of titanium atom etc. can use method such as wet type burning to reclaim the metal in the polymkeric substance, use that atom is luminous, atom extinction, Induced Coupled Plasma methods such as (ICP) measure.
The limiting viscosity of PBT of the present invention is generally 0.60～2.00dL/g, and preferred 0.65～1.50dL/g is more preferably 0.75～1.30dL/g.Limiting viscosity is during less than 0.60dL/g, and the physical strength of molding is insufficient, when surpassing 2.00dL/g, has melt viscosity to uprise, the mobile deterioration, the tendency that plasticity worsens.Above-mentioned limiting viscosity is to use the mixed solvent of phenol/tetrachloroethane (weight ratio 1/1), 30 ℃ of values of measuring down.
In the present application, also can and use the different PBT more than 2 kinds or 2 kinds of limiting viscosity.At this moment, the limiting viscosity of a plurality of PBT of use is in the scope of 0.60 above-mentioned～2.00dL/g to well with any one, in addition, also is preferably person in the above-mentioned scope as the limiting viscosity of composition.For example, the PBT (A1) of limiting viscosity 0.60～0.90dL/g and the PBT (A2) of limiting viscosity 0.91～1.50dL/g can be used with 5: 95～95: 5 mixed of weight ratio.
The end carboxy concentration of PBT of the present invention is generally 0.1～35 μ eq/g, and preferred 1～25 μ eq/g is more preferably 1～20 μ eq/g, preferred especially 1～15 μ eq/g.When end carboxy concentration was too high, the hydrolytic resistance of PBT worsened.
End carboxy concentration, preferred molecular weight is little, and alap in the lower molecular weight scope that is subjected to the influence that molecular weight that hydrolysis causes reduces easily.That is, the formula (I-1) below recommending to satisfy, preferred formula (I-2) is more preferably formula (I-3), special preferred formula (I-4).
20×IV+6≥[COOH]≥20×IV-12 (I-1)
20×IV+4≥[COOH]≥20×IV-12 (I-2)
20×IV+2≥[COOH]≥20×IV-12 (I-3)
20×IV≥[COOH]≥20×IV-12 (I-4)
(wherein, [COOH] is end carboxy concentration (unit is μ eq/g), [COOH]＞0, IV characterization viscosity).
In addition, if the end carboxy concentration of PBT reduces, but when mixing or during moulding because heat causes when rising that the result not only can make the hydrolytic resistance of goods worsen, but also cause the generation of gases such as tetrahydrofuran (THF).Therefore, at nitrogen, helium, argon gas etc. not under the reactive gas atmosphere, the rising at 245 ℃ of end carboxy concentrations of removing hydrolysis reaction when carrying out 40 minutes thermal treatment is generally 0.1～30 μ eq/g, preferred 1～10 μ eq/g is more preferably 1～8 μ eq/g.Usually, the content of catalytic specie is low, also has molecular weight high, and the rising of the end carboxy concentration when the heating has the tendency that diminishes.
In above-mentioned evaluation assessment, stipulated temperature or time be because, if temperature is crossed low or the time is too short, then the speed of the rising of end carboxy concentration is too small, opposite occasion, excessive then the evaluation becomes incorrect.In addition, if estimate under extremely high temperature, take place simultaneously to generate terminal carboxyl(group) side reaction in addition, estimating and becoming incorrect also is one of its reason.In this heat-treat condition, the reduction of the number-average molecular weight that the hydrolysis reaction reaction in addition that is caused by the moisture that is included among the PBT causes can be ignored, can think the rising part of the end carboxy concentration that causes by hydrolysis reaction and the terminal hydroxyl concentration before and after the thermal treatment rising part much at one, therefore, the rising part of the end carboxy concentration that is caused by the pyrolysis beyond the hydrolysis reaction that becomes problem when mixing or during moulding can be obtained with following formula (II).
ΔAV(d)＝ΔAV(t)-ΔAV(h)＝ΔAV(t)-ΔOH (II)
At this, the variable quantity of the end carboxy concentration that Δ AV (d) expression is caused by pyrolysis, whole variable quantities of the end carboxy concentration before and after Δ AV (t) the expression thermal treatment, the variable quantity of the end carboxy concentration that Δ AV (h) expression is caused by hydrolysis reaction, Δ OH represents the variable quantity of the terminal hydroxyl concentration before and after the thermal treatment.
From the viewpoint of the reliability of pyrolysis evaluation, the selective hydrolysis reaction is few, and the water content that is used for heat treated PBT is recommended 300ppm or below the 300ppm usually.Terminal hydroxyl concentration before and after the thermal treatment, can by 1H-NMR is quantitative.
The end carboxy concentration of PBT can use alkaline solution titration such as sodium hydroxide solution to try to achieve by PBT being dissolved in organic solvent etc. then.
In addition, the terminal ethylenyl groups concentration of PBT of the present invention is generally 15 μ eq/g or below the 15 μ eq/g, preferred 0.1～10 μ eq/g is more preferably 1～8 μ eq/g, preferred especially 1～5 μ eq/g.During the terminal ethylenyl groups excessive concentration, become the reason of tone deterioration or solid state polymerization deterioration.Productivity is reduced, and when producing the low PBT of the PBT that molecular weight is big or catalyst concn, because general requirement improves polymerization temperature or prolong the reaction times, so terminal ethylenyl groups concentration has the tendency of rising.Terminal ethylenyl groups concentration can be measured by PBT being dissolved in the mixed solvent of deuterochloroform/hexafluoroisopropanol=7/3 (volume ratio) 1H-NMR carries out quantitatively.
At the end of PBT, beyond hydroxyl-removal, carboxyl, the vinyl, the remaining sometimes methoxycarbonyl from raw material is when particularly dimethyl terephthalate (DMT) is as raw material, remaining sometimes a lot., the methoxycarbonyl end by the heat that is produced by solid state polymerization, mixing, moulding etc., produces methyl alcohol, formaldehyde, formic acid, and particularly, when being used in food uses, the toxicity of these materials becomes problem.In addition, formic acid can damage metal forming machine or the machine relevant with vacuum.Therefore, the terminal methoxycarbonyl concentration among the present invention is generally 0.5 μ eq/g or below the 0.5 μ eq/g, and preferred 0.3 μ eq/g or below the 0.3 μ eq/g is more preferably 0.2 μ eq/g or below the 0.2 μ eq/g, preferred especially 0.1 μ eq/g or below the 0.1 μ eq/g.
Each above-mentioned end group concentration beyond the terminal carboxyl(group) can be measured by PBT being dissolved in deuterochloroform/hexafluoroisopropanol=7/3 (volume ratio) 1H-NMR carries out quantitatively.At this moment, in order to prevent overlapping with solvents signals, can add the alkaline components such as deuterated pyridine of minute quantity etc.
The decrease temperature crystalline temperature of PBT of the present invention is generally 170～200 ℃, preferred 172～195 ℃, is more preferably 175～190 ℃.So-called decrease temperature crystalline temperature of the present invention is the temperature of the exothermal peak that caused by the crystallization that uses differential scanning calorimeter to show when resin fused state begins speed of cooling cooling with 20 ℃/min.The decrease temperature crystalline temperature is corresponding with crystallization speed, because the decrease temperature crystalline temperature is high more, crystallization speed is fast more, when injection forming, can shorten cooling time, boosts productivity.When the decrease temperature crystalline temperature was hanged down, when injection forming, crystallization needed the time, became to have to prolong cooling time behind the injection forming, had the prolongation shaping cycle, reduced the tendency of productivity.
The solution mist value of PBT of the present invention, have no particular limits, for the PBT with 2.7g is dissolved in the solution mist value in the mensuration in 20mL phenol/tetrachloroethane mixed solvent (weight ratio 3/2), be generally below 10% or 10%, below preferred 5% or 5%, be more preferably below 3% or 3%, below preferred especially 1% or 1%.Since when the solution mist value is high, transparency deterioration is arranged, the tendency that foreign matter also increases, and therefore at film, monofilament, fiber etc., particularly when requiring the purposes of the transparency, commodity value significantly reduces.The solution mist value, many at catalyst content, or catalyst deactivation has the tendency of rising when big.
In addition, the length 5 μ m or the foreign matter more than the 5 μ m that contain in PBT of the present invention are generally 60/10g polymkeric substance or below the 60/10g polymkeric substance.Particularly, the foreign matter in the raw material PBT resins such as film, monofilament, preferred below 50 or 50 when being used for the purposes of left and right sides product property to a great extent, be more preferably below 40 or 40, preferred especially below 30 or 30.
Above-mentioned foreign matter amount, can be by the PBT of 10g be dissolved in the mixed solvent of hexafluoroisopropanol/chloroform=2/3 (volume ratio) with the concentration of 20 weight %, after the membrane filter made from the tetrafluoroethylene of aperture 5 μ m filters, fully clean with this mixed solvent, try to achieve with the method for foreign matter amount residual on the observation by light microscope counting filter.
Then, the manufacture method to PBT of the present invention describes.The manufacture method of PBT from the raw material aspect, is divided into dicarboxylic acid as the so-called direct polymerization method of main raw material use and the ester-interchange method that dicarboxylic acid dialkyl esters is used as main raw material.Both differences are, generate water in the former esterification in the early stage, generate alcohol in latter's transesterification reaction in the early stage.
In addition, the manufacture method of PBT can be divided into interrupter method and continuous processing from the output form of raw material supplying or polymkeric substance.The esterification or the transesterification reaction at initial stage carried out in also useful operate continuously, carries out polycondensation with periodical operation then, or opposite, carries out the esterification or the transesterification reaction at initial stage, the method for carrying out polycondensation then with operate continuously with periodical operation.
In the present invention, from the cost height of the easy degree of the processing of the acquisition stability of raw material, overhead product, raw material unit consumption, by the viewpoints such as improved effect that the present invention produces, preferred direct polymerization method.In addition, in the present invention,, adopt base feed continuously, carry out the method for esterification or transesterification reaction continuously from the stability of productivity or product property, by the viewpoints such as improved effect that the present invention produces.And, in the present invention, the preferred polycondensation of after esterification or transesterification reaction, then the carrying out so-called continuous processing of also carrying out continuously.
In the present invention, preferably adopt in esterification groove (or transesterification reaction groove), in the presence of titanium catalyst, on one side with 1 of at least a portion, the 4-butyleneglycol does not supply in the esterification groove (or transesterification reaction groove) independently with terephthalic acid (or dimethyl terephthalate ester), with terephthalic acid (or dimethyl terephthalate ester) and 1, the 4-butyleneglycol carries out the operation of esterification (or transesterify) continuously on one side.
Promptly, in the present invention, in order to reduce blushing or foreign matter from catalyzer, and catalyst activity is reduced, as former slip or solution, with terephthalic acid or dimethyl terephthalate ester supply with 1,4-butyleneglycol difference, but not with terephthalic acid or dimethyl terephthalate ester and independent supply with 1, the 4-butyleneglycol supplies in esterification groove or the transesterification reaction groove.After, sometimes with this 1, the 4-butyleneglycol is called " supply with in addition 1,4-butyleneglycol ".
Above-mentioned " supply with in addition 1,4-butyleneglycol " can serve as that it doesn't matter is fresh 1 with technology, the 4-butyleneglycol.In addition, " supply with in addition 1; the 4-butyleneglycol ", can with collections such as condenser from esterification groove or transesterification reaction groove distill out 1, the 4-butyleneglycol, former state ground, or in temporarily being saved in jar etc., and then be back in the reactive tank, perhaps separate, refining impurity, as having improved 1 of purity, the 4-butyleneglycol is supplied with.After, sometimes will by collect with condenser etc. 1, " supply with in addition 1,4-butyleneglycol " that the 4-butyleneglycol constitutes is called " recirculation 1,4-butyleneglycol ".From the viewpoint of the simplification of resources effective utilization, equipment, preferably " recirculation 1,4-butyleneglycol " served as " supply with in addition 1,4-butyleneglycol ".
In addition, by esterification groove or transesterification reaction groove distill out 1, the 4-butyleneglycol except 1, beyond the 4-butyleneglycol composition, contains compositions such as water, alcohol, tetrahydrofuran (THF), dihydrofuran usually.Therefore, 1 of above-mentioned overhead product, the 4-butyleneglycol, preferably after collecting with condenser etc., perhaps, while collect compositions such as separation, Purified Water, alcohol, tetrahydrofuran (THF), and turn back in the reactive tank.
And, in the present invention, preferably in " 1 of other supply, 4-butyleneglycol ", directly turn back in the reaction solution liquid phase part with 10 weight % or more than the 10 weight %.At this, so-called reaction solution liquid phase part, liquid phase one side of the liquid-gas interface in expression esterification groove or the transesterification reaction groove, the so-called reaction solution liquid phase part that directly turns back to, be that pipe arrangement etc. is used in expression, " 1 of other supply, 4-butyleneglycol " without the gas phase part, directly supplies to liquid phase part.Directly turn back to the ratio of reaction solution liquid phase part, preferred 30 weight % or more than the 30 weight % are more preferably 50 weight % or more than the 50 weight %, preferred especially 80 weight % or more than the 80 weight %, the most preferred 90 weight % or more than the 90 weight %." supply with in addition 1,4-butyleneglycol " that directly turn back to the reaction solution liquid phase part after a little while, the tendency that has foreign matter to increase.
In addition, turn back to the temperature of " supply with in addition 1,4-butyleneglycol " when the reactor, be generally 50～220 ℃, preferred 100～200 ℃, be more preferably 150～190 ℃.When the temperature of " supply with in addition 1,4-butyleneglycol " was too high, the tendency that has the amount of by-products of tetrahydrofuran (THF) to increase was crossed when low, owing to increase thermal load, the tendency that causes power loss is arranged.
In addition, in the present invention, in order to reduce mist value or foreign matter from catalyzer, and catalyst activity is reduced, preferably 10 weight % of the titanium catalyst that will in esterification (or transesterification reaction), use or more than the 10 weight % not with terephthalic acid (or dimethyl terephthalate ester) but directly supply in the reaction solution liquid phase part independently.At this, so-called reaction solution liquid phase part, liquid phase one side of the liquid-gas interface in expression esterification groove or the transesterification reaction groove, the so-called reaction solution liquid phase part that directly supplies to, be that pipe arrangement etc. is used in expression, titanium catalyst directly supplies to liquid phase part without the gas phase part of reactor.Directly add the ratio of the titanium catalyst of reaction solution liquid phase part to, preferred 30 weight % or more than the 30 weight %, be more preferably 50 weight % or more than the 50 weight %, preferred especially 80 weight % or more than the 80 weight %, the most preferred 90 weight % or more than the 90 weight %.
Above-mentioned titanium catalyst, though also can be dissolved in solvent etc. or be not dissolved in the reaction solution liquid phase part that directly supplies to esterification groove or transesterification reaction groove in the solvent, but in order to make the feed rate stabilization, and alleviate the detrimentally affects such as sex change that come from the torrid zone of the heat-transfer medium chuck of reactor etc., preferably use 1, the dilution of 4-butyleneglycol equal solvent.The concentration of this moment as the concentration of the titanium catalyst all with respect to solution, is generally 0.01～20 weight %, and preferred 0.05～10 weight % is more preferably 0.08～8 weight %.In addition, from reducing the viewpoint of foreign matter, the moisture concentration in the solution is generally 0.05～1.0 weight %.Temperature when the obtain solution from preventing the viewpoint of inactivation or cohesion, is generally 20～150 ℃, preferred 30～100 ℃, is more preferably 40～80 ℃.In addition, catalyst solution from preventing to worsen, prevent to separate out, suppress the foreign matter aspect, preferably mixes with " supply with in addition 1,4-butyleneglycol " in pipe arrangement etc., supplies in esterification groove or the transesterification reaction groove.
One of the continuous processing of employing direct polymerization method is for example descended.Promptly, with the above-mentioned dicarboxylic acid composition and 1 of terephthalic acid as principal constituent, the 4-butyleneglycol mixes in the raw material tempering tank as the above-mentioned diol component of principal constituent, makes form slurry, in single or multiple esterification grooves, in the presence of titanium catalyst, usually at 180～260 ℃, preferred 200～245 ℃, be more preferably 210～235 ℃ temperature, in addition, usually at 10～133kPa, preferred 13～101kPa is more preferably under the pressure of 60～90kPa, usually carried out continuously 0.5～10 hour, preferred 1～6 hour esterification will be transferred in the polycondensation groove as the oligopolymer of the resultant of the esterification that obtains, in single or multiple polycondensation grooves, in the presence of polycondensation catalyst, preferably continuously, usually at 210～280 ℃, preferred 220～265 ℃ temperature, usually at 27kPa or below the 27kPa, preferred 20kPa or below the 20kPa is more preferably under the following decompression of 13kPa or 13kPa, under agitation, usually carried out preferred 3～10 hours polycondensation 2～12 hours.The polymkeric substance that is obtained by polycondensation is extracted polymkeric substance out from the bottom of polycondensation groove usually, transfers in the mold, extracts into the strand shape out, on one side after water cooling or the water cooling, cut off with cutter, granulate, the granular solid of sheet etc.
During the direct polymerization method, terephthalic acid and 1, the mol ratio of 4-butyleneglycol preferred satisfies with following formula (III).
BM/TM＝1.1～4.5(mol/mol) (III)
(in the formula, BM is illustrated in time per unit and supplies to 1 the esterification groove from the outside, and the mole number of 4-butyleneglycol, TM are illustrated in time per unit supplies to the terephthalic acid the esterification groove from the outside mole number).
The value of above-mentioned BM/TM caused transformation efficiency to reduce or catalyst deactivation than 1.1 hours, and when bigger than 4.5, not only thermo-efficiency reduces, and the tendency of secondary resultant increases such as tetrahydrofuran (THF) is arranged.The value of BM/TM is preferred 1.5～4.0, is more preferably 2.0～3.8, preferred especially 2.7～3.5.
One of the continuous processing of employing ester-interchange method is for example descended.Promptly, in single or multiple transesterification reaction grooves, in the presence of titanium catalyst, usually at 110～260 ℃, preferred 140～245 ℃, be more preferably 180～220 ℃ temperature, in addition, usually at 10～133kPa, preferred 13～120kPa, be more preferably under the pressure of 60～101kPa, carried out continuously 0.5～5 hour usually, preferred 1～3 hour successive transesterification reaction, to transfer in the polycondensation groove as the oligopolymer of the resultant of the transesterification reaction that obtains, in single or multiple polycondensation grooves, in the presence of polycondensation catalyst, preferably continuously, usually at 210～280 ℃, preferred 220～265 ℃ temperature, usually at 27kPa or below the 27kPa, preferred 20kPa or below the 20kPa, be more preferably under the following decompression of 13kPa or 13kPa, under agitation, carried out preferred 3～10 hours polycondensation common 2～12 hours.
The occasion of ester-interchange method, dimethyl terephthalate ester and 1, the mol ratio of 4-butyleneglycol preferred satisfies with following formula (IV).
BM/DM＝1.1～2.5(mol/mol) (IV)
(in the formula, BM is illustrated in time per unit and supplies to 1 the transesterification reaction groove from the outside, and the mole number of 4-butyleneglycol, DM are illustrated in time per unit supplies to the dimethyl terephthalate ester the transesterification reaction groove from the outside mole number).
The value of above-mentioned BM/DM caused transformation efficiency to reduce or the catalyst activity reduction than 1.1 hours, and when bigger than 2.5, not only thermo-efficiency reduces, and the tendency of secondary resultant increases such as tetrahydrofuran (THF) is arranged.The value of BM/DM is preferred 1.1～1.8, is more preferably 1.2～1.5.
So-called above-mentioned " supplying to 1 esterification (transesterify) reactive tank from the outside; the 4-butyleneglycol ", be meant as former slip or solution, with terephthalic acid or dimethyl terephthalate ester supply with 1, outside the 4-butyleneglycol, supply with not with these but independently 1, the 4-butyleneglycol, as the solvent of catalyzer use 1,4-butyleneglycols etc. enter into 1 in the reactive tank, the summation of 4-butyleneglycol from the reactive tank outside.
In the present invention, esterification or transesterification reaction in order to shorten the reaction times, preferably 1, are carried out under the temperature more than the boiling point of 4-butyleneglycol or the boiling point.1, the boiling point of 4-butyleneglycol depends on the pressure of reaction, is 230 ℃ under 101.1kPa (normal atmosphere), is 205 ℃ under 50kPa.
In the manufacture method of PBT of the present invention, for the keeping of esterification yield or ester exchange rate, stabilization, and then reduce foreign matter, make foreign matter amount stabilization, preferably make terephthalic acid or dimethyl terephthalate ester and with respect to they excessive 1, the 4-butyleneglycol carries out when esterification or the transesterification reaction continuously, the control time per unit supplies to terephthalic acid or dimethyl terephthalate ester and 1 the reactive tank (esterification groove or transesterification reaction groove) from the outside, the mol ratio of 4-butyleneglycol is certain.
In the present invention, supply to terephthalic acid or dimethyl terephthalate ester and 1 reactive tank from the outside as the control time per unit, the mol ratio certain method of 4-butyleneglycol, for example, can enumerate, at terephthalic acid during as raw material, to contain terephthalic acid and 1, the former slip of 4-butyleneglycol is fixed as a certain mol ratio, supplies with certain amount, simultaneously, catalyzer is by 1, and when the 4-butanediol solution constituted, its concentration and feed rate also were set at necessarily, to " 1 of other supply, 4-butyleneglycol " simultaneously with a certain amount of method that supplies in the esterification groove.
Under conditions such as high temperature, decompression, from the esterification groove, produce 1, the change of 4-butyleneglycol gas volume is big, particularly " supply with in addition 1,4-butyleneglycol " is when being made of " recirculation 1,4-butyleneglycol ", its cohesion is obtained 1, the 4-butyleneglycol with respect to above-mentioned gas generated change, has the delay of some time and changes.In preferred scheme of the present invention, also be controlled at the recirculation 1 of the supply esterification groove of this moment, it is certain that the constant dosage of 4-butyleneglycol keeps, thereby control supplies to the terephthalic acid and 1 in the esterification groove, not change of the mol ratio of 4-butyleneglycol (BM/TM).At this moment, if as the backflow control of usually carrying out, make 1 of cohesion, the amount of liquid of 4-butyleneglycol is certain, make recirculation 1, the feed rate of 4-butyleneglycol changes when controlling like that, will cause the change of transformation efficiency (esterification yield), according to circumstances, by 1, the change that 4-butyleneglycol gas produces and condense 1, the phasic difference of the amount of liquid change of 4-butyleneglycol, obtain changing the result of increase, cause the quality instability.
In addition, can also enumerate, the terephthalic acid of raw material or dimethyl terephthalate ester and remove " supply with in addition 1; the 4-butyleneglycol " 1, the mol ratio one of 4-butyleneglycol regularly, for example, even terephthalic acid and 1, the occasion that the mol ratio of the former slip of 4-butyleneglycol is certain, when its feed rate of change, that is, when change of carrying out turnout etc., corresponding to its change, supply to terephthalic acid or dimethyl terephthalate ester and 1 in esterification groove or the transesterification reaction groove, the mol ratio of 4-butyleneglycol (BM/TM or BM/DM) changes the method for the amount of " 1 of other supply, 4-butyleneglycol " in order to reach certain.The feed rate of terephthalic acid composition is increased, if do not increase the amount of " 1 of other supply, 4-butyleneglycol ", BM/TM or BM/DM reduce, and cause the reduction of transformation efficiency.On the other hand, the feed rate of terephthalic acid composition is reduced, if do not reduce the amount of " 1 of other supply; 4-butyleneglycol ", BM/TM or BM/DM rise, though the rising of transformation efficiency, but cause side reaction increases such as tetrahydrofuran (THF) generation, or cause the loss of energy.
When changing the feed rate of terephthalic acid composition, in order to make BM/TM or BM/DM keep certain, the feed rate of preferred control on one side " 1 of other supply; 4-butyleneglycol ", simultaneously, such as described above, control " supply with in addition 1; the 4-butyleneglycol " so that it can't help 1 of short-term, the generating capacity of 4-butyleneglycol gas and changing.
As esterification groove or transesterification reaction groove, can use known devices, any types such as the complete tempering tank of vertical stirring, vertical thermal convection formula tempering tank, tower successive reaction groove all can, in addition, can be used as single groove, also can be used as the placed in-line a plurality of grooves of congener or different types of groove.Wherein, the reactive tank that preferably has whipping appts, as whipping appts, except the coventional type that constitutes by power section, bearing, axle, agitating wing, also can use turborotor type high-speed rotary stirrer, disc mill type stirrer, the impeller type of rotation at a high speed such as type stirrer of milling.
The form that stirs, have no particular limits, except with the reaction solution in the reactive tank from the common stirring means that directly stir on the top of reactive tank, bottom, horizontal etc., can also adopt the outside of the part of reaction solution being taken out reactor with pipe arrangement, stir with orthoscopic agitator (ラ イ Application モ キ サ one) etc., make reaction solution round-robin method.
The kind of agitating wing can be selected knownly, particularly, can enumerate the screw propulsion wing, screw wing, the turbine wing, the wind turbine wing, the disc turbine wing, the three leaf palintrope wings, the Off Le ゾ one Application wing, greatly mix (マ Star Network ス Block レ Application De) wing etc.
In the manufacturing of PBT, use a plurality of reactive tanks usually, preferably use 2～5 reactive tanks, molecular weight is raise.Usually, then the esterification or the transesterification reaction at initial stage are carried out polycondensation.
The polycondensation operation of PBT both can be used single reactive tank, also can use a plurality of reactive tanks, but preferably used a plurality of reactive tanks.The form of reactive tank, any types such as the complete tempering tank of vertical stirring, vertical thermal convection formula tempering tank, tower successive reaction groove all can, in addition, also these can be made up.Wherein, the reactive tank that preferably has whipping appts, as whipping appts, except constitute by power section, bearing, axle, agitating wing medium-sized, also can use turborotor type high-speed rotary stirrer, disc mill type stirrer, the impeller type of rotation at a high speed such as type stirrer of milling.
The form that stirs, have no particular limits, except with the reaction solution in the reactive tank from the common stirring means that directly stir on the top of reactive tank, bottom, horizontal etc., can also adopt the outside of the part of reaction solution being taken out reactor with pipe arrangement, stir with orthoscopic agitator etc., make reaction solution round-robin method.Wherein, recommend polycondensation groove at least 1, use the horizontal reactor of the Surface Renewal and the self-stip excellence that have turning axle in the horizontal direction.To the sense of rotation of the whipping appts of horizontal reactor without limits, when 2 stir shafts were arranged, the mixing direction of preferred axes was a different directions, wherein, is more preferably at top and elongates polymkeric substance, involves in the such sense of rotation of polymkeric substance in the bottom.
In addition, in order to suppress painted or deterioration, and the increase of the end of ethene suppressing base etc., at least in 1 reactive tank, usually at 1.3kPa or below the 1.3kPa, preferred 0.5kPa or below the 0.5kPa, be more preferably the following high vacuum of 0.3kPa or 0.3kPa, usually at 225～255 ℃, preferred 230～250 ℃, be more preferably under 233～245 ℃ the temperature and carry out to good.
In addition, in the polycondensation operation of PBT, can be temporarily make after the molecular weight ratio PBT less, about for example limiting viscosity 0.1～1.0dL/g with melt phase polycondensation, then, the temperature below the fusing point of PBT is carried out solid phase polycondensation (solid state polymerization).
By carrying out solid state polymerization, because the minimizing of the terminal carboxyl(group) of the PBT that can seek to obtain, therefore make effect of the present invention such as hydrolytic resistance raising more obvious.
PBT of the present invention owing to greatly reduce from the foreign matter of catalyzer, even it is also passable not remove this foreign matter, by in the runner of the precursor of polymkeric substance or polymkeric substance strainer being set, can obtain the excellent more polymkeric substance of quality.In the present invention, because above-mentioned reason, when using the strainer of the identical sieve aperture of the strainer that uses in the producing apparatus with former PBT, work-ing life in the time of can prolonging it to replacing, in addition, if the life-span of setting when changing is identical, the littler strainer of sieve aperture can be set.
Strainer the position is set, when in manufacturing process, being the upstream, the foreign matter that one side does not produce in the downstream remove the place that the viscosity in the downstream side is high, it is big that the pressure-losses of strainer becomes, in order to keep flow, the sieve aperture of strainer must be strengthened, perhaps equipment such as the filtration area of strainer or pipe arrangement are become excessive, in addition, owing to when fluid passes through, be subjected to high-shear, because the deterioration of the PBT that the shearing heating causes is inevitable.Therefore, strainer the position is set, the limiting viscosity of selecting PBT or its precursor usually is 0.1～1.2dL/g, preferred 0.2～1.0dL/g is more preferably the position of 0.5～0.9dL/g.
As the filtering material that constitutes strainer, metallic coil, laminated metal net, metal tNonwovens, expanded metal etc. any all can, from the viewpoint of filtering accuracy, preferred laminated metal net or metal tNonwovens, particularly, preferably its sieve aperture is by the sintering processes fixed.As the shape of strainer, can be any type of basket type, collar plate shape, movable disc type, cast, flush type round tube type, pleat type round tube type etc.In addition, in order not bring influence, a plurality of strainers preferably are set replace use, or automatic filtration net interchanger etc. is set to the operation of a machine.
The absolute filtering accuracy of strainer has no particular limits, and is generally 0.5～200 μ m, and preferred 1～100 μ m is more preferably 5～50 μ m, preferred especially 10～30 μ m.When absolute filtering accuracy was excessive, the foreign matter in the goods reduced effect and disappears, and then caused the reduction of productivity or strainer exchange frequency to increase when too small.
Below, based on the embodiment preferred of the manufacture method of description of drawings PBT.Fig. 1 is the explanatory view of an example of the esterification operation that adopts in the present invention or transesterification reaction operation, Fig. 2～5th, the esterification operation that adopts in the present invention or another routine explanatory view of transesterification reaction operation, Fig. 6 is the explanatory view of an example of the polycondensation step that adopts in the present invention, Fig. 7～9th, another routine explanatory view of the polycondensation step that adopts in the present invention.
In Fig. 1, the terephthalic acid of raw material normally in raw material tempering tank (not shown) with 1, the 4-butyleneglycol mixes, and is supplied in the reactive tank (A) by the form of feed line (1) with slurry.During dimethyl terephthalate ester, usually not with 1, the 4-butyleneglycol mixes and supplies in the reactive tank (A).On the other hand, titanium catalyst is preferably adjusted in the groove (not shown) at catalyzer and is made 1, behind the solution of 4-butyleneglycol, is supplied with by catalyzer supply line (3).In Fig. 1, show catalyzer supply line (3) is attached at recirculation 1, on the re-circulation line of 4-butyleneglycol (2), after both mixing, supply to the mode of the liquid phase part in the reactive tank (A).
The gas that distills from reactive tank (A) separates high boiling point composition and low boiling point component through distillating line (5) in rectifying tower (C).Usually, the principal constituent of high boiling point composition is 1, the 4-butyleneglycol, and the principal constituent of low boiling point component is water and tetrahydrofuran (THF) in the occasion of direct polymerization method, is alcohol, tetrahydrofuran (THF), water in the occasion of ester-interchange method.
Isolating high boiling point composition is extracted out by extracting line (6) out in rectifying tower (C), and through pump (D), a part is recycled to reactive tank (A) by re-circulation line (2), and a part turns back to rectifying tower (C) by circular route (7).In addition, Sheng Xia part is extracted line (8) out by gas and is retracted to the outside.On the other hand, isolating low boiling point component is extracted out by extracting line (9) out in rectifying tower (C), with condenser (G) cohesion, temporarily is stored in jar (F) through cohesion liquidus (10).The part of the low boiling point component of collecting in jar (F) turns back to rectifying tower (C) through extracting line (11), pump (E) and circular route (12) out, and remaining part is retracted to the outside through extracting line (13) out.Condenser (G) is connected on the gas barrier (not shown) through takeoff line (14).The oligopolymer that generates in reactive tank (A) is drawn out of through extractor pump (B) and extraction line (4).
In operation shown in Figure 1, catalyzer supply line (3) is though be attached on the re-circulation line (2), and both also can be independent.In addition, feed line (1) can be connected to the liquid phase part of reactive tank (A).
Operation shown in Figure 2 is compared with operation shown in Figure 1, and difference is, goes up equipment reboiler (H) at rectifying tower (C), in addition, is provided with from the outside to the supply line (15) of rectifying tower (C) feeding liquid.By the setting of reboiler (H), the running of rectifying tower (C) control becomes easy.
Operation shown in Figure 3 is compared with operation shown in Figure 1, and difference is, is connected the gas phase part of reactive tank (A) from circular route (7) ramose bypass line (16).Therefore, in the occasion of operation shown in Figure 3, recirculation 1, the part of 4-butyleneglycol partly turns back in the reaction solution via the gas phase of reactive tank (A).
Operation shown in Figure 4, compare with operation shown in Figure 1, difference is, following control device (L) is set, and this control device (L) is in re-circulation line (2) and extracts out on the line (8), flowrate control valve (J) and flowrate control valve (K) are set respectively, in addition, detect the liquid level of rectifying tower (C), detect the opening degree of Signal Regulation flowrate control valve (K), the liquid level of rectifying tower (C) is adjusted to necessarily based on this.Because change, the distillate gas scale of construction of reactive tank (A) temperature or distillate the change of gas composition, the change of raw material supplying amount, the temperature variation of rectifying tower (C) etc., rectifying tower (C) though tower at the bottom of liquid level small, but also change thereupon, but according to operation shown in Figure 4, change by the liquid level at the bottom of the tower of rectifying tower (C), adjusting is by the extraction amount of extracting line (8) out, and the recirculation volume of keeping by re-circulation line (2) keeps certain.
Operation shown in Figure 5, compare with operation shown in Figure 2, difference is, following control device (L) is set, this control device (L) is in re-circulation line (2) and extracts out on the line (8), flowrate control valve (J) and flowrate control valve (K) are set respectively, and high boiling point composition jar (N) and a reboiler (H) are set respectively on extraction line (6) and extraction line (7), in position supply line (15) is set than reboiler (H) downstream of circular route (7), in addition, detect the liquid level of high boiling point composition, detect the opening degree of Signal Regulation flowrate control valve (K), the liquid level of high boiling point composition with jar (N) is adjusted to necessarily based on this with jar (N).Operation shown in Figure 5 plays the improved effect same with operation shown in Figure 4.Clear and definite operation shown in Figure 5 as the input signal to control device (L), can be utilized based on the signal of high boiling point composition with the liquid level change of jar (N).
In Fig. 6, by the oligopolymer of the supply of the extraction line (4) shown in above-mentioned Fig. 1～5, in the 1st polycondensation groove (a), polycondensation under reduced pressure, after becoming prepolymer, supply in the 2nd polycondensation groove (d) through extracting out with toothed gear pump (c) and extracting line (L1) out.In the 2nd polycondensation groove (d), under than the lower pressure of the 1st polycondensation groove (a), further carry out polycondensation usually, obtain polymkeric substance.The polymkeric substance that obtains is through extracting out with toothed gear pump (e) and extracting line (L3) out, and the form with fused strand shape from die head (g) is extracted out, after the cooling such as water, cuts off with rotary blade (h), obtains particle.Symbol (L2) is the takeoff line of the 1st polycondensation groove (a), and symbol (L4) is the takeoff line of the 2nd polycondensation groove (d).Operation shown in Figure 7 is compared with operation shown in Figure 6, and difference is, in the stream of extracting line (L3) out, is equipped with strainer (f).
Operation shown in Figure 8 is compared with operation shown in Figure 6, and difference is, in the back of the 2nd polycondensation groove (d), the 3rd polycondensation groove (k) is set.The 3rd polycondensation groove (k) is to be made of a plurality of agitating wing parts, has the horizontal reacting groove of 2 Self-cleaning type agitating wings.By extracting line (L3) imports to the 3rd polycondensation groove (k) from the 2nd polycondensation groove (d) polymkeric substance out, after the further here condensation, through extracting out with toothed gear pump (m) and extracting line (L5) out, form with fused strand shape from die head (g) is extracted out, after the cooling such as water, cut off with rotary blade (h), obtain particle.Symbol (L6) is the takeoff line of the 3rd polycondensation groove (k).
Operation shown in Figure 9 is compared with operation shown in Figure 8, and difference is, in the way of the extraction line (L3) between the 2nd polycondensation groove (d) and the 3rd polycondensation groove (k), is equipped with strainer (f).
＜contain the general composition of above-mentioned polybutylene terephthalate 〉
In PBT of the present invention, can add 2,6-di-t-butyl-4-octyl phenol, [3-(3 ' for tetramethylolmethane four, 5 '-tertiary butyl-4 '-hydroxyphenyl) propyl ester] etc. phenolic compound, dilauryl-3,3 '-thiodipropionate, tetramethylolmethane four sulfide compounds such as (3-lauryl thiodipropionates), triphenyl phosphite, trisnonyl phenyl phosphite, the oxidation inhibitor of tricresyl phosphite phosphorus compounds such as (2,4-di-t-butyl phenyl ester) etc., with paraffin, Microcrystalline Wax, polyethylene wax, montanic acid or montanate are the longer chain fatty acid and the ester thereof of representative, releasing agents such as silicone oil etc.
In PBT of the present invention, can cooperate the reinforcement packing material.As strengthening packing material, have no particular limits, can enumerate, for example, organic fibres such as inorganic fibre, aromatic polyamide fibre, fluororesin fiber such as glass fibre, carbon fiber, silica alumina fiber, Zirconium oxide fibre, boron fibre, boron nitride fibre, silicon nitride metatitanic acid potassium fiber, steel fiber etc.Also these can be strengthened packing material is used in combination more than 2 kinds or 2 kinds.In the above-mentioned reinforcement packing material, be particularly suitable for using glass fibre.
When the reinforcement packing material was inorganic fibre or organic fibre, its average fiber footpath had no particular limits, and is generally 1～100 μ m, and preferred 2～50 μ m are more preferably 3～30 μ m, preferred especially 5～20 μ m.In addition, average fiber length has no particular limits, and is generally 0.1～20mm, preferred 1～10mm.
In order to improve the interface adaptation with PBT, strengthen packing material and preferably use with astringent matter or surface treatment agent and carry out surface-treated.As astringent matter or surface treatment agent, can enumerate, for example functionality compounds such as epoxy compounds, acrylic compounds, isocyanate ester compound, silane compound, titanate ester compound.Strengthen packing material, can carry out surface treatment in advance, perhaps, also can when preparation PBT composition, add astringent matter or surface treatment agent and carry out surface treatment by astringent matter or surface treatment agent.Strengthen the addition of packing material, with respect to PBT resin 100 weight parts, be generally 150 weight parts or below 150 weight parts, preferred 5～100 weight parts.
Among the PBT of the present invention, can be with strengthening the packing material that packing material cooperates other.As other the packing material that cooperates, can enumerate, for example, tabular inorganic filling material, ceramic bead, asbestos, wollastonite (ワ ラ ス ト Na イ ト), talcum, clay, mica, zeolite, kaolin, potassium titanate, barium sulfate, titanium oxide, silicon oxide, aluminum oxide, magnesium hydroxide etc.By cooperating tabular inorganic filling material, can reduce the anisotropy and the warpage of molding.As tabular inorganic filling material, can enumerate, for example, glass flake, mica, tinsel etc.In the middle of these, be fit to use glass flake.
In order to give flame retardant resistance, can in PBT of the present invention, cooperate fire retardant.As fire retardant, have no particular limits, can enumerate, for example, organohalogen compound, antimony compounds, phosphorus compound, other organic fire-retardant, inorganic combustion inhibitor etc.As organohalogen compound, can enumerate, for example, bromo polycarbonate, brominated epoxy resin, bromobenzene epoxy resins, bromo polyphenylene oxide resin, Brominated Polystyrene resin, bromo dihydroxyphenyl propane, poly-(pentabromobenzyl acrylate) etc.As antimony compounds, can enumerate, for example, ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide, sodium antimonate etc.As phosphorus compound, can enumerate, for example, phosphoric acid ester, Tripyrophosphoric acid, ammonium polyphosphate, red phosphorus etc.As other organic fire-retardant, can enumerate, for example, nitrogen compounds such as trimeric cyanamide, tricyanic acid etc.As other inorganic combustion inhibitor, can enumerate, for example, aluminium hydroxide, magnesium hydroxide, silicon compound, boron compound etc.
Optionally, can also in PBT of the present invention, cooperate habitual additive etc.Additive as such has no particular limits, and for example, except that stablizers such as oxidation inhibitor, heat-resisting stabilizing agent, can also enumerate lubricant, weighting material, releasing agent, catalyst deactivation agent, crystallization nucleating agent, crystallization promoter etc.These additives can add in polymerization midway or after the polymerization.As above-mentioned crystallization nucleating agent, can enumerate talcum, potter's clay, boron nitride etc., as above-mentioned weighting material, can enumerate layered silicate, zeolite, silicon-dioxide etc.In addition, in order to give the performance of expectation, can in PBT, cooperate tinting materials such as stablizers such as UV light absorber, weather-proof stablizer, dyestuff, pigment, antistatic agent, whipping agent, softening agent, shock-resistance modifying agent etc.
Optionally, can also in PBT of the present invention, cooperate thermosetting resins such as thermoplastic resins such as polyethylene, polypropylene, polystyrene, polyacrylonitrile, polymethacrylate, ABS resin, polycarbonate, polymeric amide, polyphenylene sulfide, polyethylene terephthalate, liquid crystal polyester, polyacetal, polyphenylene oxide, resol, melamine resin, polyorganosiloxane resin, Resins, epoxy.Also these thermoplastic resins and thermosetting resin can be used in combination more than 2 kinds or 2 kinds.
The above-mentioned various additives or the fitting method of resin have no particular limits, but preferably will have the method that can use as mixing roll from the single shaft or the biaxial extruder of the equipment of relief outlet devolatilisation.Various compositions comprise additional composition, can offer mixing roll together, perhaps also can supply with successively.In addition, comprise additional composition, also the composition more than 2 kinds or 2 kinds that is selected from the various compositions can be pre-mixed.
＜contain the specific composition of above-mentioned polybutylene terephthalate 〉
PBT of the present invention as previously mentioned, can use as general resin combination with usual method in the resin field, in addition, PBT of the present invention, also can with specific additive combination, use as specific polybutylene terephthalate composition with various functions.Below, describe for these resin combinations.
(thermotolerance PBT composition)
Thermotolerance PBT composition of the present invention is characterized in that, contains above-mentioned PBT (A) and is selected from the oxidation inhibitor more than a kind or a kind in phenolic antioxidant (B1), sulfur type antioxidant (B2) and the Phosphorus oxidation inhibitor (B3).
The phenolic antioxidant (B1) that said the present invention uses, be meant the meaning of oxidation inhibitor with phenolic hydroxyl group, wherein, so-called Hinered phenols antioxidant, be meant 1 or 2 carbon atom on the carbon atom of the aromatic nucleus that abuts against the phenolic hydroxyl group bonding, the meaning of the oxidation inhibitor that replaces by carbonatoms 4 or 4 above substituting groups.Carbonatoms 4 or 4 above substituting groups can pass through the C-C bonding with the carbon atom of aromatic nucleus, also can be by the atomic linkage beyond the carbon atom.The concrete example of the phenolic antioxidant (B1) that uses as the present invention, can enumerate cyclohexylphenol, the 3-tertiary butyl-4-methoxyphenol, 4,4 '-isopropylidene biphenol, 1, non-Hinered phenols antioxidants such as two (4-hydroxyphenyl) hexanaphthenes of 1-, the 2-tertiary butyl-4-methoxyphenol, 2, the 6-ditertbutylparacresol, 2,4, the 6-tri-butyl-phenol, 4-methylol-2, the 6-DI-tert-butylphenol compounds, styrenated phenol, 2, the 5-di-tert-butyl hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester, triglycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionic ester], 1, the 6-hexane diol is two, and [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], [3-(3 for tetramethylolmethane four, 5-di-t-butyl-4-hydroxyphenyl) propionic ester], 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 2,2 '-methylene-bis (the 6-tertiary butyl-4-ethylphenol), 2,2 '-methylene-bis [4-methyl-6-(1,3,5-trimethylammonium hexyl) phenol], 4,4 '-methylene-bis (2, the 6-DI-tert-butylphenol compounds), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 2, two (the 2-hydroxyl-3-tertiary butyl-5-methyl-benzyl) the 4-methylphenols of 6-, 1,1,3-three [2-methyl-4-hydroxyl-5-tert-butyl-phenyl] butane, 1,3,5-trimethylammonium-2,4,6-three [3, the 5-di-tert-butyl-4-hydroxyl benzyl] benzene, three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, three [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionyl oxygen ethyl] isocyanuric acid ester, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-thiobis (4-methyl-6-tert butyl phenol), 4,4 '-thiobis (2-methyl-6-tert butyl phenol), thiobis Hinered phenols antioxidants such as (2-Naphthols).Particularly, Hinered phenols antioxidant owing to himself become stable free radical easily, can suit to use as free radical scavenger.The molecular weight of Hinered phenols antioxidant is generally more than 200 or 200, and more than preferred 500 or 500, its upper limit is generally 3000.
The sulfur type antioxidant (B2) that so-called the present invention uses is meant not have phenolic hydroxyl group, and has the oxidation inhibitor of sulphur atom.As the concrete example of sulfur type antioxidant (B2), can enumerate two dodecyl thiodipropionates, two tetradecyl thiodipropionate, two octadecyl thiodipropionate, tetramethylolmethane four (3-dodecyl thiopropionate), thiobis (N-Phenyl beta naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, single sulfuration tetra methylthiuram, tetramethyl-thiuram disulfide, nickel dibutyl dithiocarbamate, nickel isopropyl xanthate, trilauryl trithiophosphite etc.Particularly, have the thioether kind antioxidant of sulfide based structural, reduce, can preferably use owing to accepting oxygen from oxidized material.The molecular weight of sulfur type antioxidant is generally more than 200 or 200, and more than preferred 500 or 500, its upper limit is generally 3000.
So-called Phosphorus oxidation inhibitor of the present invention (B3) is meant not have phenolic hydroxyl group, does not also have sulphur atom, and has the oxidation inhibitor of phosphorus atom.Phosphorus oxidation inhibitor (B3) preferably has P (OR) 3The oxidation inhibitor of structure.Here, R is alkyl, alkylidene group, aryl, arylidene etc., and 3 R both can be the same or different, and 2 R can form ring structure.As so Phosphorus oxidation inhibitor, can enumerate, for example, triphenyl phosphite, phenylbenzene decyl phosphorous acid ester, phenyl diiso decyl phosphorous acid ester, tricresyl phosphite (nonyl phenyl) ester, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites etc.
In thermotolerance PBT composition of the present invention, with respect to 100 weight part PBT, the amount of phenolic antioxidant (B1) is generally 0.001～2 weight part, preferred 0.003～1 weight part.The amount of phenolic antioxidant has the danger that can not demonstrate fully antioxidant effect during less than 0.001 weight part, when surpassing 2 weight parts, has heat of oxidation poor stability, or the danger that causes that resin decomposes is arranged when melting mixing.
In thermotolerance PBT composition of the present invention, sulfur type antioxidant (B2) and/or Phosphorus oxidation inhibitor (B3) have the modified resin composition heat-resistant aging, improve the effect of the conservation rate of tone, tensile strength, elongation etc.
In thermotolerance PBT composition of the present invention, with respect to 100 weight part PBT, the amount of sulfur type antioxidant (B2) and Phosphorus oxidation inhibitor (B3) is respectively 0.001～1.9 weight part usually, preferred 0.003～1 weight part.The amount of each oxidation inhibitor has the danger that can not demonstrate fully above-mentioned effect during less than 0.001 weight part, and when surpassing 1.9 weight parts, heat of oxidation stability worsens, or the danger that causes that resin decomposes is arranged when melting mixing.
In thermotolerance PBT composition of the present invention, when containing phenolic antioxidant (B1) and sulfur type antioxidant (B2) and/or Phosphorus oxidation inhibitor (B3), with respect to phenolic antioxidant 1 weight part, the ratio of sulfur type antioxidant and/or Phosphorus oxidation inhibitor is generally 0.2～5 weight part.The ratio of sulfur type antioxidant and/or Phosphorus oxidation inhibitor is during less than 0.2 weight part or when surpassing 5 weight parts, and any, the effect that improves heat-resistant aging all has the danger that diminishes.
In thermotolerance PBT composition of the present invention, when containing phenolic antioxidant and sulfur type antioxidant and/or Phosphorus oxidation inhibitor, with respect to 100 weight part PBT, the total amount of the amount of oxidation inhibitor is generally 2 weight parts or below 2 weight parts.When the total amount of the amount of oxidation inhibitor surpassed 2 weight parts, heat of oxidation stability worsened, or the danger that causes that resin decomposes is arranged when melting mixing.
(good release property PBT composition)
Good release property PBT composition of the present invention, it is characterized in that, with respect to above-mentioned PBT (A) 100 weight parts, contain the ester (C1) of residue of the alcohol that is selected from the fatty acid residue that contains carbonatoms 12～36 and carbonatoms 1～36 and releasing agent (C) 0.01～2 weight part in paraffin and the polyethylene wax (C2).
As the lipid acid that forms the fatty acid ester (C1) that uses among the present invention, the fatty acid ester of residue that contains the alcohol of the fatty acid residue of carbonatoms 12～36 and carbonatoms 1～36 is necessary, the fatty acid ester of residue that preferably contains the alcohol of the fatty acid residue of carbonatoms 16～32 and carbonatoms 1～36 is more preferably the fatty acid ester of residue of the alcohol of the fatty acid residue that contains carbonatoms 16～32 and carbonatoms 1～20.
As the concrete example of the lipid acid that forms fatty acid ester (C1), can enumerate lauric acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, arachic acid, docosoic acid, Lignoceric acid, hexacosanoic acid, octocosoic acid, triacontanoic acid, n-Dotriacontanoic acid etc.The carbonatoms of fatty acid residue was less than 12 o'clock, and release property is low, and in addition, volatilization easily has the danger of the reason that becomes the metal die pollution.The carbonatoms of fatty acid residue surpasses at 36 o'clock, has to demonstrate fully the effect that improves release property.
As the concrete example of the alcohol that forms fatty acid ester (C1), can use the above polyvalent alcohol of monohydroxy-alcohol, dibasic alcohol and ternary or ternary.Concrete example as such alcohol, can enumerate monohydroxy-alcohol, ethylene glycol, propylene glycol, 1 such as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, hexanol, hexalin, enanthol, octanol, lauryl alcohol, Stearyl alcohol, ammediol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1, trivalent alcohol, tetramethylolmethanes, 1,2 such as dibasic alcohol such as 4-cyclohexanediol, glycerol, TriMethylolPropane(TMP), 3, tetravalent alcohols such as 4-butantetraol etc.The carbonatoms of alcohol residue surpasses at 36 o'clock, has to demonstrate fully the effect that improves release property.
Manufacture method as fatty acid ester (C1), can adopt, for example, with lipid acid and pure as raw material, in the presence of acid catalysts such as sulfuric acid, hydrochloric acid, tosic acid, carry out esterification method, be high boiling when pure, carry out the method for transesterification reaction between the lower alkyl esters of lipid acid and the high boiling alcohol by the method for lipid acid acyl chlorides and alcohol reaction, the alcohol that forms fatty acid ester.
Concrete example as fatty acid ester (C1), can enumerate Laurate methyl, methyl myristate, methyl palmitate, the octadecanoic acid methyl esters, Witconol 2301, methyl behenate, the octocosoic acid methyl esters, isopropyl myristate, the hexadecanoic acid isopropyl ester, butyl laurate, butyl octadecanoate, the hexadecanoic acid monooctyl ester, the octadecanoic acid monooctyl ester, the dodecylic acid dodecyl ester, the octadecanoic acid stearyl, ethylene glycol dilaurate, glycol dipalmitate, ethylene glycol bis octadecane acid esters, ethylene glycol bis octacosane acid esters, Rikemal PL 100, propylene glycol list octadecane acid esters, 1, the ammediol bilaurate, 1, the two octadecane acid esters of ammediol, 1, the two octacosane acid esters of ammediol, 1,4-butyleneglycol bilaurate, 1, the two octadecane acid esters of 4-butyleneglycol, 1, the two octacosane acid esters of 4-butyleneglycol, glycerine list n-Hexadecane acid esters, glycerine list octadecane acid esters, glycerine list octacosane acid esters, the two n-Hexadecane acid esters of glycerine, the two octadecane alkanoic acid esters of glycerine, glycerol dioleate, tristearin, triolein, tetramethylolmethane list n-Hexadecane acid esters, tetramethylolmethane list octadecane acid esters, the two n-Hexadecane acid esters of tetramethylolmethane, the two octadecane acid esters of tetramethylolmethane, tetramethylolmethane three (hexadecanoic acid) ester, tetramethylolmethane three (octadecanoic acid) ester, tetramethylolmethane four (octadecanoic acid) ester etc.
The molecular weight of paraffin and polyethylene wax (C2) is generally 300～5000, and preferred 500～3000.Molecular weight, was volatilized by vaccum exhaust outlet during mixing simply less than 300 o'clock, was difficult to bring into play its effect, or wax is emitted simply in shaping, became the reason of pollution metal mould.On the other hand, molecular weight was not emitted above 5000 o'clock, thereby had reduced the effect as releasing agent.
In good release property PBT composition of the present invention, with respect to 100 weight part PBT, the amount of fatty acid ester (C1) is generally 0.01～2 weight part, preferred 0.1～1 weight part.The amount of fatty acid ester (C1) is during less than 0.01 weight part, have and to demonstrate fully the danger that release property improves effect (forming period shortening effect), when surpassing 2 weight parts, can not obtain the release property that the increase with fatty acid ester matches and improve effect, the danger that has intensity or thermotolerance to reduce on the contrary.
At good release property PBT composition of the present invention, with respect to 100 weight part PBT, the amount of paraffin or polyethylene wax (C2) is generally 0.01～2 weight part, preferred 0.1～1 weight part.The amount of paraffin or polyethylene wax (C2) is during less than 0.01 weight part, have and to demonstrate fully the danger that release property improves effect (forming period shortening effect), when surpassing 2 weight parts, can not obtain the release property that the increase with paraffin or polyethylene wax matches and improve effect, the danger that has intensity or thermotolerance to reduce on the contrary.
(hydrolytic resistance PBT composition)
Hydrolytic resistance PBT composition of the present invention is characterized in that, with respect to above-mentioned PBT (A) 100 weight parts, contains epoxy compounds (E) 0.01～20 weight part and strengthens weighting agent (D) 0～200 weight part.
The epoxy compounds (E) that the present invention uses both can be simple function, two functionalities, trifunctional or multi-functional any one, also can be the mixtures more than 2 kinds or 2 kinds in the middle of these.Particularly, preferred two functionalities, trifunctional, multi-functional epoxy compounds promptly, have the compound of the epoxide group more than 2 or 2 in 1 molecule.In addition, epoxy compounds (E) can also be any one of the epoxypropyl compound that obtains of alcohol, phenolic compound or carboxylic acid and epichlorohydrin reaction, alicyclic epoxy compound etc.
As the concrete example of epoxy compounds (E), can enumerate glycidyl ethers such as methyl glycidyl ethers, butyl glycidyl ethers, 2-ethylhexyl glycidyl ethers, decyl glycidyl ethers, stearyl-glycidyl ethers, phenyl glycidyl ethers, butyl phenyl glycidyl ethers, allyl group glycidyl ethers; Diepoxy propyl ethers such as neopentyl glycol diepoxy propyl ether, ethylene glycol bisthioglycolate glycidyl ethers, glycerol diepoxy propyl ether, propylene glycol diepoxy propyl ether, dihydroxyphenyl propane diepoxy propyl ether; Lipid acid epoxy propyl ester such as phenylformic acid epoxy propyl ester, Sorbic Acid epoxy propyl ester; Diglycidyl ether such as hexanodioic acid diglycidyl ether, diglycidyl terephthalate, phthalic acid (acid of オ Le ト Off Le) diglycidyl ether; 3,4-epoxycyclohexyl methyl-3, ester ring type di-epoxy compounds such as 4-epoxycyclohexyl carboxylicesters etc.Wherein, the epoxypropyl ether compound that preferred dihydroxyphenyl propane and epichlorohydrin reaction obtain, preferred especially dihydroxyphenyl propane diepoxy propyl ether.
The kind of the reinforcement packing material (D) that uses as the present invention, can enumerate, for example, organic fibres such as inorganic fibre, aromatic polyamide fibre, fluororesin fiber such as glass fibre, carbon fiber, silica alumina fiber, Zirconium oxide fibre, boron fibre, boron nitride fibre, silicon nitride metatitanic acid potassium fiber, steel fiber etc.These are strengthened packing materials and both can a kind use separately, also can be used in combination more than 2 kinds or 2 kinds.In the middle of these, be fit to use inorganic filling material, be particularly suitable for using glass fibre.
When reinforcement packing material (D) was inorganic fibre or organic fibre, its average fiber footpath was generally 1～100 μ m, and preferred 2～50 μ m are more preferably 3～30 μ m, preferred especially 5～20 μ m.In addition, average fiber length is generally 0.1～20mm, preferred 1～10mm.
In order to improve the interface adaptation with PBT, strengthen preferred use of packing material (D) and carry out surface-treated with astringent matter or surface treatment agent.As astringent matter or surface treatment agent, can enumerate, for example, functionality compounds such as epoxy compounds, acrylic compounds, isocyanate ester compound, silane compound, titanate ester compound.Strengthen packing material (D), can carry out surface treatment in advance, perhaps, also can when preparation PBT composition, add astringent matter or surface treatment agent and carry out surface treatment by astringent matter or surface treatment agent.
As the glass fibre that the present invention uses, can enumerate, for example, various glass fibre such as E glass, C glass, A glass, S glass, S-2 glass.In the middle of these, the preferred bases composition is few, and the glass fibre of the good E glass of electrical characteristic.
The average fiber of glass fibre directly is generally 1～100 μ m, and preferred 2～50 μ m are more preferably 3～30 μ m, preferred especially 5～20 μ m.Average fiber footpath is less than the glass fibre of 1 μ m, have be difficult to make, danger that cost uprises.Average fiber directly surpasses the glass fibre of 100 μ m, and the danger of the tensile strength reduction of glass fibre is arranged.The average fiber length of glass fibre is generally 0.1～20mm, preferred 1～10mm.Average fiber length has the danger that can not demonstrate fully the reinforced effects that is produced by glass fibre during less than 0.1mm, when average fiber length surpasses 20mm, the danger that makes the shaping with the melting mixing of PBT or PBT composition become difficulty is arranged.
The glass fibre that glass fibre is preferably handled by surface treatment agent.By the surface of handling glass fibre with surface treatment agent, produce firm bonding or bonding at the interface of PBT and glass fibre, transmit stress from PBT to glass fibre, thereby embody the reinforced effects that produces by glass fibre.
As the surface treatment agent that uses, can enumerate, for example, vinyl trichloro silane, chlorosilane compounds such as methyl ethylene dichlorosilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyltriacetoxy silane, alkoxy silane compounds such as gamma-methyl allyl acyloxypropyl trimethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, epoxy silane compounds such as γ-glycidoxypropyltrime,hoxysilane, acrylic compounds, isocyanate ester compound, the titanate ester compound, epoxy compounds etc.
In addition, the glass fibre preferably handled of glass fibre by astringent matter.By handling glass fibre, can improve the use operability of glass fibre, and can prevent the damage of glass fibre with astringent matter.As the astringent matter that uses, can enumerate, for example, resin emulsions such as vinyl acetate resin, ethylene vinyl acetate, acrylic resin, Resins, epoxy, urethane resin, vibrin etc.
In hydrolytic resistance PBT composition of the present invention, with respect to 100 weight part PBT, the amount of epoxy compounds (E) is generally 0.01～20 weight part, preferred 0.03～10 weight part.The amount of epoxy compounds (E) does not almost have hydrolytic resistance to improve effect during less than 0.01 weight part, and when surpassing 20 weight parts, other mechanical properties reduces, or melting heat stability worsens.
In addition, in hydrolytic resistance PBT composition of the present invention, with respect to 100 weight part PBT, the amount of strengthening packing material (D) is generally 0～200 weight part, preferred 0～150 weight part.When the amount of reinforcement packing material (D) surpasses 200 weight parts, the danger that has the shaping that makes melting mixing or resin combination to become difficulty.
(shock-resistance PBT composition)
Shock-resistance PBT composition of the present invention is characterized in that, with respect to above-mentioned PBT (A) 100 weight parts, contains shock-resistant improvement material (F) 0.5～40 weight part and strengthens weighting agent (D) 0～200 weight part.
The shock-resistant modifying agent (F) that so-called the present invention uses is the material that impact values such as Ai Zuoshi impact value, pendulum impact test value, face impact value are improved, and for example, can enumerate acrylic rubber, butadiene type rubber, polysiloxane-based rubber etc.Particularly preferred acrylic rubber.Acrylic rubber is by the polymerization of acrylate or with its rubber-like elastic body that obtains as the copolymerization of main body, as representational material, can enumerate on the polymkeric substance that the such cross-linkable monomer polymerization of the such acrylate of butyl acrylate and a spot of butylene glycol diacrylate is obtained the graft polymerization monomer that the graft polymerization methyl methacrylate is such and the elastomeric polymkeric substance that obtains.
As above-mentioned acrylate, except that butyl acrylate, can also enumerate methyl acrylate, ethyl propenoate, propyl acrylate, Ethyl acrylate, ethyl acrylate etc.In addition, as cross-linkable monomer, except butylene glycol diacrylate, can enumerate butylene glycol dimethacrylate, the ester class of polyvalent alcohol that trimethylolpropane trimethacrylate is such and acrylic or methacrylic acid, Vinylstyrene, vinyl acrylate, the vinyl compound that the methacrylic vinyl acetate is such, allyl acrylate, allyl methacrylate(AMA), diallyl maleate, diallyl fumarate, the methylene-succinic acid diallyl, toxilic acid monoene propyl ester, fumaric acid monoene propyl ester, the allylic cpd that triallyl cyanurate is such etc.
In addition, as above-mentioned graft polymerization monomer, except methyl methacrylate, can enumerate the such methacrylic ester of Jia Jibingxisuanyizhi, butyl methacrylate, N-Hexyl methacrylate, methacrylic acid-2-ethylhexyl, lauryl methacrylate(LMA), vinylbenzene, vinyl cyanide etc.These graft polymerization monomers can use its part when aforesaid propylene acid esters and cross-linkable monomer polymerization manufacturing polymkeric substance, and carry out copolymerization.
In shock-resistance PBT composition of the present invention, with respect to 100 weight part PBT, the amount of shock-resistant modifying agent (F) is generally 0.5～40 weight part, and preferred 1～35 weight part is more preferably 2～30 weight parts.The amount of shock-resistant modifying agent (F) can not be confirmed the raising of shock-resistance or resistance to sudden heating during less than 0.5 weight part, and when surpassing 40 weight parts, mechanical characteristicies such as tensile strength, flexural strength descend significantly.
In shock-resistance PBT composition of the present invention, strengthen the kind of packing material (D) and amount and be with aforesaid hydrolytic resistance PBT composition in the same kind and the amount that illustrate.
(flame retardant resistance PBT composition)
Flame retardant resistance PBT composition of the present invention, it is characterized in that, with respect to above-mentioned PBT (A) 100 weight parts, contain bromo aromatics based flame retardant (G) 3～50 weight parts, antimony compounds (H) 1～30 weight part, dripping inhibitor (I) 0～15 weight part and strengthen packing material (D) 0～200 weight part.
Bromo aromatics based flame retardant (G) as the present invention's use, be as the known aromatic series compounds of brominated flame retardant that in resin, uses, for example, can enumerate the epoxy oligomer of tetrabromo-bisphenol, poly-(pentabromobenzyl acrylate), poly-bromobenzene ether, Brominated Polystyrene, bromo epoxy, bromo imide, bromo polycarbonate etc.
As the antimony compounds (H) that the present invention uses, can enumerate, for example, weisspiessglanz or stibnate as concrete example, can be enumerated ANTIMONY TRIOXIDE SB 203 99.8 PCT (Sb 2O 3), four weisspiessglanz (Sb 2O 4), antimony pentaoxide (Sb 2O 5) wait stibnates such as oxide compound or sodium antimonate.
The dripping inhibitor (I) that so-called the present invention uses, be meant the compound of the character of dripping of the resin that has when preventing to burn, as its concrete example, can enumerate silicone oil, silicon-dioxide, asbestos, fluoro-resin, talcum, also have layered silicate such as mica etc. in addition.Particularly, from the flame retardant resistance of composition, preferred dripping inhibitor is polymkeric substance or the layered silicate that contains fluorine.
The concrete example of the fluoro-resin that uses as dripping inhibitor (I) can be enumerated fluoro polyolefine such as tetrafluoroethylene, tetrafluoroethylene/perfluoro alkyl vinyl ether co-polymer, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene multipolymer, vinylidene, voltalef etc.In the middle of these, preferably polytetrafluoroethylene, tetrafluoroethylene/perfluoro alkyl vinyl ether co-polymer, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene multipolymer are more preferably tetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene copolymer.
As tetrafluoroethylene, preferably has the tetrafluoroethylene that protofibril forms energy.That is, this tetrafluoroethylene is to disperse easily in resin, and bonding between the polymkeric substance, shows the material of the tendency that forms fibrous material, works as dripping inhibitor.Tetrafluoroethylene with protofibril formation energy, be divided into 3 types according to the ASTM specification, for example, can obtain from " Port リ Off ロ Application FA-500 " or " F-201L ", " the Off Le オ Application CD-123 " of Asahi Glass (strain), " テ Off ロ Application (R) 6J " of Mitsui デ ユ Port Application Off ロ ロ ケ ヤ カ Le (strain) of the big aurification industry of commercial conduct (strain).
The melt viscosity at 350 ℃ of the fluoro-resin that uses as dripping inhibitor (I) is generally 1.0 * 10 2～1.0 * 10 15(Pas), preferred 1.0 * 10 3～1.0 * 10 14(Pas), be more preferably 1.0 * 10 10～1.0 * 10 12(Pas).Melt viscosity is less than 1.0 * 10 2(Pas) time, dripping during burning prevents can be insufficient.Than 1.0 * 10 15When (Pas) big, the mobile of composition significantly reduces.
Use layered silicate as dripping inhibitor (I), the viewpoint of the flowability during from resin combination fusion of the present invention sees it is preferred.As layered silicate, can enumerate layered silicate, modified sheet silicate (having inserted 4 valency organic cations layered silicates) at interlayer, the layered silicate or the modified sheet silicate of reactive functional group have been given, but from the dispersed of laminar silicic acid salt pair resin combination of the present invention and drip prevent can viewpoint, preferred modified sheet silicate, pay the layered silicate or the modified sheet silicate that have added the reactive functional group, particularly, pay and added epoxy group(ing), amino oxazoline, carboxyl, the layered silicate of acid anhydrides isoreactivity functional group or modified sheet silicate are fit to use more.As the method for giving functional group, the method for using functionalized reagent's (silane coupling agent) processing is because easy and preferred.
As the functionalized reagent, can enumerate, for example, have epoxy group(ing) the chlorosilane class, have carboxyl the chlorosilane class, have sulfydryl the chlorosilane class, have amino alkoxyl silicone alkanes, have the alkoxyl silicone alkanes of epoxy group(ing) etc.Particularly, preferred 3-glycidoxy propyl-dimethyl chlorosilane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl dimethyl chlorosilane, 3-glycidoxy propyltrichlorosilan etc. has the chlorosilane class of epoxide group, the 3-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane etc. has amino alkoxyl silicone alkanes, 3-glycidoxy propyl group methyldiethoxysilane, the 3-glycidoxypropyltrime,hoxysilane, γ-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc. has the organoalkoxysilane of epoxide group.These functionalized reagents are preferably undertaken by mixing solvent-free or in polar solvent the contact of layered silicate.
The concrete example of the layered silicate that uses as the present invention, can enumerate swelling synthetic mica, vermiculite, fluorine vermiculite, halloysites etc. such as montmorillonite, hectorite, fluorine hectorite, saponite, beidellite, ス Block チ Application サ イ ト smectitess such as (subtincite) clay mineral, Li type fluorine taincolite, Na type fluorine taincolite, Na type tetrasiuicic fluoromica, Li type tetrasiuicic fluoromica, natural product, synthetics all can.Particularly, swelling synthetic micas such as smectites clay mineral, Li type fluorine taincolite, Na type fluorine taincolite, Na type tetrasiuicic fluoromica such as preferred montmorillonite, hectorite.
The 4 valency organic cations that insert as the interlayer of the modified sheet silicate that uses in the present invention, can enumerate, for example, dimethyl dialkyl ammoniums such as trimethylalkyl ammoniums such as trimethylammonium octyl group ammonium, trimethylammonium decyl ammonium, trimethyldodecane base ammonium, trimethylammonium tetradecyl ammonium, trimethylammonium cetyltrimethyl ammonium, trimethylammonium octadecyl ammonium, dimethyl dioctyl ammonium, dimethyl didecyl ammonium, dimethyl two (dodecyl) ammonium, dimethyl two (tetradecyl) ammonium, dimethyl two (hexadecyl) ammonium, dimethyldioc-tadecylammonium etc.
As dripping inhibitor (I), preferred silicone oil.As silicone oil; it is the compound of the dimethyl polysiloxane skeleton of following general formula (1) expression; also can be that part or all of end or side chain is subjected to amino modified, epoxide modified, carboxy-modified, methyl alcohol modification, methacryloyl modification, sulfhydryl modified, phenol modification, polyether-modified, vinyl toluene base modification, alkyl-modified, higher fatty acid is ester modified, senior alkoxy-modified, fluorine modification, and carry out the functional groupization.
The viscosity of the silicone oil that uses as dripping inhibitor (I) is generally 1000～30000 (cs.) at 25 ℃, and preferred 2000～25000 (cs.) are more preferably 3000～20000 (cs.).Viscosity is during less than 1000 (cs.), and aflame dripping prevents that effect from becoming insufficient, and flame retardant resistance reduces greatly, and when bigger than 30000 (cs.), because the tackify effect, the mobile of composition significantly reduces.
In flame retardant resistance PBT composition of the present invention, with respect to 100 weight part PBT, the amount of bromo aromatics based flame retardant (G) is generally 3～50 weight parts, and preferred 5～40 weight parts are more preferably 6～30 weight parts.The amount of bromo aromatics based flame retardant (G) is during less than 3 weight parts, and flame retardant effect is insufficient, and when surpassing 50 weight parts, physical strength reduces, and thermal stability during melting reduces easily.
In flame retardant resistance PBT composition of the present invention, with respect to 100 weight part PBT, the amount of antimony compounds (H) is generally 1～30 weight part, and preferred 2～25 weight parts are more preferably 3～20 weight parts.The amount of antimony compounds (H) can not obtain sufficient flame retardant effect during less than 1 weight part, and when surpassing 30 weight parts, physical strength reduces, and thermal stability during melting reduces easily.
In flame retardant resistance PBT composition of the present invention, with respect to 100 weight part PBT, the amount of dripping inhibitor (I) is generally 0～15 weight part.When the amount of dripping inhibitor (I) surpasses 15 weight parts, the danger that causes flowability or mechanical properties to reduce is arranged.
In flame retardant resistance PBT composition of the present invention, strengthen the kind of packing material (D) and amount and be with aforesaid hydrolytic resistance PBT composition in the same kind and the amount that illustrate.
(non-halogen fire retardant PBT composition)
Flame retardant resistance PBT composition of the present invention, it is characterized in that, total 100 weight parts with respect to aforesaid PBT (A) 50～95 weight parts and polyphenylene oxide resin (J) 5～50 weight parts contain solubility promoter (K) 0.05～10 weight part, are selected from least a kind compound (L) 2～45 weight parts, reinforcement packing material (D) 0～200 weight part, dripping inhibitor (I) 0～15 weight part, melamine cyanurate (M) 0～45 weight part and borate metal salt (N) 0～50 weight part in phosphoric acid ester or the phosphonitrile.
The polyphenylene oxide resin that so-called the present invention uses (J) (following brief note is PPE) is homopolymer or the multipolymer with structure of following general formula (2) expression.
Figure C20038010991200371
(in the formula, R 10Expression hydrogen atom, the first step or second stage alkyl, aryl, aminoalkyl group or-oxyl, R 11The expression first step or second stage alkyl, aryl or alkylamino, r represents the integer more than 10 or 10).
As R 10The first step alkyl of expression can be enumerated, for example, and methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, isopentyl, 2-methyl butyl, 2,3-dimethylbutyl, 2-, 3-or 4-methyl amyl or heptyl.As the suitable example of second stage alkyl, can enumerate sec.-propyl, sec-butyl or 1-ethyl propyl.As the homopolymer of suitable PPE, be for example to contain, 2,6-dimethyl-1, the material that the 4-phenylene ether units constitutes.As suitable multipolymer, be said units and 2,3,6-trimethylammonium-1, the random copolymers that constitutes of 4-phenylene ether units.
The PPE (J) that the present invention uses 30 ℃ of limiting viscosities of measuring down in chloroform are generally 0.20～0.80dL/g, and preferred 0.25～0.70dL/g is more preferably 0.30～0.60dL/g.Limiting viscosity is during less than 0.20dL/g, and the shock-resistance of composition is insufficient, when surpassing 0.80dL/g, has gel component too much, the tendency that the molding outward appearance worsens.
The solubility promoter (K) that so-called the present invention uses, be the compound that the dispersiveness of the PPE among the PBT is improved, can use polycarbonate resin, have the compound that is selected from the functional group in carboxyl, carboxylic acid ester groups, carboxylic acyloxy amido, imide, anhydride group, epoxy group(ing), oxazolinyl, amino, the hydroxyl more than 1 or 1, bi-ester of phosphite etc.
As the concrete example of compound with functional group, can enumerate epoxy group(ing) addition PPE resin, hydroxyalkylation PPE resin, Mo Duan oxazoline PPE resin, C-terminal by the polyester of polystyrene modification, C-terminal by PE modified polyester etc.
As solubility promoter (K), viewpoint from the hydrolytic resistance of composition of the present invention, crystallinity, mechanical properties, flame retardant resistance, preferred phosphorous acid ester or polycarbonate resin, in phosphorous acid ester, preferred tris phosphite, particularly, preferred following general formula (3) or the tris phosphite of (4) expression.
(in the formula, R 12～R 14Independent separately, can contain Sauerstoffatom, nitrogen-atoms, sulphur atom, the alkyl of expression carbonatoms 1～20 or the replacement or the non-substituted aryl of carbonatoms 6～30).
Concrete example as general formula (3), can enumerate the tricresyl phosphite monooctyl ester, tridecyl phosphite, trilauryl phosphite, tricresyl phosphite (octadecyl) ester, the different monooctyl ester of tricresyl phosphite, tricresyl phosphite (nonyl benzene) ester, tricresyl phosphite (2,4-dinonyl benzene) ester, tricresyl phosphite (2, the 4-di-tert-butyl) ester, triphenyl phosphite, tricresyl phosphite (octyl group benzene) ester, the different monooctyl ester of phosphorous acid phenylbenzene, phosphorous acid phenylbenzene isodecyl ester, phosphorous acid octyl group diphenyl ester, phosphorous acid dilauryl phenyl ester, phosphorous acid diiso decyl phenyl ester, two (nonyl phenyl) phenyl esters of phosphorous acid, phosphorous acid diisooctyl phenyl ester etc.
Figure C20038010991200391
(in the formula, u is 1 or 2, R 15Can be the same or different, can contain Sauerstoffatom, nitrogen-atoms, sulphur atom, the alkyl of expression carbonatoms 1～20 or the replacement or the non-substituted aryl of carbonatoms 6～30.R 16At u is 1 o'clock, and the alkylidene group of expression carbonatoms 1～20 or the replacement or the non-replacement arylidene of carbonatoms 6～30 are 2 o'clock at u, alkyl four bases of expression carbonatoms 4～18).
As R 15Example, can enumerate methyl, ethyl, propyl group, octyl group, iso-octyl, isodecyl, decyl, octadecyl, lauryl, phenyl, 2-, 3-or 4-aminomethyl phenyl, 2,4-or 2,6-3,5-dimethylphenyl, 2,3, the 6-trimethylphenyl, 2-, 3-or 4-ethylphenyl, 2-, 4-or 2-, 6-diethyl phenyl, 2,3,6-triethyl phenyl, 2-, 3-or 4-tert-butyl-phenyl, 2,4-or 2, the 6-di-tert-butyl-phenyl, 2,6-di-t-butyl-4-aminomethyl phenyl, 2,6-di-t-butyl-4-ethylphenyl, octyl phenyl, the iso-octyl phenyl, 2-, 3-or 4-nonyl phenyl, 2,4-dinonyl phenyl, xenyl, naphthyl etc.Particularly, preferably replace or the aryl of non-replacement.As R 16, in general formula (4), during u=1, can enumerate 1, polymethylenes such as 2-phenylene, ethylidene, propylidene, trimethylene, tetramethylene, hexa-methylene.
Concrete example as the compound of general formula (4), at u is 1 o'clock, can enumerate, (phenyl) (1 for example, the 3-propane diol) phosphorous acid ester, (4-aminomethyl phenyl) (1, the 3-propane diol) phosphorous acid ester, (2, the 6-3,5-dimethylphenyl) (1, the 3-propane diol) phosphorous acid ester, (4-tert-butyl-phenyl) (1, the 3-propane diol) phosphorous acid ester, (2, the 4-di-tert-butyl-phenyl) (1, the 3-propane diol) phosphorous acid ester, (2, the 6-di-tert-butyl-phenyl) (1, the 3-propane diol) phosphorous acid ester, (2,6-di-t-butyl-4-aminomethyl phenyl) (1, the 3-propane diol) phosphorous acid ester, (phenyl) (1, the 2-ethane diol) phosphorous acid ester, (4-aminomethyl phenyl) (1, the 2-ethane diol) phosphorous acid ester, (2, the 6-3,5-dimethylphenyl) (1, the 2-ethane diol) phosphorous acid ester, (4-tert-butyl-phenyl) (1, the 2-ethane diol) phosphorous acid ester, (2, the 6-di-tert-butyl-phenyl) (1, the 2-ethane diol) phosphorous acid ester, (2,6-di-t-butyl-4-aminomethyl phenyl) (1, the 2-ethane diol) phosphorous acid ester, (2,6-di-t-butyl-4-aminomethyl phenyl) (1, the 4-butanediol) phosphorous acid ester etc.
In addition, during u=2, R 16Can enumerate four groups etc. of the tetramethylolmethane structure of following general formula (5) expression.
Figure C20038010991200401
(in the formula, v, w, x, y represent 0～6 integer respectively).
As concrete example, can enumerate the diiso decyl pentaerythritol diphosphites, the dilauryl pentaerythritol diphosphites, two octadecyl pentaerythritol diphosphites, the diphenyl pentaerythritol diphosphites, two (2-aminomethyl phenyl) pentaerythritol diphosphites, two (3-aminomethyl phenyl) pentaerythritol diphosphites, two (4-aminomethyl phenyl) pentaerythritol diphosphites, two (2, the 4-3,5-dimethylphenyl) pentaerythritol diphosphites, two (2, the 6-3,5-dimethylphenyl) pentaerythritol diphosphites, two (2,3, the 6-trimethylphenyl) pentaerythritol diphosphites, two (2-tert-butyl-phenyl) pentaerythritol diphosphites, two (3-tert-butyl-phenyl) pentaerythritol diphosphites, two (4-tert-butyl-phenyl) pentaerythritol diphosphites, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2, the 6-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, two (xenyl) pentaerythritol diphosphites, dinaphthyl pentaerythritol diphosphites etc.
In the above-mentioned tris phosphite, in formula (4), preferred u is 1 or 2 represented compounds, in addition, when being more preferably the u=2 of formula (4), R 16Compound for four groups of the tetramethylolmethane structure of general formula (5) expression etc.Wherein, be more preferably two (nonyl phenyl) pentaerythritol diphosphites, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites etc., preferred especially two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites.In addition, composition of the present invention also can contain the compound by decomposition (hydrolysis, the thermolysis etc.) generation of these tris phosphites.
As the polycarbonate resin that uses as solubility promoter (K) in the present invention, that can enumerate diester reaction manufacturing by making aromatic dihydroxy compound or itself and a spot of polyol and phosgene or carbonic acid also can ramose thermoplasticity aromatic polycarbonate polymers or multipolymer.
As aromatic dihydroxy compound, can enumerate 2, two (4-hydroxyphenyl) propane (=dihydroxyphenyl propane) of 2-, tetramethyl-dihydroxyphenyl propane, two (4-hydroxyphenyl)-p-Diisopropylbenzene, quinhydrones, cresorcin, 4,4-dihydroxybiphenyl etc., preferred dihydroxyphenyl propane.
In order to obtain the ramose polycarbonate resin, can be with Phloroglucinol monomethyl ether, 4,6-dimethyl-2,4,6-three (4-hydroxyphenyl) heptene-2,4,6-dimethyl-2,4,6-three (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-three (4-hydroxyphenyl) teracrylic acid, 1,3,5-three (4-hydroxyphenyl) benzene, 1,1, the polyol of expression such as 1-three (4-hydroxyphenyl) ethane, perhaps 3, two (4-hydroxyaryl) the oxygen base indoles (=isatin bis-phenol) of 3-, the 5-chlorisatide, 5,7-two chlorisatides, 5-bromoisatins etc. use as the part of above-mentioned aromatic dihydroxy compound, its usage quantity is generally 0.01～10 mole of %, preferred 0.1～2 mole of %.
As aromatic polycarbonate resin, preferably can enumerate by 2 two (4-hydroxyphenyl) propane deutero-polycarbonate resins of 2-or by 2, two (4-hydroxyphenyl) propane of 2-and other aromatic dihydroxy compound deutero-Copolycarbonate.
The molecular weight of the polycarbonate resin that uses as solubility promoter (K) as by using methylene dichloride as solvent, in the viscosity-average molecular weight that 25 ℃ of soltion viscosities of measuring down of temperature convert, is generally 16000～30000, preferred 18000～23000.As polycarbonate resin, the polycarbonate resin that can mix more than 2 kinds or 2 kinds uses.
As the phosphate compound (L) that the present invention uses, can comprise the phosphoric acid ester of wide scope.As its concrete example, can enumerate trimethyl phosphate, triethyl phosphate, Tributyl phosphate ester, trioctylphosphine phosphoric acid ester, three butoxyethyl group phosphoric acid ester, triphenyl, three cresyl phosphoric acid ester, cresyl diphenyl phosphoester, octyl group diphenyl phosphoester etc.Particularly, the compound of preferred following general formula (6) expression.
Figure C20038010991200411
(in the formula, R 1～R 8The alkyl of representing hydrogen atom or carbonatoms 1～6 independently of one another, m are 0 or 1～4 integer, R 9For to phenylene, metaphenylene, 4,4 '-biphenylene group or be selected from following divalent group).
Figure C20038010991200412
In above-mentioned general formula (6), R 1～R 8From the viewpoint of the hydrolytic resistance that improves the present composition, preferred carbonatoms 6 or 6 following alkyl are more preferably carbonatoms 2 or 2 following alkyl, special preferable methyl.M is preferred 1～3, is more preferably 1.R 9Preferably, be more preferably metaphenylene to phenylene or metaphenylene.
In addition, as composition (L), suitable use has the phosphazene compound of the group of following general formula (7) expression.
Figure C20038010991200421
(in the formula, X represents-O-,-S-,-NH-or Direct Bonding, R 17And R 18Aryl, alkyl, the cycloalkyl of expression carbonatoms 1～20, R 17-X-, R 18-X-both can be the same or different, and n represents 1～12 integer).
In general formula (7), as R 17And R 18Concrete example, can enumerate aryl such as cycloalkyl, phenyl, naphthyl such as the alkyl that can be replaced by methyl, ethyl, butyl, hexyl, benzyl etc., cyclohexyl.N is preferred 3～10, is more preferably 3 or 4.The phosphazene compound of general formula (7) both can be that simple linear polymer also can be a cyclic polymer, but preferred cyclic polymer.X is preferred-O-or-NH-, preferred-O-especially.
As the concrete example of the phosphazene compound shown in the general formula (7), can enumerate hexaphenoxycyclotriphosphazene, six (hydroxyphenoxy) ring three phosphonitriles, eight phenoxy group rings, four phosphonitriles, eight (hydroxyphenoxies) ring, four phosphonitriles etc.
The melamine cyanurate (M) that so-called the present invention uses, it is the roughly equimolar reactant of cyanuric acid and trimeric cyanamide, for example, can be by the aqueous solution of mixing cyanuric acid and the aqueous solution of trimeric cyanamide, stirring reaction under 90～100 ℃ temperature obtains the sedimentation and filtration that generates then.The particle diameter of melamine cyanurate is generally 0.01～1000 μ m, preferred 0.01～500 μ m.Several in the amino of melamine cyanurate or the hydroxyl also can be replaced by other substituting group.
The borate metal salt (N) that so-called the present invention uses is stable under normally used treatment condition preferably, and does not have the material of volatile component.As borate metal salt (N), can enumerate an alkali metal salt (for example, sodium tetraborate, potassium metaborate etc.), alkaline earth salt (for example, lime borate, orthoboric acid magnesium, orthoboric acid barium, zinc borate etc.) of boric acid etc.In the middle of these, preferred boric acid zinc.Zinc borate is generally with 2ZnO3B 2O 3XH 2O (x=3.3～3.7) expression.As hydration zinc borate, preferably with 2ZnO3B 2O 33.5H 2The formula of O is represented and at 260 ℃ or even the material also more stable than this higher temperature.
In halogen-free flame-retardant PBT composition of the present invention, polyphenylene oxide (J) amount (PPE) as the weight ratio of PBT: PPE, is 95: 5～50: 50, preferred 92: 8～55: 45, is more preferably 90: 10～60: 40.The ratio of PPE was less than 5 o'clock, and the flame retardant resistance of composition or hydrolytic resistance become insufficient, surpassed at 50 o'clock, and the flowability or the resistance of composition significantly reduce.
In halogen-free flame-retardant PBT composition of the present invention, with respect to total 100 weight parts of PBT and PPE, the amount of solubility promoter (K) is 0.05～10 weight part, and preferred 0.1～8 weight part is more preferably 0.3～5 weight part.The amount of solubility promoter (K) is during less than 0.05 weight part, and the rerum natura of composition, particularly physical strength or flame retardant resistance reduce, and when surpassing 10 weight parts, the appearance of flame retardant resistance, goods reduces.In halogen-free flame-retardant PBT composition of the present invention, with respect to total 100 weight parts of PBT and PPE, the amount of phosphate Huo Phosphonium (L) is 2～45 weight parts, and preferred 3～40 weight parts are more preferably 5～30 weight parts.When the amount of phosphate Huo Phosphonium (L) surpassed 2 weight parts, the flame retardant resistance of composition was insufficient, and when surpassing 45 weight parts, mechanical properties, hydrolytic resistance, plasticity significantly reduce.
In halogen-free flame-retardant PBT composition of the present invention, strengthen the kind of packing material (D) and amount and be with aforesaid hydrolytic resistance PBT composition in the same kind and the amount that illustrate.
In halogen-free flame-retardant PBT composition of the present invention, the kind of dripping inhibitor (I) and amount be with aforesaid flame retardant PBT composition in the same kind and the amount that illustrate.
In halogen-free flame-retardant PBT composition of the present invention, when using layered silicate as dripping inhibitor (I), with respect to total 100 weight parts of PBT and PPE, its amount is generally 0～15 weight part, preferred 0.3～12 weight part is more preferably 0.5～10 weight part.Containing when surpassing 15 weight parts of layered silicate, flowability or mechanical properties reduce terrifically.In addition, layered silicate can use a kind, also can be also with more than 2 kinds or 2 kinds.
In halogen-free flame-retardant PBT composition of the present invention, when using silicone oil as dripping inhibitor (I), with respect to total 100 weight parts of PBT and PPE, its amount is 0～15 weight part, and preferred 0.005～8 weight part is more preferably 0～5.0 weight part.When the amount of silicone oil surpassed 15 weight parts, mobile, mechanical character significantly reduced.
In halogen-free flame-retardant PBT composition of the present invention, with respect to total 100 weight parts of PBT and PPE, the amount of melamine cyanurate (M) is 0～45 weight part, and preferred 3～40 weight parts are more preferably 5～30 weight parts.When the amount of melamine cyanurate (M) surpassed 45 weight parts, toughness or ductility reduced, or caused and ooze out or separate out (plate-out) a kind of component.
In halogen-free flame-retardant PBT composition of the present invention, the ratio that is selected from least a kind compound (L) and melamine cyanurate (M) in phosphoric acid ester or the phosphonitrile is generally 1: 9～and 9: 1, preferred 2: 8～8: 2, be more preferably 2.5: 7.5～7.5: 2.5.
In halogen-free flame-retardant PBT composition of the present invention, with respect to total 100 weight parts of PBT and PPE, the amount of borate metal salt (N) is 0～50 weight part, and preferred 2～45 weight parts are more preferably 3～40 weight parts.When the amount of borate metal salt (N) surpassed 50 weight parts, mechanical properties reduced easily.
(other functional PBT composition-1)
Other functional PBT composition-1 of the present invention, it is characterized in that, with respect to above-mentioned PBT (A) 100 weight parts, contain polycarbonate resin (O) 5～100 weight parts, organo phosphorous compounds (P) 0.01～1 weight part, strengthen packing material (D) 0～200 weight part and shock-resistant modifying agent (F) 0～50 weight part.This functional PBT composition-1, particularly when as molding, shrinking percentage or allowance for camber reduce, excellent in dimensional stability.
As the polycarbonate resin (O) that the present invention uses, can enumerate by aromatic dihydroxy compound or its diester with a spot of polyol and phosgene or carbonic acid react manufacturing also can ramose carbonate polymer or multipolymer.
As aromatic dihydroxy compound, can enumerate 2, two (4-hydroxyphenyl) propane (=dihydroxyphenyl propane) of 2-, tetramethyl-dihydroxyphenyl propane, two (4-hydroxyphenyl)-p-Diisopropylbenzene, quinhydrones, cresorcin, 4,4-dihydroxybiphenyl etc., preferred dihydroxyphenyl propane.
In order to obtain the ramose aromatic polycarbonate resin, can be with Phloroglucinol monomethyl ether, 4,6-dimethyl-2,4,6-three (4-hydroxyphenyl) heptene-2,4,6-dimethyl-2,4,6-three (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-three (4-hydroxyphenyl) teracrylic acid, 1,3,5-three (4-hydroxyphenyl) benzene, 1,1, the polyol of expression such as 1-three (4-hydroxyphenyl) ethane, perhaps 3, two (4-hydroxyaryl) the oxygen base indoles (=isatin bis-phenol) of 3-, the 5-chlorisatide, 5,7-two chlorisatides, 5-bromoisatins etc. use as the part of above-mentioned aromatic dihydroxy compound, its usage quantity is generally 0.01～10 mole of %, preferred 0.1～2 mole of %.
As aromatic polycarbonate resin, preferably can enumerate 2, two (4-hydroxyphenyl) propane of 2-and phosgene or carbonic diester react the polycarbonate resin of making or use 2, the Copolycarbonate that two (4-hydroxyphenyl) propane of 2-and other aromatic dihydroxy compound are made.In addition, the polycarbonate resin that also can mix more than 2 kinds or 2 kinds uses.
The molecular weight of polycarbonate resin as by using methylene dichloride as solvent, in the viscosity-average molecular weight that 25 ℃ of soltion viscosities of measuring down of temperature convert, is generally 15000～30000, preferred 16000～25000.
As the organo phosphorous compounds (P) that the present invention uses, can enumerate organophosphorus compounds, organic phosphorous acid ester cpds or organic phosphinate compound etc.In the middle of these, preferred organophosphorus compounds, particularly, the chain alkyl phosphate ester acid compound of preferred following general formula (8) expression.
(R-O) nP(O)(OH) 3-n (8)
(in the formula, R represents the alkyl of carbonatoms 8～30, and n is 1 or 2).
In general formula (8), as the concrete example of the alkyl of the carbonatoms of representing with R 8～30, can enumerate n-octyl, 2-ethylhexyl, iso-octyl, nonyl, different nonyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, triacontyl etc.In addition, also can use n is that 1 monoalkyl phosphate ester acid, n are 2 dialkyl group phosphate ester acid or their mixture.
In other functional PBT composition-1 of the present invention, with respect to 100 weight part PBT, the amount of polycarbonate resin (O) is 5～100 weight parts, and preferred 7～90 weight parts are more preferably 10～80 weight parts.The amount of polycarbonate resin (O) is during less than 5 weight parts, and the minimizing effect of the shrinking percentage of molding or allowance for camber is insufficient, and when surpassing 100 weight parts, crystallization speed is slow, and melt viscosity raises, and plasticity extremely worsens.
In other functional PBT composition-1 of the present invention, with respect to 100 weight part PBT, the amount of organo phosphorous compounds (P) is generally 0.01～1 weight part, and preferred 0.05～0.6 weight part is more preferably 0.1～0.4 weight part.The amount of organo phosphorous compounds (P) is during less than 0.01 weight part, and the raising effect that adds thermostability and be detained stability of composition reduces, and when surpassing 1 weight part, causes the reduction of hydrolytic resistance.Organo phosphorous compounds (P) also can a kind of or also usefulness use more than two kinds or two kinds.
In other functional PBT composition-1 of the present invention, strengthen the kind of packing material (D) and amount and be with aforesaid hydrolytic resistance PBT composition in the same kind and the amount that illustrate.
In other functional PBT composition-1 of the present invention, kind as shock-resistant modifying agent (F), can use the material of the same kind that illustrates in the aforesaid shock-resistance PBT composition, with respect to 100 weight part PBT, its amount is 0～50 weight part, preferred 1～45 weight part is more preferably 2～40 weight parts.When the amount of shock-resistant modifying agent (F) surpassed 50 weight parts, mechanical characteristicies such as tensile strength, flexural strength reduced significantly.
(other functional PBT composition-2)
Other functional PBT composition-2 of the present invention is characterized in that, with respect to above-mentioned PBT (A) 100 weight parts, contains 5～100 heavy parts of aromatic polyester-based resins (Q) beyond the PBT and strengthens packing material (D) 0～200 weight part.This functional PBT composition-2, particularly when as molding, appearance (transparency) excellence.
As the PBT aromatic polyester-based resin (Q) in addition that the present invention uses, can enumerate polyalkylene terephthalates, poly-naphthalic acid alkylidene diol ester etc.As these concrete example, can enumerate poly terephthalic acid-1,4 cyclohexane dimethanol ester (PCT), polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PPT), PEN (PEN), poly-naphthalic acid propylene glycol ester (PPN), PBN (PBN) etc.In the middle of these, preferred polyethylene terephthalate and Poly(Trimethylene Terephthalate) are more preferably polyethylene terephthalate.
Here said polyethylene terephthalate, being to make the aklylene glycol of terephthalic acid or its ester formation property derivative and carbonatoms 2 or the polymkeric substance that the polycondensation of its ester formation property derivative obtains, also can be to contain polyethylene terephthalate 70 weight % or the above multipolymer of 70 weight %.Monomer as copolymerization, as the dicarboxylic acid component beyond terephthalic acid and the low-carbon-ester thereof, can enumerate m-phthalic acid, naphthalene dicarboxylic acids, hexanodioic acid, sebacic acid, trimellitic acid, aliphatics such as Succinic Acid, aromatic series polyprotonic acid or its ester formation property derivative etc., in addition, as the diol component beyond the ethylene glycol, be generally aklylene glycol, for example, remove Diethylene Glycol, propylene glycol, 1, ammediol, 1, the 6-hexylene glycol, neopentyl glycol, outside the cyclohexanedimethanol etc., can also enumerate 1, low-grade alkylidene glycol such as 3-ethohexadiol, 2 moles of affixtures of the oxyethane of dihydroxyphenyl propane, 3 moles of alkylene oxide adducts alcohol such as affixture of the propylene oxide of dihydroxyphenyl propane, glycerol, polyol such as tetramethylolmethane and ester thereof form property derivative etc.
In the present invention, so-called polytrimethylene terephthalate is meant with terephthalic acid or its ester formation property derivative and 1, polymkeric substance or multipolymer that ammediol obtains by condensation reaction as principal constituent.In this polymkeric substance, both can be a part and other omega-dicarboxylic acids or its ester formation property derivatives class metathetical material with terephthalic acid, also can be with 1, the part of ammediol and other glycols and/or three alcohols metathetical materials.As ester formation property derivative, preferred ester, preferred especially dimethyl terephthalate (DMT).
In other functional PBT composition-2 of the present invention, with respect to 100 weight part PBT, the amount of the aromatic polyester (Q) beyond the PBT is 5～100 weight parts, and preferred 7～90 weight parts are more preferably 10～70 weight parts.The amount of the aromatic polyester (Q) beyond the PBT is during less than 5 weight parts, almost do not find the improvement of the appearance of molding, when surpassing 100 weight parts, produce the increase of forming period, the deterioration of release property etc., and the reduction of the mechanical characteristics of problem in the generation shaping and molding.
In other functional PBT composition-2 of the present invention, strengthen the kind of packing material (D) and amount and be with aforesaid hydrolytic resistance PBT composition in the same kind and the amount that illustrate.In addition, as the method for further raising appearance (transparency), add and promote that the catalyzer of transesterification reaction is effective.Transesterify promotes catalyzer can be subordinated in the oxide compound of the metal of 1A family, 2A family, 2B family, 4A family, 4B family, 5B family, 7A family, 8 families, oxyhydroxide, the organic metal salt to select, but wherein, as metal, preferred sodium, calcium, lithium zinc, cobalt, manganese etc., organic metal salts such as particularly preferred sodium stearate, calcium stearate, Magnesium Stearate.Addition is generally 0.001～1 weight %.
(other functional PBT composition-3)
Other functional PBT composition-3 of the present invention, it is characterized in that, with respect to above-mentioned PBT (A) 100 weight parts, contain styrene resin (R) 5～100 weight parts, maleic anhydride modified polystyrene resin (S) or polycarbonate resin (O) 0～40 weight part, strengthen packing material (D) 0～200 weight part.This functional PBT composition-3, particularly when as molding, shrinking percentage or allowance for camber reduce, excellent in dimensional stability.
The styrene resin (R) that the present invention uses, it can be rubber-modified styrene resin, for example, can use the homopolymerization of (1) aromatic vinyl monomer or multipolymer, (2) to be selected from multipolymer of at least a kind in aromatic vinyl monomer and comonomer (for example, nitrilation vinyl monomer) and the rubber constituent etc.Styrene resin can be used in combination separately or more than 2 kinds or 2 kinds.
As above-mentioned aromatic vinyl monomer, can enumerate vinylbenzene, Vinyl toluene, alpha-methyl styrene etc., special optimization styrene.As above-mentioned nitrilation vinyl monomer, can enumerate, for example, unsaturated nitriles such as vinyl cyanide, methacrylonitrile.These nitrilation vinyl monomers can be used in combination separately or more than 2 kinds or 2 kinds.As preferred nitrilation vinyl monomer is vinyl cyanide.As rubber-modified styrene resin, can enumerate, for example, ABS resin, HIPS resin etc.
The number-average molecular weight of above-mentioned styrene resin (parent resin in the rubber-modified styrene resin) is generally 0.5 * 10 4～200 * 10 4, preferred 1 * 10 4～100 * 10 4Scope.Number-average molecular weight is less than 0.5 * 10 4The time, intensity reduces, than 200 * 10 4When big, the mobile reduction.
The maleic anhydride modified polystyrene resin (S) that so-called the present invention uses is meant the material that contains maleic anhydride in polystyrene.As making maleic anhydride contain method in polystyrene, can enumerate with both merely machinery the blended method, with the method for styrene monomer etc. and maleic anhydride copolymerization etc.As the latter's copolymerization method, can enumerate emulsion polymerization, solution polymerization process, suspension polymerization etc.The containing ratio of maleic anhydride is generally 1～40 weight %, and preferred 2～30 weight % are more preferably 3～20 weight %.
In PBT composition-3 of the present invention, with respect to 100 weight part PBT, the amount of styrene resin (R) is 5～100 weight parts, and preferred 7～90 weight parts are more preferably 10～80 weight parts.The amount of styrene resin (R) is during less than 5 weight parts, and it is insufficient that the shrinking percentage of molding or anti-flexible reduce effect, and when surpassing 100 weight parts, the reduction of mechanical properties is remarkable.
In PBT composition-3 of the present invention, maleic anhydride modified polystyrene resin (S) or polycarbonate resin (O) are to work as styrene resin that does not contain nitrilation vinyl monomer such as HIPS and the solubility promoter of PBT.With respect to 100 weight part PBT, the amount of these resins is 0～40 weight part, and preferred 5～30 weight parts are more preferably 10～20 weight parts.When the amount of these resins surpassed 40 weight parts, mechanical properties reduced.
In PBT composition-3 of the present invention, strengthen the kind of packing material (D) and amount and be with aforesaid hydrolytic resistance PBT resin in the same kind and the amount that illustrate.In addition, for above-mentioned polycarbonate resin (O), also can use with aforesaid hydrolytic resistance PBT resin in the material of the same kind that illustrates.
In the present invention, as the method that in PBT, contains various additives, preferably add the method for additive by melting mixing.As the melting mixing method, can use the normally used compounding process of thermoplastic resin.For example, with various compositions with the additional composition that adds optionally, after the mixing of homogeneous such as Henschel mixer, propeller type mixing machine, V-Mixer, use single shaft mixing extruder, multiaxis mixing extruder, roller, banbury mixers, Bradley Bender machine (Block ラ ベ Application ダ one) to carry out mixing.
Each composition comprises additional composition, can supply to mixing roll together.In addition, also can supply with successively, in addition, also the composition more than 2 kinds or 2 kinds that is selected from each composition that comprises additional composition can be pre-mixed.Glass fibre etc. are strengthened the class packing material, can be by in the way of extruding, adding after the resin fusion, thus avoid broken, can bring into play high characteristic.In addition, when adding aqueous epoxy compounds, also can be in the way of extruding, by adding in the machine that epoxy compounds is pressed into the PBT melting mixing.
The method for processing forming of PBT of the present invention and composition thereof has no particular limits, can use the general moulding method of using of thermoplastic resin, that is, and moulding methodes such as injection forming, hollow forming, extrusion molding, die forming.
PBT of the present invention, owing to tone, hydrolytic resistance, thermostability, the transparency, have excellent formability, is suitable as electric, electronic component, automobile with injection forming parts such as parts, particularly, because few foreign, the transparency or excellent heat stability, in purposes such as film, monofilament, fiber, improved effect is remarkable.
Then, film of the present invention is described.Film of the present invention is characterised in that, contains PBT, and described PBT contains titanium, and is 33ppm or below the 33ppm in its content of titanium atom.As such PBT, can use above-mentioned PBT.The limiting viscosity of the PBT that film is used is generally 0.80～2.50dL/g, and preferred 0.90～1.80dL/g is more preferably 1.00～1.30dL/g.The physics value of other of PBT is same as described above.
The film forming and machining method of PBT of the present invention has no particular limits, can use the general moulding method of using of thermoplastic resin, that is, and T die casting moulding method, air-cooled expansion-molded method, the expansion-molded injection molding method of water-cooled, polishing roll method etc.
In addition, PBT film of the present invention, can become the compoundization film of resin molding with other, as the resin of the resin molding of compoundization, preferred polyolefm resinoid (new LDPE (film grade): LDPE), straight-chain low density polyethylene: LLDPE), high density polyethylene(HDPE): HDPE), homo-polypropylene), with the olefines of carbonatoms 2～8 block copolymerization polypropylene as the comonomer copolymerization, atactic copolymerized polypropene, ethylene-vinyl acetate copolymer, the partly-hydrolysed thing (EVOH) of ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, the ionomer class, styrene-ethylene copolymers, ethylene-butene copolymer, styrene-ethylene-butylene copolymer etc.
Insufficient bonding with PBT, the occasion of the combination of the polyolefin resin of splitting simply can be at interlayer, and complex acid modification or epoxy modified resin (so-called adhesive resin) become 3 kind of 3 tunic.
In addition, can also enumerate in order to gain in strength, replace polyolefin resin to use 3 kind of 3 tunic (PBT/ bonding/polymeric amide) of polymeric amide or between PBT and polymeric amide, polymeric amide and polyolefine, cooperate 5 kind of 5 tunic (PBT/ bonding/polymeric amide/bonding/polyolefine), the replacement polymeric amide of adhesive resin to cooperate 5 kinds 5 layers of EVOH (PBT/ is bonding/EVOH/ is bonding/polyolefine) etc. respectively.In addition, consider when having intensity and oxygen barrier concurrently, also can become and between PBT and polyolefine, cooperated 6 tunics (PBT/EVOH/ polyamide/polyolefine) of polymeric amide and EVOH, cooperated 6 tunics (PBT/ bonding/EVOH/ polymeric amide/bonding/polyolefine) of adhering resin at interlayer respectively.
Manufacturing means as compoundization film, the general coetrusion that uses, but also can utilize in case be shaped after the PBT film, use dried laminating that tackiness agent fits, PBT is being extruded known methods such as extruding layer platen press on the PBT film on polyolefin film or the polyester film etc. or with other molten resin.
In the extruding layer platen press, can be on the film surface of making in advance, coupler or reaction-ing adhesives such as coating epoxies, amino formate, titanate ester, type siloxane, or apply known surface treatment such as corona discharge.
The thickness of PBT film of the present invention (occasion of compoundization film is the thickness of PBT rete) is generally 5～200 μ m.Particularly, in the occasion of unitary film, be generally 10～150 μ m, preferred 20～100 μ m, the occasion of compoundization film (PBT rete) is generally 5～100 μ m, preferred 10～80 μ m, all thickness of compoundization film is generally 20～300 μ m, preferred 50～200 μ m.
Usually, the mist value of PBT film is subjected to the influence of thickness, molding condition, film thick more or extrude after cooling temperature the high fog value is high more more.Therefore, in the present invention, when being shaped the PBT film of 50 μ m by T die casting moulding method, water-cooled plavini, preferably the mist value of its film is less than 2%.Obtain the cooling temperature in such film, that is, the surface temperature of first section cooling roller of the occasion of teeming practice is below 60 ℃ or 60 ℃, is below 70 ℃ or 70 ℃ at the temperature of cooling water of the occasion of water-cooled plavini.The mist value of the film that is shaped under this molding condition surpasses at 2% o'clock, and in appearance, the film albefaction loses transparent, thus the infringement commodity value.In addition, when cooperating additive in PBT of the present invention, the crystallized temperature that its addition preferably is adjusted to the PBT resin combination is no more than 200 ℃, and in addition, the mist value in the film that is configured as 50 μ m thickness is no more than 2% addition.
PBT of the present invention, as previously mentioned, can copolymerizationization or with other mixed with resinization (alloying), particularly in film, PBT of the present invention, the control of the crystallinity or the transparency is easy, in addition, in order to improve various mechanical properties, preferably with other mixed with resinization.At the suitable hybrid resin of the occasion of film, can enumerate polyester, polycarbonate, polymeric amide, polyphenylene oxide, polystyrene, polymethyl acrylic acid or polymethacrylate, polyacrylic acid or polyacrylic ester, polyolefine etc. as particularly.In addition, as hybrid resin, also can be the PBT beyond the PBT of the present invention.In addition, can mix composition or the different PBT of the present invention of molecular weight.In the middle of these, from the viewpoint of the intermiscibility or the transparency, preferred polyester, special optimization aromatic polyester.In aromatic polyester, the preferred aromatic polyester that in above-mentioned " other functional PBT composition-2 ", exemplifies.
Usually, with the mixture of PBT and other the polyester film as raw material, in order to make its maximizing performance, the transesterification reaction of controlling between them is important, if catalyzer is too much, remaining in PBT, then transesterification reaction is too fast, and the control difficulty becomes., PBT of the present invention, owing to reduced the amount of catalyzer significantly, the control of transesterification reaction becomes easily, can adopt wide compound or molding condition.Particularly, comparing with PBT, the fusing point height, in the mixed system of the polyethylene terephthalate of the mold temperature that necessary setting is high, PEN etc., its improved effect is also big.
In addition, even with copolymerization owing to remaining catalyzer make that decomposition reaction quickens poly-1, in the mixed system of the polyester of 4-butyleneglycol (optimization aromatic polyester),, can more reduce decomposition owing to use the significantly reduced PBT of the present invention of remaining catalyzer.
The mixture ratio of PBT of the present invention and other resin (weight ratio) has no particular limits, and is generally 99: 1～1: 99, preferred 95: 5～5: 95, is more preferably 90: 1010: 90.
PBT film of the present invention, owing to possess above-mentioned characteristic, has the feature that clearly to see content, except food packaging film, industrial goods packing film, pack these usefulness bag with the former film, also be fit to be used in the sheet pack tunic used with surface-coated material membrane, construction applications or food cans headed by the shrink film etc. with pattern.
Embodiment
Below, by embodiment the present invention is described in further detail, but the present invention is only otherwise exceed its purport, is not subjected to any restriction of following embodiment.In addition, the measuring method of rerum natura that adopts in each following embodiment and assessment item is as follows.
(1) esterification yield:
Calculate by acid number and saponification value by following calculating formula V.Acid number uses the KOH/ methanol solution titration of 0.1N to obtain by oligopolymer is dissolved in the dimethyl formamide.Saponification value is the KOH/ ethanolic soln hydrolyzed oligomers with 0.5N, tries to achieve with the salt acidometric titration of 0.5N.
Esterification yield=[(saponification value-acid number)/(saponification value)] * 100 (V)
(2) end carboxy concentration:
In the 25mL phenylcarbinol, dissolving 0.5gPBT or oligopolymer use the benzyl alcohol solution titration of 0.01 mole/L of sodium hydroxide.
(3) limiting viscosity (IV):
Use ubbelohde viscometer to try to achieve according to following main points.That is, use the mixed solvent of phenol/tetrachloroethane (weight ratio 1/1), under 30 ℃, measure the polymers soln and second number that falls that is solvent of concentration 1.0g/dL, (VI) obtains according to following formula.
[VI]＝((1+4K Hη sp) 0.5-1)/(2KHC) (VI)
(in the formula, η Sp=η/η 0-1, η be polymers soln fall a second number, η 0Be second number that falls of solvent, C is polymer solution concentration (g/dL), K HBe Kieren Perkins constant, K HAdopt 0.33).
(4) the titanium concentration among the PBT:
With used in electronic industry high purity sulfuric acid and nitric acid the PBT wet type is decomposed, use high de-agglomeration to measure by ICP (InducedCoupled Plasma)-MS (Mass Spectrometer) (サ one モ Network エ ス ト society system).
(5) terminal methoxy group carbonyl concentration, terminal ethylenyl groups concentration and terminal hydroxyl concentration:
In the mixed solvent of deuterochloroform/hexafluoroisopropanol=7/3 of 1mL (volume ratio), the about 100mg of dissolving PBT adds 36 μ L deuterated pyridines, measures down at 50 ℃ 1H-NMR tries to achieve." α-400 " or " JNM270 " that the NMR device uses NEC (strain) to make.
(6) the above foreign matter number of 5 μ m among the PBT or 5 μ m:
In the mixed solvent of hexafluoroisopropanol/chloroform=2/3 (volume ratio), dissolve the PBT of 10g with the concentration of 20 weight %, after the tetrafluoroethylene made membrane strainer filtration with aperture 5 μ m, fully clean with above-mentioned mixed solvent, count the foreign matter number that remains on the strainer with observation by light microscope.
(7) decrease temperature crystalline temperature (Tc):
Use differential scanning calorimeter (パ one キ Application エ Le マ one society, model DSC7), be warmed up to 300 ℃ with the heat-up rate of 20 ℃/min from room temperature after, be cooled to 80 ℃ with the cooling rate of 20 ℃/min, with the temperature of heating well heater as the decrease temperature crystalline temperature.Tc is high more, and crystallization speed is fast more, and forming period shortens.
(8) solution mist value:
In the mixing solutions of 20mL phenol/tetrachloroethane=3/2 (weight ratio), descend dissolving after 30 minutes at 110 ℃ the PBT of 2.70g, cooling is 15 minutes in 30 ℃ Water Tank with Temp.-controlled, the turbidometer (NDH-300A) that uses Japanese electric look (strain) to make, and long 10mm measures with cell.Be worth low more, the expression transparency good more.
(9) particle tone:
The colour-difference meter (Z-300A type) that uses Japanese electric look (strain) to make is calculated yellowness index b value, estimates.Be worth lowly more, to be yellow few more in expression, and tone is good more
(10) rising (Δ [COOH]) of the end carboxy concentration that causes by thermolysis
With PBT vacuum-drying to moisture 300ppm or after below the 300ppm, in Glass tubing, under dry nitrogen atmosphere, carry out 45 minutes thermal treatment with 245 ℃ oil baths, measure the end carboxy concentration and the terminal hydroxyl concentration of thermal treatment front and back, (VII) calculates with following formula.
Terminal hydroxyl change in concentration amount (VII) before and after end carboxy concentration variable quantity before and after Δ [COOH]=thermal treatment-thermal treatment
(11) fusion molecule flow rate:
According to ISO1133, under 250 ℃, 2.16kg loading, measure.
(12) tensile strength and tension fracture elongation rate:
(Sumitomo heavy-duty machine tool (strain) system: model S-75MIII), under 80 ℃ of 250 ℃ of barrel temperatures, metal die temperature, the ISO test film of shaping resin composition according to ISO527, is measured tensile strength (TS) and tension fracture elongation rate to use injection machine.These, any all adopts 5 times mean value.
(13) crooked rerum natura:
According to ISO178,, measure flexural strength and bending elastic modulus for above-mentioned same ISO test film.
(14) pendulum shock strength (summer is than shock strength):
On ISO test film same as described above, apply breach processing after, according to ISO179, measure the pendulum shock strength.
(15) hydrolytic resistance (strength retention behind the hydrolysis experiment)
ISO test film same as described above is joined in the pressurized vessel of filling pure water, and make it directly not contact with water, after airtight, depress 121 ℃ add and to handle 100 hours, carry out tension test same as described above (tensile strength after will handling on average as TS ').And (VIII) calculates strength retention according to following formula.But wet heat treatment is 100 hours in the occasion that contains the resin combination of strengthening packing material, is 60 hours in the occasion that does not conform to the resin combination that the reinforcement packing material is arranged.Strength retention is big, and the expression hydrolytic resistance is good.
Strength retention (%)=(TS '/TS) * 100 (VIII)
(16) terminal stud hinge characteristic:
Under 80 ℃ of 270 ℃ of barrel temperatures, metal die temperature, injection forming has the automobile metal electric wire terminal stud of hinge portion, estimates the warpage of hinge portion.-10 ℃ with hinge portion warpage 90 degree when, be determined at the crackle number that the hinge portion produces.Mensuration is that 40 terminal stud is carried out.
(17) release property:
By injection machine (Sumitomo heavy-duty machine tool (strain) system: continuous molding 16 utmost point terminal studs model SG-75 MIII), obtain molding not in the fixing metal mould residual ground can continuous molding the shortest cooling time of 20 times.Filling time is that 1 second, dwell time are 8 seconds, after the pressurize as cooling time.Barrel temperature is set at 250 ℃, initial stage metal die temperature and is set at 45 ℃.So-called the shortest above-mentioned cooling time, be meant in the time of to foreshorten to cooling time than its shorter time, causing molding residual bad cooling time of the demoulding in the fixing metal mould, in other words, is exactly quantity-produced the shortest cooling time stably.
(18) produce gas:
The 5g resin composition pellet is encased in the glass phial of volume 26mL, partly takes sample with microsyringe from gas phase after 2 hours in heating under 150 ℃.Pass through gc analysis.Obtain the peak area of color atlas, the ratio (ppm) of resin combination is represented with the tetrahydrofuran (THF) weight of the amount that is equivalent to its area.The major part (about 90%) that produces gas is a tetrahydrofuran (THF).
(19) camber amount:
The use injection machine (Sumitomo heavy-duty machine tool (strain) system: model SG-75 MIII), at the plectane of barrel temperature 250 ℃ of following form diameter 100mm, thickness 1.6mm.Door (ゲ one ト) is 1 door on circumference.One end of plectane is fixed on the flat board, measures distance that an opposite side breaks away from from flat board as the camber amount.
(20) the mist value of film:
The automatic mist value instrument (model TC-H3DPK) that uses Tokyo electricity look (strain) society to make is measured the mist value of 50 μ m thickness.
Embodiment 1
By esterification step shown in Figure 1 and polycondensation step shown in Figure 6, carry out the manufacturing of PBT by following main points.At first, will be with respect to 1.00 moles of terephthalic acids, 1, the 4-butyleneglycol with 60 ℃ slurries of 1.80 moles mixed from the slurries Preparation tank by feed line (1), supply to continuously in the esterification groove (A) of PBT oligopolymer of esterification yield 99% that had being pre-charged with of spiral type stirrer with 41kg/h.Simultaneously, from re-circulation line (2) with the tower of 185 ℃ rectifying tower (C) at the bottom of composition supply with 17.2kg/h, supply with as 1 of 6.0 weight % of 65 ℃ tetrabutyl titanate ester of catalyzer, 4-butanediol solution (is 30ppm with respect to theoretical polymkeric substance receipts amount) with 97g/h from catalyzer supply line (3).Moisture in this solution is 0.20 weight %.
The interior temperature of reactive tank (A) is that 230 ℃, pressure are 78kPa, and with the water that generates and tetrahydrofuran (THF) and remaining 1, the 4-butyleneglycol distillates from distillating line (5), separation high boiling point composition and low boiling point component in rectifying tower (C).High boiling point composition at the bottom of the tower after system is stable is 1 more than 98 weight % or the 98 weight %, and the 4-butyleneglycol is certain for the liquid level that keeps rectifying tower (C), by extracting line (8) out its part is retracted to the outside.On the other hand, low boiling point component is extracted out with the form of gas by cat head, and is certain for the liquid level that keeps jar (F) with condenser (G) cohesion, is retracted to the outside by extracting line (13) out.
The oligopolymer of generation is a certain amount of in reactive tank (A), uses pump (B) to extract out by extracting line (4) out, and the control liquid level is so that the average retention time of the interior liquid of reactive tank (A) is 3.3hr.Supply to continuously the 1st polycondensation groove (a) from the oligopolymer of extracting line (4) extraction out.After system was stable, the esterification yield of the oligopolymer of taking in the outlet of reactive tank (A) was 97.5%.
The interior temperature of the 1st polycondensation groove (a) is that 240 ℃, pressure are 2.1kPa, carries out tank level control so that the residence time is 120 minutes.From being connected the takeoff line (L2) on the negative booster (not shown), Yi Bian extract water, tetrahydrofuran (THF), 1 out, the 4-butyleneglycol, Yi Bian the initial stage of carrying out polycondensation, the reaction solution of extraction supplies in the 2nd polycondensation groove (d) continuously.
The interior temperature of the 2nd polycondensation groove (d) is that 245 ℃, pressure are 130Pa, carry out tank level control so that the residence time is 90 minutes, from being connected the takeoff line (L4) on the negative booster (not shown), Yi Bian extract water, tetrahydrofuran (THF), 1 out, the 4-butyleneglycol is Yi Bian further carry out polycondensation.The polymkeric substance that obtains, is extracted out with the form of strand shape from die head (g) via extracting line (L3) out continuously by extracting out with toothed gear pump (e), cuts off with rotary blade (h).
The limiting viscosity of the polymkeric substance that obtains is 0.85dL/g, and end carboxy concentration is 12.2 μ eq/g.Other analytical value is concluded and is shown in table 1.Can obtain few foreign, tone excellence, the transparency is good and the PBT of excellent heat stability.
Embodiment 2
In embodiment 1, except adopting polycondensation step shown in Figure 7, carry out similarly to Example 1.As the strainer (f) of polycondensation step shown in Figure 7, use the fold-type round tube type strainer of the absolute filtering accuracy 20 μ m that constitute by the metal tNonwovens.Can obtain having reduced more the PBT of foreign matter than embodiment 1.Analytical value is concluded and is shown in table 1.
Embodiment 3 and embodiment 4
In embodiment 1, except the feed rate of regulating the tetrabutyl titanate ester so that the titanium amount in the polymkeric substance is as shown in table 1, and to make the pressure of the 2nd polycondensation groove (d) be beyond the 100Pa, to carry out similarly to Example 1.Can obtain few foreign, tone excellence, the transparency is good and the PBT of excellent heat stability.Analytical value is concluded and is shown in table 1.
Embodiment 5
In embodiment 1, except the feed rate of regulating the tetrabutyl titanate ester so that the titanium amount in the polymkeric substance is as shown in table 1, and to make the temperature of the 2nd polycondensation groove (d) be beyond 250 ℃, to carry out similarly to Example 1.Can obtain few foreign, tone excellence, the transparency is good and the PBT of excellent heat stability.Analytical value is concluded and is shown in table 1.
Embodiment 6
In embodiment 1, except adopting polycondensation step shown in Figure 8, carry out similarly to Example 1.At this moment, use condition similarly to Example 1 to carry out up to the 2nd polycondensation groove (d), the interior temperature of the 3rd polycondensation groove (k) is that 240 ℃, pressure are that 130Pa, residence time are 60 minutes.Can obtain few foreign, tone excellence, transparent good and excellent heat stability, and than the high PBT of embodiment 1 molecular weight.Analytical value is concluded and is shown in table 1.
Embodiment 7
In embodiment 6, except adopting polycondensation step shown in Figure 9, carry out similarly to Example 6.As the strainer (f) of polycondensation step shown in Figure 9, use the fold-type round tube type strainer of the absolute filtering accuracy 20 μ m that constitute by the metal tNonwovens.Can obtain having reduced more the PBT of foreign matter than embodiment 6.Analytical value is concluded and is shown in table 2.
Embodiment 8
In embodiment 1, change to the 8.0kg/h except supplying at the bottom of the tower of rectifying tower (C) of reactive tank (A) components in proportions by re-circulation line (2), carry out similarly to Example 1.Can obtain few foreign, tone excellence, the transparency is good and the PBT of excellent heat stability.Analytical value is concluded and is shown in table 2.
Embodiment 9
In embodiment 7, use condition similarly to Example 1 to carry out up to the 2nd polycondensation groove (d), the interior temperature of the 3rd polycondensation groove (k) is that 245 ℃, pressure are that 130Pa, residence time are 70 minutes.Can obtain 7 full-bodied PBT than embodiment.
Comparative example 1
In embodiment 1, except the catalyzer supply line (3) with esterification step shown in Figure 1 is connected on the feed line (1), and make re-circulation line (2) be positioned at the gas phase portion of reactive tank (A), and, 1 of tetrabutyl titanate ester, the feed rate of 4-butanediol solution is that the feed rate of composition is beyond the 17.1kg, to carry out similarly to Example 1 at the bottom of the tower of 194g/h, rectifying tower (C).It is as shown in the table, and mist value, tone worsen, and foreign matter is also many.Analytical value is concluded and is shown in table 2.
Comparative example 2
In the stainless steel reaction vessel of the volume 200L that possesses the Scroll-type agitating wing, 1 of 272.9mol terephthalic acid, 491.3mol packs into, 4-butyleneglycol, 0.126 mole of (as the titanium amount, every theoretical yield polymkeric substance 100ppm) tetrabutyl titanate ester carry out sufficient nitrogen exchange.Then, system is heated up, after 60 minutes, temperature reaches 220 ℃, pressure and reaches 80kPa, on one side with the water and the tetrahydrofuran (THF), remaining 1 that generate, the 4-butyleneglycol distillates outside the system, carries out 2 hours esterification (the reaction time opening is set at the moment that reaches specified temperature, specified pressure).At this moment, taking a part of test portion to measure esterification yield is 99%.
After the above-mentioned oligopolymer that obtains being transferred in the stainless steel reactor of the volume 200L with swan neck and double helical form agitating wing, reach 245 ℃ of temperature, pressure 100Pa through 60 minutes, keep the polycondensation that this state carries out 1.5 hours.After reaction finishes, polymkeric substance is extracted out with the strand shape, be cut to particulate state.The limiting viscosity of the polymkeric substance that obtains is 0.85, and end carboxy concentration is up to 44.5 μ eq/g, and thermostability is also bad, and Tc is also low.Analytical value is concluded and is shown in table 2.
Comparative example 3
In the stainless steel reaction vessel of the volume 200L that possesses the Scroll-type agitating wing, 1 of the 272.9mol dimethyl terephthalate (DMT) of packing into (DMT), 327.5mol, 4-butyleneglycol, 0.126 mole are (as the titanium amount, every theoretical yield polymkeric substance 100ppm) tetrabutyl titanate ester carries out sufficient nitrogen exchange.Then, system is heated up, after 60 minutes, temperature is 210 ℃, at nitrogen environment, under atmospheric pressure, on one side with the methyl alcohol, 1 that generates, 4-butyleneglycol, tetrahydrofuran (THF) distillate outside the system, Yi Bian carry out 2 hours transesterification reaction (the reaction time opening is set at the moment that reaches specified temperature, specified pressure).
After the above-mentioned oligopolymer that obtains being transferred in the stainless steel reactor of the volume 200L with delivery pipe and double helical form agitating wing, reach 245 ℃ of temperature, pressure 100Pa through 60 minutes, keep the polycondensation that this state carries out 1.5 hours.After reaction finishes, polymkeric substance is extracted out with the strand shape, be cut to particulate state.The limiting viscosity of the polymkeric substance that obtains is 0.85, and end carboxy concentration is up to 37.4 μ eq/g, and thermostability is also bad, and Tc is also low.Analytical value is concluded and is shown in table 2.
Comparative example 4
In embodiment 1, except the catalyzer supply line (3) with esterification step shown in Figure 1 is attached on the feed line (1), and make the gas phase portion that is positioned at reactive tank (A) at circular route (2), and, 1 of tetrabutyl titanate ester, the feed rate of 4-butanediol solution is that the feed rate of composition is 17.1kg at the bottom of the tower of 194g/h, rectifying tower (C), adopts polymerization process shown in Figure 8 to replace carrying out similarly to Example 1 beyond the polycondensation step shown in Figure 6.At this moment, use condition similarly to Example 1 to carry out up to the 2nd polymerization reaction trough (d), the interior temperature of the 3rd polymerization reaction trough (k) is that 240 ℃, pressure are that 130Pa, residence time are 60 minutes.The PBT foreign matter that obtains is many, mist value or b value are also high.Analytical value is concluded and is shown in table 2.
Comparative example 5
In comparative example 2, except the Intake Quantity of tetrabutyl titanate ester is 0.044 mole (as titanium amount, every theoretical yield polymkeric substance 35ppm), the time of esterification is beyond 5 hours, similarly carries out esterification with comparative example 2.Esterification yield after the esterification is 99%.
Then, oligopolymer is transferred in the polycondensation groove, with comparative example 2 similarly, reached 245 ℃ of temperature, pressure 100Pa through 60 minutes, keep the polycondensation that this state carries out 5 hours, culminate, when viscosity does not rise, extract polymkeric substance out owing to stirring power.The limiting viscosity of the polymkeric substance that obtains is 1.03, and end carboxy concentration, terminal ethylenyl groups concentration are all high.
Table 1
Project Unit Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7
BM/TM Mol/ mol 3.35 3.35 3.35 3.35 3.35 3.35 3.35
Ti content ppm 30 30 25 10 10 30 30
IV dL/g 0.85 0.85 0.85 0.76 0.85 1.20 1.20
End carboxy concentration μeq/g 12.2 12.2 11.3 8.0 11.5 22.2 22.2
Tc ℃ 177.5 177.5 176.4 176.0 176.5 175.8 175.8
Terminal ethylenyl groups concentration μeq/g 6.5 6.5 6.3 5.5 9.2 9.5 9.5
Terminal methoxy group carbonyl concentration μeq/g 0.1 or below 0.1 0.1 or below 0.1 0.1 or below 0.1 0.1 or below 0.1 0.1 or below 0.1 0.1 or below 0.1 0.1 or below 0.1
5 μ m or the above foreign matter number of 5 μ m Individual/the 10g polymkeric substance 11 5 9 7 8 12 6
The solution mist value ％ 0.3 0.3 0.2 0.1 0.1 0.3 0.3
Δ[COOH] μ eq/g (40 minutes) 4.3 4.3 3.6 1.7 1.7 1.8 1.8
Particle b value -1.6 -1.6 -1.8 -2.0 -0.5 -1.2 -1.2
Table 2
Project Unit Embodiment 8 Embodiment 9 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
BM/TM Mol/ mol 2.52 3.35 3.35 1.80 1.20 3.35 1.80
Ti content ppm 30 30 60 100 100 60 35
IV dL/g 0.85 1.26 0.85 0.85 0.85 1.20 1.03
End carboxy concentration μeq/g 13.0 28.4 13.5 44.5 37.4 25.6 36.0
Tc ℃ 179.1 175.0 178.5 175.6 168.7 175.9 172.4
Terminal ethylenyl groups concentration μeq/g 7.8 10.7 6.9 7.0 6.7 10.5 12.5
Terminal methoxy group carbonyl concentration μeq/g 0.1 or below 0.1 0.1 or below 0.1 0.1 or below 0.1 0.1 or below 0.1 2.3 0.1 or below 0.1 0.1 or below 0.1
5 μ m or the above foreign matter number of 5 μ m Individual/the 10g polymkeric substance 20 5 67 20 15 70 29
The solution mist value ％ 1.0 0.2 22.5 0.4 0.1 21.7 0.4
Δ[COOH] μ eq/g (40 minutes) 2.9 1.5 4.5 9.0 10.1 2.0 2.9
Particle b value -1.0 -0.8 0.2 0.0 -1.5 0.8 1.5
Embodiment 10～12 and comparative example 6～8 (mixing PBT)
Use high viscosity PBT, the low viscosity PBT of comparative example 1, the high viscosity PBT of comparative example 4 of low viscosity PBT, the embodiment 6 of embodiment 1; form mixing with the cooperation shown in the table 3; the biaxial extruder that has venting port [(strain) JSW: TEX30C] by screw rod footpath 30mm; under the condition of 260 ℃ of temperature, screw rod rotation number 200rpm, carry out melting mixing, extrude strand shape and granulating.And, carry out the evaluation shown in table 3 and the table 4, the results are shown in the same table.
Table 3
Figure C20038010991200601
Table 4
Shown in table 3 and table 4, be 33ppm or below the 33ppm and the different PBT of limiting viscosity by the mixed with titanium atom, can obtain the PBT of the hinge excellent of mobile adjusted, hydrolytic resistance, ultimate elongation rate, terminal stud.This be because, because the titanium catalyst amount reduces, hydrolytic resistance improves, the cohesion foreign matter of titanium catalyst tails off.
Embodiment 13～16 and comparative example 9～10 (thermotolerance PBT composition)
Particle 99.7 weight parts of each PBT that obtains with respect to embodiment 1, embodiment 6, comparative example 1, comparative example 2 are formed the composition that mixes following (1)～(3) with the cooperation of table 5, and method is similarly to Example 9 carried out granulation.
(1) tetramethylolmethane four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester] (チ バ ガ イ ギ one system, trade(brand)name: Irganox1010)
(2) (シ プ ロ changes into (strain) system, trade(brand)name: SEENOX412S) to tetramethylolmethane four (3-lauryl thiodipropionate)
(3) two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites (rising sun electrochemical industry (strain) system, trade(brand)name:, measure tone b value, tensile strength, tensile fracture elongation ア デ カ ス Block PEP36) by above-mentioned shaping particles ISO test film.In addition, in order to estimate heat-resistant aging,, measure tone b value, tensile strength, tensile fracture elongation for the ISO test film of processing after 250 hours or 500 hours in 150 ℃ hot air drier.In addition, also use the ISO test film to estimate hydrolytic resistance.These the results are shown in table 5 and the table 6.
Table 5
Figure C20038010991200611
Figure C20038010991200621
Table 6
Shown in table 5 and table 6,, can obtain stable on heating and do not have the PBT composition that tonal variation and tensile elongation reduce, hydrolytic resistance is also excellent by in titanium atom 33ppm or the PBT below the 33ppm, adding oxidation inhibitor.This is because because the titanium catalyst amount is less, suppressed thermolysis, oxidation, hydrolysis.
Embodiment 17～18 and comparative example 11～13 (good release property PBT composition)
In the various PBT that embodiment 1, comparative example 1, the comparative example 2 of 100 weight parts obtains, cooperate following (1) and (2) composition according to the composition of table 7, by biaxial extruder, 260 ℃ mixing down, be extruded into the strand shape and carry out granulation.
(1) montanate (Japan ペ ト ロ ラ イ ト (strain) system, trade(brand)name: Le ザ ワ Star Network ス EP, molecular weight 800)
(2) polyethylene wax (Mitsui Chemicals (strain) system, trade(brand)name: Ha イ ワ Star Network ス 100P, molecular weight 900)
Above-mentioned montanate molecular weight is measured as follows by the melt viscosity method.Fill thermostatic oil bath with polyoxyethylene glycol, regulate Atlas (Atlantic) type viscosity and count 135 ℃, viscometer is kept vertical, with the necessary amount of naphthane dilution wax, second number that flows down with automatic viscometer mensuration sample solution is scaled molecular weight.
By above-mentioned shaping particles ISO test film, also estimated release property.In addition, estimated hydrolytic resistance.These the results are shown in table 7.
Table 7
Figure C20038010991200631
As shown in table 7, by in titanium atom 33ppm or the PBT below the 33ppm, adding montanate, can obtain the PBT composition of hydrolytic resistance and release property excellence (forming period is shortened) as releasing agent.
Implement profit 19～20 and comparative example 14～15 (hydrolytic resistance PBT composition)
Particle with respect to the various PBT of the embodiment 1 of 100 weight parts, comparative example 1, comparative example 2.According to the composition of the composition cooperation of table 8 following (1) and (2), method granulation similarly to Example 9.
(1) glass fibre (NEG society system, trade mark T-187, diameter 13 μ m, staple length 3mm)
(2) diglycidylether of dihydroxyphenyl propane (rising sun electrification (strain) system, trade(brand)name: ア デ カ サ イ ザ one EP-17)
By above-mentioned shaping particles ISO test film, estimated hydrolytic resistance.Also estimated release property in addition.These the results are shown in table 8.
Table 8
Figure C20038010991200641
As shown in table 8, strengthen serial packing material (glass fibre) and epoxy compounds by in titanium atom 33ppm or the PBT below the 33ppm, cooperating, can obtain the reinforcement Series P BT composition of hydrolytic resistance excellence.
Implement profit 21～22 and comparative example 16～17 (shock-resistance PBT composition)
Particle with respect to the various PBT of the embodiment 1 of 100 weight parts, comparative example 1, comparative example 2.According to the composition of the composition cooperation of table 9 following (1) and (2), method granulation similarly to Example 10.
(1) acrylic rubber (chemical name: alkyl acrylate alkyl methacrylate multipolymer, Wu Yu chemical industry (strain) system, trade(brand)name: (2) glass fibre (with the identical glass fibre of embodiment 19 uses) Network レ Ha パ ラ ロ イ De EXL2315)
Make the ISO test film by above-mentioned particle by injection machine, measured tensile strength, flexural strength, bending elastic modulus, Charpy impact value.Estimated hydrolytic resistance in addition.These the results are shown in table 9.
Table 9
Figure C20038010991200651
As shown in table 9, contain in titanium atom 33ppm or the PBT below the 33ppm by making shock-resistant modifying agent (acrylic rubber) and strengthening packing material (glass fibre), can obtain having the excellent hydrolytic resistance and the PBT composition of impact.
Implement profit 23～24 and comparative example 18～19 (flame retardant resistance PBT composition)
Particle with respect to the various PBT of the embodiment 1 of 100 weight parts, comparative example 1, comparative example 2.According to the composition of following (1)～(4) of the composition cooperation of table 10, method granulation similarly to Example 10.
(1) bromo aromatics: poly-(pentabromobenzyl acrylate) (プ ロ モ ケ system Off ア one イ one ス ト society, trade(brand)name: PBBPA-FR1025)
(2) ANTIMONY TRIOXIDE SB 203 99.8 PCT (gloomy six society's systems)
(3) polytetrafluoroethylene (PTFE) (Daikin Industries society system, trade(brand)name: Port リ Off ロ Application FA-500)
(4) glass fibre (with the identical glass fibre of embodiment 19 uses)
By above-mentioned shaping particles UL-94 (1/32 inch) test film, carry out combustible test according to UL-94.The UL-94 test film is by injection machine (JSW's system: model J28SA), be shaped for 80 ℃ times in 270 ℃ of barrel temperatures, metal die temperature.In addition, by above-mentioned shaping particles ISO tension test sheet, estimated hydrolytic resistance.In addition, measured by particle generation gas.These results are recorded in table 10.
Table 10
As shown in table 10, by in titanium atom 33ppm or the PBT below the 33ppm, cooperating bromo aromatics based flame retardant (PBBPA), antimony compounds (ANTIMONY TRIOXIDE SB 203 99.8 PCT), dripping inhibitor (PTFE), strengthening packing material (glass fibre), can obtain having excellent hydrolytic resistance and flame retardant resistance, and produce the few PBT composition of gas.
Embodiment 25～27 and comparative example 20～21 (non-halogen fire retardant PBT composition)
Particle with respect to the various PBT of the embodiment 1 of 100 weight parts, comparative example 1, comparative example 2.According to the composition of following (1)～(7) of the composition cooperation of table 11, method granulation similarly to Example 10.
(1) polyphenylene oxide (PPE) (エ of Mitsubishi Application ジ ニ ア リ Application グ プ ラ ス チ Star Network (strain) system, trade(brand)name: ユ ピ エ one ス (registered trademark), limiting viscosity 0.36dL/g)
(2) polycarbonate (PC) (エ of Mitsubishi Application ジ ニ ア リ Application グ プ ラ ス チ Star Network (strain) system, grade 7022PJ, viscosity-average molecular weight: about 21000)
(3) phosphoric acid ester of following formula (8) expression
(4) melamine cyanurate (Mitsubishi Chemical's (strain) system)
(5) glass fibre (with the identical glass fibre of embodiment 19 uses)
(6) polytetrafluoroethylene (PTFE) (Daikin Industries society system, trade(brand)name: Port リ Off ロ Application FA-500)
(7) zinc borate (ボ ラ Star Network ス ジ ヤ パ Application (strain) system, trade(brand)name: Firebrake ZB)
Figure C20038010991200671
By above-mentioned shaping particles UL-94 (1/32 inch) test film, carry out combustible test according to UL-94.The UL-94 test film is by injection machine (JSW's system: model J28SA), be shaped for 80 ℃ times in 270 ℃ of barrel temperatures, metal die temperature.In addition, by above-mentioned shaping particles ISO tension test sheet, estimated hydrolytic resistance.These results are recorded in table 11.
Table 11
Figure C20038010991200672
As shown in table 11, by in titanium atom 33ppm or PBT below the 33ppm and polyphenylene oxide resin, cooperating solubility promoter (polycarbonate), phosphoric acid ester, melamine cyanurate, reinforcement packing material (glass fibre), dripping inhibitor (PTFE), borate metal salt, can obtain having the excellent hydrolytic resistance and the PBT composition of flame retardant resistance.
Implement profit 28～30 and comparative example 22～25 (other functional PBT composition-1)
Particle with respect to the various PBT of the embodiment 1 of 100 weight parts, comparative example 1, comparative example 2.According to the composition of following (1)～(4) of the composition cooperation of table 12 and table 13, method granulation similarly to Example 10.
(1) polycarbonate resin (PC) (with the identical PC of embodiment 25 uses)
(2) phosphorus compound: octadecanoic acid phosphoric acid ester [rising sun electrochemical industry (strain) system, trade(brand)name: AX-71 (mixture of monoalkyl body and dioxane matrix)]
(3) glass fibre (with the identical glass fibre of embodiment 19 uses)
(4) acrylic rubber (chemical name: alkyl acrylate alkyl methacrylate multipolymer, Wu Yu chemical industry (strain) system, trade(brand)name: Network レ Ha パ ラ ロ イ De EXL2315) measured above-mentioned particulate decrease temperature crystalline temperature.In addition, by above-mentioned granule manufacture ISO test film, tensile strength, flexural strength, bending elastic modulus, Charpy impact value have been measured.Estimated hydrolytic resistance in addition.These the results are shown in table 12 and table 13.
Table 12
Figure C20038010991200691
Table 13
Figure C20038010991200692
Shown in table 12 and table 13, by in titanium atom 33ppm or the PBT below the 33ppm, cooperating polycarbonate, organo phosphorous compounds, reinforcement packing material (glass fibre), can obtain hydrolytic resistance excellence, crystallized temperature height (therefore, can shorten forming period, boost productivity) the PBT composition.
Implement sharp 31～34 and comparative example 26～28 (other functional PBT composition-2) with respect to the particle of the various PBT of the embodiment 1 of 100 weight parts, comparative example 1, comparative example 2.
According to the composition of following (1)～(3) of the composition cooperation of table 14 and table 15, method granulation similarly to Example 10.
(1) polyethylene terephthalate (Mitsubishi Chemical's (strain) system, trade(brand)name: GS385, limiting viscosity 0.65dL/g)
(2) Poly(Trimethylene Terephthalate) [シ エ Le ケ ミ カ Le ズ society system, trade(brand)name: コ Le テ ラ CP509200, limiting viscosity 0.92dL/g: in methylene dichloride-trifluoroacetic acid (weight ratio 1 to 1) mixed solvent, measure down] at 30 ℃
(3) glass fibre (with the identical glass fibre of embodiment 19 uses)
Measured above-mentioned particulate decrease temperature crystalline temperature by DSC.In addition, by above-mentioned granule manufacture ISO test film, tensile strength, flexural strength, bending elastic modulus, Charpy impact value have been measured.
Estimated hydrolytic resistance in addition.These the results are shown in table 14 and table 15.
Table 14
Figure C20038010991200701
Figure C20038010991200711
Table 15
Figure C20038010991200712
Shown in table 14 and table 15, by in titanium atom 33ppm or the PBT below the 33ppm, cooperating polyethylene terephthalate or Poly(Trimethylene Terephthalate) and reinforcement packing material (glass fibre), can obtain hydrolytic resistance excellence, crystallized temperature height (therefore, can shorten forming period, boost productivity) the PBT composition.
Implement profit 35～39 and comparative example 29～32 (other functional PBT composition-3)
Particle with respect to the various PBT of the embodiment 1 of 100 weight parts, comparative example 1, comparative example 2.
According to the composition of following (1)～(4) of the composition cooperation of table 16 and table 17, method granulation similarly to Example 10.
(1) HIPS: rubber (polyhutadiene) containing ratio 8.8 weight %, average rubber particle diameter 1.8 μ m, number-average molecular weight 92000, weight-average molecular weight 230000,1.8g/10 minute rubber modified polystyrene resin (A﹠amp of melt flow rate (200 ℃ of temperature, loading 5kgf); M society system, trade(brand)name: ダ イ ヤ レ Star Network ス HT478)
(2) AS: number-average molecular weight 96000, the acrylonitrile styrene resin of weight-average molecular weight 240000 (テ Network ノ Port リ マ one Co., Ltd.'s system, trade(brand)name: SANREX S90)
(3) ダ イ ラ one Network (DIELARK): maleic anhydride amount 9 weight %, weight-average molecular weight 240000, melt flow rate (230 ℃ of temperature, loading 2.16kgf) 2.0g/10 minute maleic anhydride modified polystyrene (ノ バ ケ ミ カ Le ジ ヤ パ Application society system, trade(brand)name: ダ イ ラ one Network D232)
(4) polycarbonate resin (PC) (with the identical PC of embodiment 25 uses)
(5) glass fibre (with the identical glass fibre of embodiment 19 uses)
By above-mentioned granule manufacture ISO test film, tensile strength, flexural strength, bending elastic modulus, Charpy impact value have been measured.Estimated hydrolytic resistance in addition.These the results are shown in table 16 and table 17.
Table 16
Table 17
Figure C20038010991200732
Embodiment 40～47 and comparative example 33～34
As raw material, use the PBT of aforesaid embodiment and comparative example 4, obtain unitary film according to following main points.Above-mentioned PBT is put in the Vacuumdrier, vacuumize dry more than 4 hours or 4 hours later on again while arrive 120 ℃ at particle temperature.Then, dried PBT particle is put into inserted in the hopper of forcing machine that bore 40 φ, L/D=25 and compression ratio are 3.5 full flight screw (full flightscrew).At the front end of forcing machine the T pattern of wide 600mm, die lip opening 0.4mm is installed, under about 260 ℃ of resin temperature, is extruded into the curtain shape with discharge-amount 5kg/hr.With the resin extruded 60 ℃ of surface temperatures and with circumferential speed about 3m/ divide rotation enforcement extrude continuously on the metallic roll of polishing, quick cooling obtains unitary film.Analytical value is concluded and is shown in table 18.
Table 18
Raw material PBT The mist value (%) of unitary film (50 μ m) The outward appearance of film
Embodiment 40 Embodiment 1-PBT 1.2 No problem
Embodiment 41 Embodiment 2-PBT 1.2 No problem
Embodiment 42 Embodiment 3-PBT 1.1 No problem
Embodiment 43 Embodiment 5-PBT 1.1 No problem
Embodiment 44 Embodiment 6-PBT 0.5 No problem
Embodiment 45 Embodiment 7-PBT 0.5 No problem
Embodiment 46 Embodiment 8-PBT 1.6 No problem
Embodiment 47 Embodiment 9-PBT 0.5 No problem
Comparative example 33 Comparative example 1-PBT 2.5 Foreign matter is many
Comparative example 34 Comparative example 4-PBT 2.5 Foreign matter is many
Embodiment 48
The polymkeric substance that uses embodiment 9 to obtain is made composite membrane by coetrusion according to following main points.As device, 3 kinds 3 layers water cooling multilayer expanded film building mortion have been used.In this device, outer to insert bore 40 φ, L/D=24 and compression ratio with forcing machine be 3.5 full flight screw, and it is 2.5 full flight screw that each forcing machine that middle layer and internal layer are used inserts bore 40 φ, L/D=24 and compression ratio.
At first, PBT is put in the Vacuumdrier, vacuumize dry more than 4 hours or 4 hours later on again while arrive 120 ℃ at particle temperature.Then, fill PBT at skin in forcing machine, fill LLDPE (MI=2.0 in each forcing machine that the middle layer is used and internal layer is used, density=0.925g/cc), under the condition of spreading rate (BUR) 1.3, carry out the coextrusion of PBT and olefine kind resin, with the water cooling of 30 ℃ of water temperatures, obtain the folding footpath and be 170mm, and have 2 tunics of PBT layer 50 μ m and olefin layer 30 μ m.This film PBT layer and olefin layer can be peeled off simply, have wherein only estimated the PBT layer.When measuring the mist value of PBT layer is 0%, in addition, does not almost observe foreign matter, obtains good surface appearance.
Embodiment 50
The PBT film of the 50 μ m that use is made in order to measure the mist value at embodiment 49 is made composite membrane by the dry laminate method according to following main points.That is, at first, use the pull bar coating machine, 2 liquid type dry laminates are coated on the above-mentioned PBT film with tackiness agents (Japan モ one ト Application society system: host (TM-51), 6/1 weight ratio mixture of solidifying agent 5 (CAT-RT8)), and to make dry weight be 5g/m 2, dry then.Then, on above-mentioned coated face, at 100 ℃ of temperature, pressure 5g/m 2Condition under, the straight chain shape new LDPE (film grade) of dry laminate thickness 50 μ m (Japanese Port リ ケ system society's system " ノ バ テ Star Network UF230 ", MI:21.1, density 0.921g/cc).Obtaining the mist value is 1.5%, and the transparency is high, does not almost have the good film of foreign matter.
Industrial applicibility
According to the present invention described above, tone, hydrolytic resistance, heat endurance, the transparency are provided, have had excellent formability, and foreign matter reduced, and can be applicable to the PBT of the stabilizing quality of film, monofilament, fiber, electrical/electronic part, auto parts etc., and industrial value of the present invention is remarkable.

Claims (47)

1. a polybutylene terephthalate is characterized in that, this polybutylene terephthalate is to use titanium catalyst to obtain, and wherein contains titanium, and in titanium atom, its content is 1ppm～33ppm.
2. according to the polybutylene terephthalate of claim 1 record, wherein, the decrease temperature crystalline temperature of measuring with differential scanning calorimeter under 20 ℃/min of cooling rate is 170～200 ℃.
3. according to the polybutylene terephthalate of claim 1 record, wherein, terminal ethylenyl groups concentration is 0.1～10 μ eq/g.
4. according to the polybutylene terephthalate of claim 2 record, wherein, terminal ethylenyl groups concentration is 0.1～10 μ eq/g.
5. according to the polybutylene terephthalate of claim 1 record, wherein, be dissolving 2.7g polybutylene terephthalate in 3/2 phenol/tetrachloroethane mixed solvent in the 20mL weight ratio, the mist value of the solution of mensuration is below 10% or 10%.
6. according to the polybutylene terephthalate of claim 2 record, wherein, be dissolving 2.7g polybutylene terephthalate in 3/2 phenol/tetrachloroethane mixed solvent in the 20mL weight ratio, the mist value of the solution of mensuration is below 10% or 10%.
7. according to the polybutylene terephthalate of claim 3 record, wherein, be dissolving 2.7g polybutylene terephthalate in 3/2 phenol/tetrachloroethane mixed solvent in the 20mL weight ratio, the mist value of the solution of mensuration is below 10% or 10%.
8. according to the polybutylene terephthalate of claim 4 record, wherein, be dissolving 2.7g polybutylene terephthalate in 3/2 phenol/tetrachloroethane mixed solvent in the 20mL weight ratio, the mist value of the solution of mensuration is below 10% or 10%.
9. according to the polybutylene terephthalate of claim 1 record, wherein, under reactive gas atmosphere not, the end carboxy concentration except hydrolysis reaction when carrying out 40 minutes thermal treatment for 245 ℃ rise to 0.1～30 μ eq/g.
10. according to the polybutylene terephthalate of claim 2 record, wherein, under reactive gas atmosphere not, the end carboxy concentration except hydrolysis reaction when carrying out 40 minutes thermal treatment for 245 ℃ rise to 0.1～30 μ eq/g.
11. according to the polybutylene terephthalate of claim 3 record, wherein, under reactive gas atmosphere not, the end carboxy concentration except hydrolysis reaction when carrying out 40 minutes thermal treatment for 245 ℃ rise to 0.1～30 μ eq/g.
12. according to the polybutylene terephthalate of claim 4 record, wherein, under reactive gas atmosphere not, the end carboxy concentration except hydrolysis reaction when carrying out 40 minutes thermal treatment for 245 ℃ rise to 0.1～30 μ eq/g.
13. according to the polybutylene terephthalate of claim 5 record, wherein, under reactive gas atmosphere not, the end carboxy concentration except hydrolysis reaction when carrying out 40 minutes thermal treatment for 245 ℃ rise to 0.1～30 μ eq/g.
14. according to the polybutylene terephthalate of claim 6 record, wherein, under reactive gas atmosphere not, the end carboxy concentration except hydrolysis reaction when carrying out 40 minutes thermal treatment for 245 ℃ rise to 0.1～30 μ eq/g.
15. according to the polybutylene terephthalate of claim 7 record, wherein, under reactive gas atmosphere not, the end carboxy concentration except hydrolysis reaction when carrying out 40 minutes thermal treatment for 245 ℃ rise to 0.1～30 μ eq/g.
16. according to the polybutylene terephthalate of claim 8 record, wherein, under reactive gas atmosphere not, the end carboxy concentration except hydrolysis reaction when carrying out 40 minutes thermal treatment for 245 ℃ rise to 0.1～30 μ eq/g.
17. according to the polybutylene terephthalate of each record in the claim 1～16, wherein, the above foreign matter of 5 μ m or 5 μ m is 50 a/10g polymkeric substance or below the 50/10g polymkeric substance.
18. according to the polybutylene terephthalate of each record in the claim 1～16, wherein, the following 3ppm that is limited to of the amount of titanium.
19. according to the polybutylene terephthalate of claim 17 record, wherein, the following 3ppm that is limited to of the amount of titanium.
20. polybutylene terephthalate according to each record in the claim 1～16, wherein, it is the polybutylene terephthalate of 0.91～1.50dL/g that this polybutylene terephthalate contains polybutylene terephthalate and the limiting viscosity that limiting viscosity is 0.60～0.90dL/g, and its weight ratio is 5～95: 95～5 ratio.
21. polybutylene terephthalate according to claim 17 record, wherein, it is the polybutylene terephthalate of 0.91～1.50dL/g that this polybutylene terephthalate contains polybutylene terephthalate and the limiting viscosity that limiting viscosity is 0.60～0.90dL/g, and its weight ratio is 5～95: 95～5 ratio.
22. polybutylene terephthalate according to claim 18 record, wherein, it is the polybutylene terephthalate of 0.91～1.50dL/g that this polybutylene terephthalate contains polybutylene terephthalate and the limiting viscosity that limiting viscosity is 0.60～0.90dL/g, and its weight ratio is 5～95: 95～5 ratio.
23. polybutylene terephthalate according to claim 19 record, wherein, it is the polybutylene terephthalate of 0.91～1.50dL/g that this polybutylene terephthalate contains polybutylene terephthalate and the limiting viscosity that limiting viscosity is 0.60～0.90dL/g, and its weight ratio is 5～95: 95～5 ratio.
24. heat resistant poly butylene terephthalate composition, it is characterized in that said composition contains the polybutylene terephthalate and the oxidation inhibitor more than a kind or a kind that is selected from phenolic antioxidant (B1), sulfur type antioxidant (B2) and the Phosphorus oxidation inhibitor (B3) of each record in the claim 1～23.
25. the polybutylene terephthalate composition of a good release property, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts of each record in the claim 1～23, contain the fatty acid ester (C1) of the pure residue that is selected from the fatty acid residue that contains carbonatoms 12～36 and carbonatoms 1～36 and releasing agent (C) 0.01～2 weight part of paraffin and polyethylene wax (C2).
26. hydrolytic resistance polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts of each record in the claim 1～23, contain and strengthen weighting agent (D) 0～200 weight part and epoxy compounds (E) 0.01～20 weight part.
27. shock-resistance polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts of each record in the claim 1～23, contain shock-resistant improvement material (F) 0.5～40 weight part and strengthen weighting agent (D) 0～200 weight part.
28. flame retardance poly butylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts of each record in the claim 1～23, contain bromo aromatics based flame retardant (G) 3～50 weight parts, antimony compounds (H) 1～30 weight part, dripping inhibitor (I) 0～15 weight part and strengthen packing material (D) 0～200 weight part.
29. non-halogen fire retardant polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 50～95 weight parts of each record in the claim 1～23 and total 100 weight parts of polyphenylene oxide resin (J) 5～50 weight parts, contain solubilizing agent (K) 0.05～10 weight part, be selected from least a kind compound (L) 2～45 weight parts of phosphoric acid ester or phosphonitrile, strengthen packing material (D) 0～200 weight part, dripping inhibitor (I) 0～15 weight part, melamine cyanurate (M) 0～45 weight part and borate metal salt (N) 0～50 weight part.
30. polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts of each record in the claim 1～23, contain polycarbonate resin (O) 5～100 weight parts, organo phosphorous compounds (P) 0.01～1 weight part, strengthen packing material (D) 0～200 weight part and shock-resistant modifying agent (F) 0～50 weight part.
31. polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts of each record in the claim 1～23, contain polybutylene terephthalate aromatic polyester-based resin (Q) 5～100 weight parts and reinforcement packing material (D) 0～200 weight part in addition.
32. polybutylene terephthalate composition, it is characterized in that, with respect to polybutylene terephthalate 100 weight parts of each record in the claim 1～23, contain styrene resin (R) 5～100 weight parts, maleic anhydride modified polystyrene resin (S) or polycarbonate resin (O) 0～40 weight part, strengthen packing material (D) 0～200 weight part.
33. a film is characterized in that this film contains polybutylene terephthalate, wherein, described polybutylene terephthalate contains titanium and is 1ppm～33ppm in its content of titanium atom.
34. according to the film of claim 33 record, wherein, the decrease temperature crystalline temperature of measuring with differential scanning calorimeter under 20 ℃/min of cooling rate of polybutylene terephthalate is 170～200 ℃.
35. according to the film of claim 33 record, wherein, the limiting viscosity of polybutylene terephthalate is 0.60～2.50dL/g.
36. according to the film of claim 34 record, wherein, the limiting viscosity of polybutylene terephthalate is 0.60～2.50dL/g.
37. according to the film of claim 33 record, wherein, the end carboxy concentration of polybutylene terephthalate is 1～45 μ eq/g.
38. according to the film of claim 34 record, wherein, the end carboxy concentration of polybutylene terephthalate is 1～45 μ eq/g.
39. according to the film of claim 35 record, wherein, the end carboxy concentration of polybutylene terephthalate is 1～45 μ eq/g.
40. according to the film of claim 36 record, wherein, the end carboxy concentration of polybutylene terephthalate is 1～45 μ eq/g.
41. according to the film of each record in the claim 33～40, wherein, the above foreign matter of 5 μ m of polybutylene terephthalate or 5 μ m is 50 a/10g polymkeric substance or below the 50/10g polymkeric substance.
42. according to the film of each record in the claim 33～40, wherein, the thickness of described film is 5～200 μ m.
43. according to the film of claim 41 record, wherein, the thickness of described film is 5～200 μ m.
44. compoundization film, it is characterized in that this compoundization film is the compoundization film that contains the different resin layer more than 2 kinds or 2 kinds, wherein, at least 1 layer is the polybutylene terephthalate film of each record in the claim 33～43, and other at least 1 layer is the polyolefins film.
45. according to the compoundization film of claim 44 record, wherein, outermost layer is made of polybutylene terephthalate film and/or polyolefin resin.
46. film, it is characterized in that, this film contains polybutylene terephthalate 1～99 weight % and polyethylene terephthalate 1～99 weight %, and both add up to 100 weight %, wherein, described polybutylene terephthalate contains titanium and is 1ppm～33ppm in its content of titanium atom.
47. film, it is characterized in that, this film has contained polybutylene terephthalate 1～99 weight % and copolymerization aromatic polyester 1～99 weight % of polytetramethylene glycol, and both add up to 100 weight %, wherein, described polybutylene terephthalate contains titanium and is 1ppm～33ppm in its content of titanium atom.
CNB2003801099122A 2002-12-27 2003-12-22 Polybutylene terephthalate and method for production thereof, and composition comprising the same and film Expired - Lifetime CN100434452C (en)

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