WO2007074603A1

WO2007074603A1 - Aromatic polycarbonate resin composition and molded resin

Info

Publication number: WO2007074603A1
Application number: PCT/JP2006/323787
Authority: WO
Inventors: Makoto Nakamura; Hiroshi Nakano; Kouji Iwaki
Original assignee: Mitsubishi Chemical Corporation
Priority date: 2005-12-27
Filing date: 2006-11-29
Publication date: 2007-07-05

Abstract

An aromatic polycarbonate resin composition which comprises an aromatic polycarbonate resin (ingredient (A)) and a polybutylene terephthalate resin (ingredient (B)) and optionally further contains a rubbery polymer and/or an inorganic filler, characterized in that the amounts of the aromatic polycarbonate resin (ingredient (A)) and the polybutylene terephthalate resin (ingredient (B)) are 51-99 parts by weight and 1-49 parts by weight, respectively, per 100 parts by weight of the sum of the aromatic polycarbonate resin (ingredient (A)) and the polybutylene terephthalate resin (ingredient (B)) and that the polybutylene terephthalate resin (ingredient (B)) has a titanium compound content of 1-75 ppm, excluding 1 ppm, in terms of titanium atom amount and a terminal carboxy group content of 39 µeq/g or lower. This aromatic polycarbonate resin composition has an excellent balance among various properties, i.e., is satisfactory in all of flowability, rigidity, impact resistance, chemical resistance, fatigue characteristics, heat resistance, thermal stability in residence, and suitability for recycling.

Description

Specification

Aromatic polycarbonate resin composition and resin molded article

Technical field

[0001] The present invention relates to an aromatic polycarbonate resin composition mainly composed of an aromatic polycarbonate resin and a polybutylene terephthalate resin, and more specifically, fluidity, rigidity, impact resistance, chemical resistance, fatigue characteristics, The present invention relates to an aromatic polycarbonate resin composition excellent in various properties such as heat resistance and residence heat stability, and at the same time excellent in recycling characteristics, and a resin molded product formed by molding the same.

Background art

[0002] Aromatic polycarbonate resin is a general-purpose engineering plastic with excellent transparency, impact resistance, heat resistance, dimensional stability, etc., and its excellent characteristics make it suitable for electrical, electronic, electronic device parts, machine parts, and vehicles. It is used in a wide range of parts and other fields. Furthermore, the polymer alloy composed of aromatic polycarbonate resin and polybutylene terephthalate resin, while utilizing the above-mentioned excellent features of aromatic polycarbonate resin, chemical resistance and molding, which are disadvantages of aromatic polycarbonate resin. It is a material with improved processability, and is used in a wide range of fields such as vehicle interior / exterior parts, various housing members.

[0003] An aromatic polycarbonate resin composition (polymer alloy) mainly composed of aromatic polycarbonate resin and polybutylene terephthalate (ΡΒΤ) resin is a polymer alloy having a micro-structure of sea-island structure. Depending on whether it constitutes the sea phase (continuous layer), its characteristics vary greatly. In the case where the aromatic polycarbonate resin constitutes a continuous layer (the content power of the aromatic polycarbonate resin is larger than that of the polybutylene terephthalate resin), the resistance is higher than that of the polymer alloy having a high content of polybutylene terephthalate resin. Although it has excellent impact properties and dimensional characteristics, it has problems such as low fluidity and low chemical resistance and low fatigue properties and heat resistance (thermal deformation temperature). When such a resin composition is used for vehicle parts, a material having higher fatigue characteristics and heat resistance has been demanded.

[0004] Furthermore, in a polymer alloy having a high content of aromatic polycarbonate resin, transesterification reaction is caused by excessive heating during melt kneading by an extruder or during residence in an injection molding machine. There was a problem that it progressed excessively and the heat resistance of the resin composition decreased.

[0005] In addition, vehicle parts and the like have been painted for design and coloration, and a material having higher heat resistance that can withstand the coating temperature has been desired. In recent years, it has become essential to recycle materials used to grind used products and non-conforming products such as sprue, return them to virgin raw materials, and process them into resin products through a melt-forming process. Materials with low heat resistance deterioration even after receiving heat history from Al recycling are becoming very important.

[0006] Furthermore, in parts that require higher impact resistance, such as vehicle exterior parts, a rubber polymer is blended in a polymer alloy mainly composed of aromatic polycarbonate resin and polybutylene terephthalate resin. A resin composition having improved impact resistance has been proposed. (For example, see Patent Documents 1 and 2). However, although the impact resistance is improved by including the rubbery polymer in this way, there is a problem that the rigidity, heat resistance, and fatigue characteristics are lowered with the increase in the content thereof. There has been a demand for a polymer alloy having a good impact resistance, in which the amount of polymer added is minimized. In addition, if the impact resistance is improved by increasing the molecular weight of a resin component such as an aromatic polycarbonate resin, the fluidity of the polymer alloy is reduced, so that there are limitations on the use.

[0007] Furthermore, materials that are excellent in rigidity and dimensional stability (thermal expansibility) are required for fields that are expected to be greased from steel sheets, such as vehicle exterior parts, and parts that require thinning. In general, an inorganic filler is blended into a polymer alloy composed of an aromatic polycarbonate resin and a polybutylene terephthalate resin. Also, in fields where good appearance is required, such as vehicle exterior parts, silicate-based inorganic pulverized products and synthetic whiskers are used as inorganic fillers.

[0008] By blending these inorganic fillers, rigidity and dimensional stability are improved, but there is a problem that impact resistance and molding processability (fluidity) are lowered. Especially in vehicle exterior parts, the elongation at break, surface impact strength, V, and impact resistance are more important than the Izod impact strength in relation to the strain rate, and inorganic fillers are added to improve these impact resistance. Materials are needed.

[0009] Further, among the inorganic fillers, most of crushed products of silicate-based inorganic substances that can obtain a good appearance. However, when the blended resin is an aromatic polycarbonate resin, there is a problem that the thermal stability of the resin deteriorates due to decomposition of the resin or decomposition accompanying the transesterification reaction. there were.

[0010] As described above, the content of the aromatic polycarbonate resin is high, and the polymer alloy with polybutylene terephthalate resin has fluidity, rigidity, impact resistance, chemical resistance, fatigue characteristics, retention time. There has been a demand for a material having an excellent balance of physical properties, such as excellent thermal stability and recyclability.

[0011] In response to this, for example, as a means for solving the problem of the above-mentioned residence heat stability, a technique of blending a phosphorus compound into a polymer alloy of an aromatic polycarbonate resin and a polyester resin is known ( For example, see Patent Documents 3 and 4). However, simply adding a phosphorus compound does not always satisfy the balance of impact resistance, fatigue characteristics, heat resistance, residence heat stability, and recycling characteristics.

[0012] As means for solving the problems such as impact resistance and residence heat stability, a specific phosphite compound or a resin composition using a phosphate compound (for example, Patent Document 5, 6), a resin composition using acid-modified olefin wax (see, for example, Patent Document 7), and a resin composition using surface treatment talc and Z or surface treatment My power (eg, Patent Document 8) has been proposed. These conventional technologies have an excellent balance in physical properties such as fluidity, rigidity, impact resistance, heat resistance, fatigue characteristics, and stagnant heat stability. It was not satisfactory.

[0013] Further, a thermoplastic resin composition characterized in that it is a polymer alloy comprising a polycarbonate resin and a polybutylene terephthalate resin and has a melt viscosity stability index of 2.5% or less ( (See Patent Document 9). Specifically, a technique in which a branched component of polycarbonate resin, a terminal carboxy concentration of polybutylene terephthalate resin, and a specific stabilizer is disclosed.

[0014] However, the technique disclosed in Patent Document 9 and the concretely exemplified composition have no impact resistance, fatigue characteristics, heat resistance, residence heat stability, and recycling characteristics. It was always a satisfying force. Furthermore, the titanium content of the polybutylene terephthalate resin is only described in general terms, and a specific amount of titanium content. And the importance of a polybutylene terephthalate resin having a specific amount of terminal carboxy concentration was not disclosed.

[0015] On the other hand, a thermoplastic resin composition excellent in mechanical properties comprising a polybutylene terephthalate resin and a polycarbonate resin containing an impact strength improver and having a specific end group concentration has been proposed. (See Patent Document 10). However, by simply adjusting the terminal group concentration, the content of aromatic polycarbonate resin is not necessarily satisfactory in terms of impact resistance, fatigue characteristics, heat resistance, residence heat stability, and recycling characteristics. It was not a technology that was excellent in fluidity, impact resistance, rigidity, chemical resistance, fatigue resistance, heat resistance, residence heat stability, and recycling characteristics in polymer alloys with many polybutylene terephthalate resins.

[0016] In addition, the polybutylene terephthalate resin specifically exemplified as a thread and composition has a high titanium content, a high content of aromatic polycarbonate resin, and a polybutylene terephthalate resin. The polymer alloy has the problem of poor residence heat stability and recycling characteristics.

[0017] On the other hand, a composition in which a transesterification reaction between a polybutylene terephthalate resin produced using a polycondensation catalyst containing a phosphorus component and a titanium component and polycarbonate resin is suppressed has been proposed (patent) (Ref. 11). However, the polybutylene terephthalate resin is exemplified as a composition which is not sufficient to simply use the phosphorus component and the titanium component as the polycondensation catalyst. The polybutylene terephthalate resin has a high titanium content. When the oil composition was used, the balance of impact resistance, fluidity, rigidity, chemical resistance, fatigue characteristics, heat resistance, residence heat stability, recycling characteristics, etc. was not satisfactory.

[0018] Furthermore, for 100 parts by weight of a polybutylene terephthalate resin having a titanium content of 33 ppm or less as titanium atoms, the mechanical properties and crystallization rate of polycarbonate resin 5 to: LOO parts by weight and other components are included. In addition, a resin composition with improved hydrolysis resistance has been proposed (see Patent Document 12). However, this technology only discloses a polymer alloy technology with a polycarbonate resin having a high content of polybutylene terephthalate resin, which is different from a field in which a polymer alloy having a high content of aromatic polycarbonate resin is applied. There was only a technology that disclosed.

Patent Document 1: Japanese Patent Laid-Open No. 49 41442

Patent Document 2: JP-A-58-117247

Patent Document 3: Japanese Patent Laid-Open No. 3-97752

Patent Document 4: Japanese Patent Laid-Open No. 63-265949

Patent Document 5: JP-A-5-222283

Patent Document 6: JP-A-6-49343

Patent Document 7: JP-A-9-12846

Patent Document 8: JP-A-8-127711

Patent Document 9: Japanese Patent Laid-Open No. 2002-294060

Patent Document 10: Japanese Patent Application Laid-Open No. 2004-18558

Patent Document 11: Japanese Patent Laid-Open No. 7-138354

Patent Document 12: Japanese Unexamined Patent Application Publication No. 2004-307794

Disclosure of the invention

Problems to be solved by the invention

[0020] The purpose of the present invention is to eliminate the above-mentioned drawbacks of the prior art, and to be excellent in fluidity, rigidity, impact resistance, chemical resistance, fatigue characteristics, heat resistance and residence heat stability, and also in recycling characteristics. Another object of the present invention is to provide an aromatic polycarbonate resin composition excellent in the above.

Means for solving the problem

[0021] As a result of intensive studies to achieve the above object, the present inventors have found that the content of aromatic polycarbonate resin is high, and aromatic polycarbonate resin and polybutylene terephthalate resin have In polymer alloy, polybutylene terephthalate resin contains a specific amount of titanium compound and has a specific terminal carboxyl group concentration, and if necessary, a specific amount of rubbery polymer and Z or inorganic filler is blended. Aromatic polycarbonate with improved physical properties such as fluidity, rigidity, impact resistance, chemical resistance, fatigue characteristics, heat resistance, residence heat stability and recycling characteristics, and excellent physical property balance The present invention was completed by discovering that it was a fat composition (hereinafter, sometimes simply referred to as “wax composition”). [0022] A first gist of the present invention is an aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin (component A) and a polybutylene terephthalate resin (component B), which is an aromatic polycarbonate resin. A total of 100 parts by weight of fat (component A) and polybutylene terephthalate resin (component B), 51 to 99 parts by weight of aromatic polycarbonate resin (component A), 1 to 49 parts of polybutylene terephthalate resin (component B) Aromatics characterized in that, in polybutylene terephthalate resin (component B), the titanium compound content is greater than 1 ppm and less than or equal to 75 ppm, and the terminal carboxyl group is less than or equal to 39 eqZg It resides in a polycarbonate resin composition.

[0023] A second aspect of the present invention is the aromatic polycarbonate resin composition according to the first aspect, further comprising an aromatic polycarbonate resin (component A) and a polybutylene terephthalate resin (component B). An aromatic polycarbonate resin composition containing 0.5 to 40 parts by weight of a rubbery polymer (component C) with respect to 100 parts by weight in total.

[0024] The third aspect of the present invention is the aromatic polycarbonate resin composition according to the first aspect, further comprising an aromatic polycarbonate resin (component A) and a polybutylene terephthalate resin (component B). The aromatic polycarbonate resin composition contains 1 to 50 parts by weight of inorganic filler (component D) with respect to 50 to 99 parts by weight in total.

The invention's effect

[0025] The aromatic polycarbonate resin composition of the present invention satisfies the physical properties of fluidity, rigidity, impact resistance, chemical resistance, fatigue properties, heat resistance, residence heat stability, and recycling properties at the same time. It is a rosin composition excellent in balance.

[0026] The aromatic polycarbonate resin composition of the present invention having such a feature can be used in a wide range of fields, and is used in electrical and electronic equipment parts, OA equipment, machine parts, vehicle parts, and architecture. It is useful for various applications such as parts, various containers, leisure goods and miscellaneous goods, and can be expected to be applied especially to vehicle exterior / skin components and vehicle interior components.

[0027] Vehicle exterior parts include outer door handles, bumpers, fenders, door panels, trunk lids, front panels, rear panels, roof panels, bonnets, pillars, side moldings, garches, wheel caps, hood bulges, Examples include fuel lids, various types of boilers, and cowlings for motorbikes. As vehicle interior parts, Examples include display doors such as inner door hand handles, center panel boards, instrument panel panels, console boxes, luggage floor boards, and car navigation systems.

Brief Description of Drawings

[0028] FIG. 1 is an explanatory diagram of an example of an esterification reaction step or a transesterification reaction step employed in the present invention.

FIG. 2 is an explanatory diagram of an example of a polycondensation process employed in the present invention.

FIG. 3 is an explanatory diagram of an example of a polycondensation process employed in the present invention.

Explanation of symbols

[0029] 1: Raw material supply line

2: Recirculation line

3: Catalyst supply line

4: Extraction line

5: Distillation line

6: Extraction line

7: Circulation line

8: Extraction line

9: Gas extraction line

10: Condensate line

11: Extraction line

12: Circulation line

13: Extraction line

14: Vent line

A: Reaction tank

B: Extraction pump

C: Rectifying tower

D: Pump

E: Pump F: Tank

G: Capacitor

LI: Extraction line

L3, L5: Extraction line

L2, L4, L6: Vent line

L7: Group 1 Z2 metal compound catalyst supply line

L8: 1,4-Butanediol supply line

a: First polycondensation reactor

d: Second polycondensation reactor

k: Third polycondensation reactor

c, e, m: gear pump for extraction

g: Dusshead,

h: Rotary cutter

BEST MODE FOR CARRYING OUT THE INVENTION

[0030] Hereinafter, the present invention will be described in detail. In the specification of the present application, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In the present specification, the “group” of various compounds may have a substituent without departing from the gist of the present invention.

[0031] “1Ί ¾ ^ polycarbonate steel (A5¾ min):

The aromatic polycarbonate resin (component A) used in the present invention (hereinafter sometimes abbreviated as “component A”) includes, for example, an aromatic dihydroxy compound and a carbonate precursor, or In addition, it is a linear or branched thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting a small amount of a polyhydroxy compound.

[0032] As the aromatic polycarbonate resin (component A) used in the present invention, those obtained by any conventionally known production method can be used. Specific examples include an interfacial polymerization method, a melt ester exchange method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Among them, it is advantageous in the chemical industry to use an interfacial polymerization method or a melt transesterification method. Hereafter, how to produce aromatic polycarbonate resin As a method, these two methods will be described as examples.

[0033] Specific examples of the aromatic dihydroxy compound used as a raw material include 2,2-bis (4 hydroxyphenol) propane (= bisphenol A), 2,2bis (3 , 5 Dibromo 4-hydroxyphenol) propane (= tetrabromobisphenol A), bis (4-hydroxyphenol) methane, 1,1-bis (4hydroxyphenol) ethane, 2,2bis (4 hydroxyphenol) butane, 2,2 bis (4 hydroxyphenol) octane, 2,2-bis (4 hydroxy-3-methylphenol) propane, 1,1-bis (3-tert-butyl-) 4-hydroxyphenol) propane, 2,2-bis (4-hydroxy-1,3,5-dimethylphenol) propane, 2,2-bis (3-bromo-4-hydroxyphenol) propane, 2,2-bis (3,5-dichloro-one) 4 Hydroxyphenol) propane, 2, 2 Bis (3-Fuel loop 4 — Hydroxyphenol) propane, 2,2 bis (3 cyclohexyl 4 hydroxyphenol) pronone, 1,1 bis (4-hydroxyphenol) 1 ferroethane, bis (4-hydroxyphenol) 1) Diphenylmethane, 2, 2 bis (4 hydroxyphenyl) 1, 1, 1 to 1 Trichloropropane, 2, 2 bis (4 hydroxyphenyl) 1, 1, 1, 3, 3, 3 hexachloropronone, 2,2 bis (4 hydroxyphenol) -1,1,1,3,3,3 bis (hydroxyaryl) alkanes exemplified by hexafluoropropanol, etc .;

[0034] 1,1 bis (4-hydroxyphenol) cyclopentane, 1,1 bis (4-hydroxyphenol) cyclohexane, 1,1-bis (4-hydroxyphenol) 1, 3, 3 , 5 Trimethyl bis Bis (hydroxyaryl) cycloalkanes exemplified by hexane and the like;

[0035] Forced structure-containing bisphenols exemplified by 9, 9bis (4hydroxyphenol) fluorene, 9,9bis (4hydroxy-1-methylphenol) fluorene; 4, 4 'dihydroxy Diphenyl ethers such as diphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, etc .;

[0036] Dihydroxydiarylsulfides exemplified by 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxy-3,3'dimethyldiphenylsulfide, and the like; 4,4'dihydroxydiphenylsulfoxide 4,4'-dihydroxy 3,3'-dimethyldiphenyl sulfoxide, and the like; 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxysulfone, 4,4'-dihydroxy-1,3'-dimethyldiphenyl -Examples with lusulfone And dihydroxydiaryl sulfones shown; noduloquinone, resorcin, 4, 4 'dihydroxydiphenyl and the like.

[0037] Among these, bis (4-hydroxyphenol) alkanes are preferable, and 2,2bis (4-hydroxyphenol) propane [= bisphenol A is particularly preferable from the viewpoint of impact resistance. ]. These aromatic dihydroxy compounds may be used alone or in combination of two or more!

[0038] Carbonate precursors, carbonate esters, haloformates and the like are used as the carbonate precursor to be reacted with the aromatic dihydroxy compound, specifically, phosgene; diphenyl carbonate, ditolyl carbonate and the like. Diaryl carbonates; Dialkyl carbonates such as dimethyl carbonate and jetyl carbonate; and dino-mouth formate of divalent phenol. These carbonate precursors can also be used alone or in combination of two or more.

[0039] The aromatic polycarbonate resin (component A) used in the present invention may be a branched aromatic polycarbonate resin obtained by copolymerizing a trifunctional or more multifunctional aromatic compound. Trifunctional or higher polyfunctional aromatic compounds include fluorodalcine, 4,6 dimethyl-2, 4,6 tri (4 hydroxyphenol) heptene-2, 4,6 dimethyl-2, 4, 6 tri (4 — Hydroxyphenyl) heptane, 2,6 dimethyl-1,2,4,6 tri (4hydroxyphenyl) heptene-1,3,1,3,5 tri (4hydroxyphenyl) benzene, 1,1,1-tri (4-Hydroxyphenol) polyhydroxy compounds such as ethane, etc., or 3,3-bis (4-hydroxyaryl) oxyindole (= isatin bisphenol), 5-chloroisatin 5, 7 dichloroisatin, 5 bromysatin and the like. Of these, 1, 1, 1-tri (4-hydroxyphenyl) ethane is preferable. The polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound, and the amount used is preferably 0.01 to 10 mol% with respect to the aromatic dihydroxy compound. Among them, 0.1 to 2 mol% is preferable.

[0040] In the reaction by the interfacial polymerization method, for example, in the presence of an organic solvent inert to the reaction and an aqueous alkali solution, the pH is usually kept at 9 or higher, and the aromatic dihydroxy compound is separated as necessary. Phosgene with quantity regulator (end stopper), antioxidant of aromatic dihydroxy compound React with. Next, a method of obtaining a polycarbonate by adding a polymerization catalyst such as tertiary amine or quaternary ammonium salt and performing interfacial polymerization can be mentioned. The temperature of the phosgenation reaction is usually 0 to 40 ° C., and the reaction time is several minutes (for example, 10 minutes) to several hours (for example, 6 hours). Also, the timing of addition of the molecular weight regulator may be appropriately selected and determined after the phosgene reaction until the start of the polymerization reaction.

[0041] Here, the organic solvent inert to the reaction includes chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, black mouth form, monochrome mouth benzene and dichlorobenzene, and aromatics such as benzene, toluene and xylene. A hydrocarbon etc. are mentioned. Examples of the alkaline compound used in the alkaline aqueous solution include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.

Examples of the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group. Examples of the compound having a monovalent phenolic hydroxyl group include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol and p-long chain alkyl-substituted phenol. It is done.

[0042] The amount of the molecular weight regulator used is preferably 0.5 to 50 mol, more preferably 1 to 30 mol, per 100 mol of the aromatic dihydroxy compound. Polymerization catalysts include tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, pyridine; trimethylbenzyl ammonium chloride, tetramethyl ammonium chloride, triethylbenzyl. Quaternary ammonia salts such as ammonium chloride.

[0043] The reaction by the melt transesterification method is carried out, for example, by an ester exchange reaction between a carbonic acid diester and an aromatic dihydroxy compound. Examples of the carbonic acid diester include dialkyl carbonates such as dimethyl carbonate, jetyl carbonate, and di-tert-butyl carbonate, and substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate. Of these, diphenyl carbonate and substituted diphenol carbonate are preferred. Particularly preferred is diphenyl carbonate!

[0044] In the case of aromatic polycarbonate resin, the amount of terminal hydroxyl groups greatly affects the thermal stability, hydrolysis stability, color tone, etc. of the product polycarbonate. It may be appropriately adjusted by any known method. In the melt transesterification reaction, usually, an aromatic polycarbonate having a desired molecular weight and terminal hydroxyl group amount adjusted by adjusting the mixing ratio of the carbonic diester and the aromatic dihydroxy compound and the degree of vacuum during the transesterification reaction. Can be obtained. Usually, in the melt transesterification reaction, carbonic acid diester is used in an equimolar amount or more relative to 1 mol of aromatic dihydroxy compound, among which 1.01-: L is preferably used in an amount of 30 mol. .

[0045] Further, as a more aggressive adjustment method, there is a method of adding a terminal terminator separately at the time of the reaction, and examples of the terminal terminator in this case include monovalent phenols, monovalent carboxylic acids, carbonic acid diesters Kind.

[0046] When a polycarbonate is produced by a melt transesterification method, a transesterification catalyst is usually used. The transesterification catalyst is not particularly limited, but alkali metal compounds and Z or alkaline earth metal compounds are preferred. In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination. The transesterification reaction using the above raw materials is 100

The reaction may be performed at a temperature of ˜320 ° C., and finally, a melt polycondensation reaction may be performed under reduced pressure of 2 mmHg or less while removing by-products such as aromatic hydroxy compounds.

[0047] The melt polycondensation can be carried out by either a batch method or a continuous method. Among these, in consideration of the aromatic polycarbonate resin used in the present invention and the stability of the resin composition of the present invention, it is preferable to carry out the process continuously. As the catalyst deactivator used in the melt transesterification method, it is preferable to use a compound that neutralizes the transesterification reaction catalyst, for example, a thio-containing acidic compound or a derivative formed therefrom. The compound neutralizing such a catalyst is preferably added in an amount of 0.5 to 10 equivalents, more preferably 1 to 5 equivalents, relative to the alkali metal contained in the catalyst. In addition, the compound neutralizing such a catalyst is added to the polycarbonate in an amount of preferably 1 to: LOO ppm, more preferably 1 to 20 ppm.

[0048] The molecular weight of the aromatic polycarbonate resin (component A) used in the present invention may be appropriately selected and determined, but the viscosity average molecular weight [Mv] converted from the solution viscosity is in the range of 10,000 to 50,000. Those are preferred. The viscosity average molecular weight of aromatic polycarbonate is 10000 or more By setting it as above, the mechanical strength tends to be further improved, and it is more preferable when used for applications requiring high mechanical strength. On the other hand, when the viscosity average molecular weight is 50000 or less, there is a tendency that flowability can be further reduced, and the viewpoint power of ease of molding processability is more preferable.

[0049] The viscosity average molecular weight is more preferably 12000 to 40000, and still more preferably 1400 to 30000. Also, two or more types of aromatic polycarbonate resin having different viscosity average molecular weights may be mixed. Of course, aromatic polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed.

[0050] Here, the viscosity average molecular weight [Mv] refers to the intrinsic viscosity [η] (unit: dlZg) at a temperature of 20 ° C using a Ubbelohde viscometer using methylene chloride as a solvent. The degree formula, that is, r? = 1. 23 Χ 10 ^_4 · ° · ⁸³ , which means the force is calculated. Here, the intrinsic viscosity [r?] Is the specific viscosity [7?] Measured at each solution concentration [C] (gZdl) and calculated by the following formula.

It is the value that was issued.

[0051] [Equation 1]

[0052] The terminal hydroxyl group concentration of the aromatic polycarbonate resin used in the present invention is usually ΙΟΟΟρρm or less, preferably 700 ppm or less, more preferably 400 ppm or less, and particularly preferably 300 ppm or less. The lower limit is preferably 10 ppm or more, more preferably 20 ppm or more, more preferably 30 ppm or more, and particularly preferably 40 ppm or more.

[0053] By setting the terminal hydroxyl group concentration to 10 ppm or more, a decrease in molecular weight can be suppressed, and the mechanical properties and fatigue properties of the resin composition tend to be further improved. In addition, it is preferable that the terminal group hydroxyl group concentration is 1 OOOppm or less because the heat resistance, residence heat stability, color tone, and recycling characteristics of the resin composition tend to be improved.

[0054] The terminal hydroxyl group unit is the weight of the terminal hydroxyl group expressed in ppm with respect to the weight of the aromatic polycarbonate resin, and the measuring method is a colorimetric determination (Macromol by the titanium tetrachloride Z acetic acid method). Chem. 88 215 (1965)).

[0055] Further, in order to improve the appearance of the molded article and the fluidity, the aromatic polymer used in the present invention is used. Carbonate resin (component A) may contain an aromatic polycarbonate oligomer. The viscosity average molecular weight [Mv] of the aromatic polycarbonate oligomer is preferably 1500 to 9500, more preferably <2000 to 9000. It is preferable to use the aromatic positive carbon sesame digoma in a range of 30% by weight or less of the cocoon component.

[0056] Further, the aromatic polycarbonate resin (component A) used in the present invention is a used product power that is not limited to virgin raw materials. Recycled aromatic polycarbonate resin, so-called material-recycled aromatic polycarbonate resin. Fats may be used. Used products include optical recording media such as optical discs, light guide plates, automobile window glass, automotive transparent parts such as automotive headlamp lenses' windshields, containers such as water bottles, eyeglass lenses, and sound barriers. A building member such as a corrugated sheet is preferably mentioned. It is also possible to use non-conforming products, pulverized products with sprue, runner strength, etc., or pellets obtained by melting them. The regenerated aromatic polycarbonate resin is preferably 80% by weight or less of the component A, more preferably 50% by weight or less.

[0057] "2Ί polybutylene terephthalate oil (component B):

The polybutylene terephthalate resin used in the present invention (hereinafter sometimes abbreviated as “component B”) is a polyester having a structure in which terephthalic acid units and 1,4 butanediol units are ester-bonded. least 50 mol% of acid units composed of terephthalic acid units, indicates a polymer 50 mole ^_0/0 or more diol units consists of 1, 4-butanediol unit, a lppm content of Chitani匕合product as a titanium atom It is a polybutylene terephthalate resin having a concentration of 75 ppm or less and a terminal carboxyl group of 39 μeqZg or less.

[0058] The proportion of terephthalic acid units in all dicarboxylic acid units is preferably 70 mol% or more, more preferably 80 mol% or more, and particularly preferably 95 mol% or more. The proportion of butanediol units is preferably 70 mol% or more, more preferably 80 mol% or more, and particularly preferably 95 mol% or more. By setting the terephthalic acid unit or 1,4 butanediol unit to 50 mol% or more, the decrease in the crystallization rate of the B component can be suppressed and the moldability can be improved.

[0059] In the polybutylene terephthalate resin used in the present invention, dicarbonate other than terephthalic acid is used. Any conventionally known rubonic acid component with no particular limitation can be used. Specifically, for example, phthalic acid, isophthalic acid, 4,4′-diphenoldicarboxylic acid, 4,4′-diphenole noetreo-resisting norevonic acid, 4,4′monobenzophenone dicanolevonic acid, 4 , 4'-diphenoxyethaneethane dicarboxylic acid, 4, 4'-diphenylsulfone dicarboxylic acid, 2,6 naphthalene dicarboxylic acid and other aromatic dicarboxylic acids, 1, 2 cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc. I can list them. These dicarboxylic acid components can be introduced into the polymer skeleton as a dicarboxylic acid, or using a dicarboxylic acid derivative such as a dicarboxylic acid ester or a dicarboxylic acid halide as a raw material.

[0060] In the polybutylene terephthalate resin (component B) used in the present invention, any conventionally known diol component other than 1,4 butanediol can be used without any particular limitation. Specifically, for example, ethylene glycol, diethylene glycol, polyethylene darconol, 1,2 propanediol, 1,3 propanediol, polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5 pentanediol, neopentyl glycol 1, 6 hexanediol, 1,8 octanediol and other aliphatic diol, 1,2 cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexane Cycloaliphatic diols such as sanjimethylol, xylylene glycol, 4,4'-dihydroxybiphenyl, 2,2 bis (4-hydroxyphenyl) propane, bis (4 hydroxyphenol) sulfone, etc. And aromatic diols.

[0061] In the polybutylene terephthalate resin (component B) used in the present invention, lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, ρ-β-hydroxy Monofunctional components such as hydroxycarboxylic acid such as ethoxybenzoic acid, alkoxycarboxylic acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid, tri-force valeric acid, trimellitic acid, trimesic acid , Pyromellitic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, etc. An active ingredient or the like can be used as a copolymerization component.

[0062] The polybutylene terephthalate resin (component B) used in the present invention is obtained by polycondensing, for example, 1,4-butanediol and terephthalic acid (or dialkyl terephthalate) in the presence of a catalyst such as a titanium compound. can get. The feature of the polybutylene terephthalate resin (B) used in the present invention is that the titanium content is more than 1 ppm and less than 75 ppm as titanium atoms. This value is the weight ratio of titanium atoms to polybutylene terephthalate resin. The titanium atom content can be measured by recovering the metal in the polymer by a method such as wet ashing and using a method such as atomic emission, atomic absorption, or inductively coupled plasma (ICP). .

[0063] The lower limit of the titanium content is preferably 1 ppm as titanium atoms, especially 10 ppm, more preferably 20 ppm, particularly 25 ppm, and the upper limit is 75 ppm as titanium atoms, especially 50 ppm, especially 45 ppm. preferable. When the titanium content is less than 1 ppm as titanium atom, the polymerization reaction rate of the polybutylene terephthalate resin decreases, so the polymerization reaction has to proceed at a high temperature for a long time, and the color tone of the polybutylene terephthalate resin is poor. This is not preferable because the reaction does not proceed during kneading with an aromatic polycarbonate which only promotes the heat deterioration reaction, and the mechanical properties and fatigue characteristics of the polymer alloy are lowered.

[0064] On the other hand, if the titanium content exceeds 75 ppm as titanium atoms, it becomes difficult to control the transesterification reaction, which only causes the generation of gas during kneading and molding and the poor thermal stability. Further, it is preferable because the polymer alloy with the aromatic polycarbonate deteriorates the heat resistance, the residence heat stability and the recycling characteristics, and further deteriorates the mechanical properties and color tone.

[0065] The polybutylene terephthalate resin (component B) used in the present invention contains a titanium compound as described above, and this titanium compound is preferably a polycondensation catalyst for a polybutylene terephthalate resin. Specific examples of the titanium compound used as the polycondensation catalyst include, but are not limited to, inorganic titanium compounds such as titanium oxide and tetrasalt titanium; tetramethyl titanate, tetraisopropyl titanate, tetra And titan alcoholates such as butyl titanate; titanium phenolates such as tetraphenol titanate; and the like. Of these, titanium alcoholates are preferred, and tetraalkyl titanates are preferred, and tetrabutyl titanate is particularly preferred. [0066] The polybutylene terephthalate resin (component B) used in the present invention preferably contains a group 1 metal compound and a Z or group 2 metal compound in addition to the titanium compound. The content of the Group 1 metal compound and the Z or Group 2 metal compound in the polybutylene terephthalate resin (component B) is preferably more than 1 ppm and 50 ppm or less in terms of metal atoms. The metal atom content can be measured in the same manner as the above-described titanium measurement method.

[0067] The lower limit of the content of the Group 1 metal compound and the Z or Group 2 metal compound is preferably 3 ppm, particularly 5 ppm, in terms of metal atoms. The upper limit is preferably 50 ppm, in particular 30 ppm, particularly 20 ppm in terms of metal atoms. By setting the content of the Group 1 metal compound and the Z or Group 2 metal compound to 1 ppm or more, the mechanical properties and fatigue characteristics of the resin composition tend to be improved. When the content of the metal compound is less than 50 ppm, the heat resistance and residence heat stability of the resin composition tend to improve the recycling characteristics.

[0068] The polybutylene terephthalate resin (component B) used in the present invention preferably contains a Group 1 metal compound and Z or a Group 2 metal compound titanium compound as described above. The compound is preferably a polycondensation catalyst for polybutylene terephthalate resin (component B) or a co-catalyst for a titanium compound catalyst. There are no particular restrictions on the Group 1 metal compound and the Z or Group 2 metal compound used as the polycondensation catalyst. Specifically, examples of the Group 1 metal compound include lithium, sodium, potassium, rubidium, and cesium hydroxides. And various organic compounds such as acetates, phosphates, carbonates, and the like. In addition, Group 2 metal compounds include beryllium, magnesium, calcium, strontium and barium hydroxides; oxides; alcoholates; various organic acid salts such as acetates, phosphates and carbonates;匕 composites.

[0069] These may be used alone or in combination. Among these, from the viewpoint of easy handling and availability, and a catalyst effect, compounds such as lithium, sodium, potassium, magnesium, and calcium are preferable, and a compound of lithium or magnesium that is excellent in catalytic effect and color tone is preferable. M, especially preferred are magnesium compounds.

[0070] Specific examples of magnesium compounds include magnesium acetate and magnesium hydroxide. Examples include shim, magnesium carbonate, magnesium oxide, magnesium alkoxide, magnesium hydrogen phosphate, and the like. Of these, organic acid salts are preferred, and in particular, magnesium acetate is preferred.

[0071] The terminal carboxyl group concentration of the polybutylene terephthalate resin (component B) used in the present invention is 39 μeqZg or less, preferably 5 to 35 μeqZg, particularly preferably 10 to 30 μeqZg. By setting the terminal carboxyl group concentration to 39 eq / g or less, the mechanical properties and fatigue properties of the resin composition tend to improve, and by setting the terminal carboxyl group concentration to 5 eqZg or more, the resin composition The heat resistance, residence heat stability and recyclability of the product tend to be improved, which is preferable.

[0072] The terminal carboxyl group concentration of the polybutylene terephthalate resin was determined by dissolving 0.5 g of polybutylene terephthalate resin in 25 mL of benzyl alcohol and titrating with 0.01 mol ZL benzyl alcohol solution of sodium hydroxide. You can ask for it.

[0073] At the end of the polybutylene terephthalate resin, there may be a hydroxyl group or a bur group in addition to the carboxyl group, and a methoxy carbo yl group derived from the raw material may remain. In particular, dimethyl terephthalate is used as the raw material. In many cases, it may remain.

[0074] In addition, the terminal methoxycarbonyl group in polybutylene terephthalate resin causes toxic methanol, formaldehyde, formic acid, etc. to be generated due to the heat generated during molding, such as formic acid. This may affect other molding equipment and vacuum related equipment. Therefore, in the polybutylene terephthalate resin (component B) used in the present invention, it is preferable that the terminal methoxycarbol group concentration is 0.5 eqZg or less, 0.3 / z eqZg or less, 2 / z eqZg or less, particularly 0.1 eqZg or less is preferable.

[0075] Further, the terminal bur group concentration of the polybutylene terephthalate resin (component B) used in the present invention is usually 0.1 lS / z eq / g, and more preferably 0.5 to: LO eq / g Especially preferred is 1-8 eq / g. If the terminal vinyl group concentration is too high, it may cause a deterioration in the color tone of the resin composition, and the terminal vinyl group concentration tends to further increase due to the heat history during molding. In the case of the manufacturing method, the color tone May decrease.

[0076] The concentration of each end group is as follows: deuterated form Z-hexafluoroisopropanol = 7Z3

It can be quantified by dissolving polybutylene terephthalate resin in a (volume ratio) mixed solvent and measuring 1H-NMR. At this time, in order to prevent overlap with the solvent signal, a very small amount of a basic component such as heavy pyridine may be added.

[0077] The inherent viscosity of the polybutylene terephthalate resin (component B) used in the present invention is appropriately selected from 0.5 to 2 dL / g, and more preferably 0.6 to 1.5 dL / g, further ί 0.8 to 1.3 dL / g, especially 0.95 to L 25 dL / g By setting the intrinsic viscosity to 0.5 dL Zg or more, the mechanical properties, fatigue properties, and residence heat stability of the resin composition of the present invention tend to be improved. Conversely, by setting the intrinsic viscosity to less than 2 dLZg, the fluidity of the resin composition tends to be improved. The above intrinsic viscosity is a value measured at 30 ° C. using a mixed solvent of phenol Z tetratalrethane (weight ratio 1Z1).

[0078] Further, the polybutylene terephthalate resin (component B) used in the present invention is a polybutylene terephthalate resin regenerated from a used product made only of virgin raw materials, so-called material-recycled polybutylene terephthalate resin. Use is also possible. Used products include containers, films, sheets, fibers, non-conforming products, sprues, runners, etc., and pulverized products obtained from them or pellets obtained by melting them are also used. Is possible.

[0079] Next, a method for producing polybutylene terephthalate resin (component B) used in the present invention will be described. The production method of polybutylene terephthalate resin is roughly divided into a direct polymerization method using dicarboxylic acid as a main raw material and a transesterification method using dialkyl dicarboxylate as a main raw material. In the former, water is generated in the initial esterification reaction, and in the latter, alcohol is generated in the initial transesterification reaction.

[0080] The method for producing the polybutylene terephthalate resin is roughly divided into a batch method and a continuous method depending on the raw material supply or the polymer discharge form. Perform the initial esterification reaction or ester exchange reaction in a continuous operation, then perform the polycondensation performed in a batch operation, or conversely perform the initial esterification reaction or ester exchange reaction in a batch operation. Degeneracy There is also a method of performing the combination by continuous operation.

[0081] The polybutylene terephthalate resin (component B) used in the present invention has a direct weight from the viewpoint of the availability of raw materials, the ease of processing of distillate, the superiority of raw material units, and the effects of the present invention. It is preferable to use polybutylene terephthalate resin manufactured by a legal method. In the present invention, from the viewpoint of productivity, stability of product quality, and the effect of the present invention, it is preferable to use a method in which raw materials are continuously supplied and an esterich reaction or transesterification reaction is continuously performed. In particular, it is preferable to produce polybutylene terephthalate resin by a so-called continuous method in which the polycondensation reaction following the esterification reaction or transesterification reaction is also carried out continuously.

[0082] In the method for producing polybutylene terephthalate resin (component B) used in the present invention, at least a portion of 1,4 butanediol is terephthalic acid in an esterification reaction tank in the presence of a titanium catalyst. (Or dialkyl terephthalate) is supplied to the ester reaction tank (or transesterification reaction tank) independently, and terephthalic acid (or dialkyl terephthalate) and 1,4 butanediol are continuously added to ester ester (or A process of transesterification is preferably employed.

That is, as a method for producing polybutylene terephthalate resin (component B) used in the present invention, haze and foreign matters derived from the catalyst are reduced and the catalytic activity is not lowered. In addition to 1,4 butanediol supplied with dialkyl terephthalate, it is also possible to supply 1,4 butanediol to the esterification tank or transesterification tank independently of terephthalic acid or dialkyl terephthalate. preferable. Hereinafter, the 1,4 butanediol is sometimes referred to as “separately supplied 1,4 butanediol”.

[0084] The above-mentioned "separately supplied 1,4 butanediol" can be filled with fresh 1,4 butanediol independent of the process. “Separately supplied 1,4 butanediol” collects 1,4-butanediol distilled in the ester tank or transesterification tank with a condenser and holds it as it is or in a temporary tank. It can be supplied to 1,4 butanediol, which is refluxed to the reaction vessel or purified by separating and purifying impurities. After that, 1,4 butanediol force collected by condensers etc. is also configured. “Supply 1,4 butanediol” is sometimes referred to as “recycled 1,4 butanediol”. From the viewpoint of effective utilization of resources and simplicity of equipment, it is preferable to allocate “recycled 1,4 butanediol” to “separately supplied 1,4 butanediol”.

[0085] In addition, 1,4-butanediol distilled from the esterification tank or transesterification reaction tank usually contains components such as water, alcohol, tetrahydrofuran (THF) and dihydrofuran in addition to the 1,4 butanediol component. Contains. Therefore, the 1,4-butanediol distilled above can be separated and purified from components such as water, alcohol, THF, etc. while being collected by a condenser or the like, and returned to the reaction vessel. preferable.

In the present invention, it is preferable that 10% by weight or more of “separately supplied 1,4 butanediol” is directly returned to the reaction liquid phase part. Here, the reaction liquid phase part refers to the liquid phase side of the gas-liquid interface in the esterification reaction tank or transesterification reaction tank. To return directly to the reaction liquid phase part, use piping or the like. This means that “separately supplied 1, 4 butanediol” is supplied directly to the liquid phase part without going through the gas phase part. The ratio of returning directly to the liquid phase of the reaction liquid is preferably 30% by weight or more, more preferably 50% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more. If the amount of “separately supplied 1,4 butanediol” returned directly to the reaction liquid phase is small, the titanium catalyst tends to be deactivated.

[0087] The temperature of "separately supplied 1,4 butanediol" when returning to the reactor is usually 50 to 220. C, preferably 100 to 200 ° C, more preferably 150 to 190 ° C. If the temperature of “separately supplied 1, 4 butanediol” is too high, the amount of THF by-product tends to increase, and if it is too low, the heat load tends to increase, leading to energy loss.

[0088] As the polycondensation catalyst for producing the polybutylene terephthalate resin (component B) used in the present invention, the above-mentioned titanium compounds, Group 1 metal compounds and Z or Group 2 metal compounds (hereinafter referred to as "Both") are used. These may be referred to as “titanium catalyst”, “Group 1 metal catalyst” and “Group 2 metal catalyst”, respectively), and for example, tin and compounds thereof.

[0089] Tin is usually used as a tin compound, specifically, for example, dibutyltin oxide, methylphenol tin oxide, tetraethyltin, hexethyldistinoxide, cyclohexahexyldis. Zuoxide, didodecyltin oxide, triethyltin hydride oxide, trifruzuzuno, idooxide, triisobutyltin acetate , Dibutinoles diacetate, diphenyltin dilaurate, monobutyltin trichloride, tributyltin chloride, dibutyltin sulfide, butylhydroxytin oxide, methylstannic acid, ethylstannic acid, and butylstannic acid.

[0090] However, in general, tin-tin compounds have a poor color tone of the polybutylene terephthalate resin, so the content of tin compounds in the polybutylene terephthalate resin used in the present invention is lower. However, it is preferable not to contain it. Specifically, the content power of the tin compound is usually 200 ppm or less in terms of tin atom, preferably 10 ppm or less, more preferably 10 ppm or less.

[0091] In the production of the polybutylene terephthalate resin (component B) used in the present invention, another catalyst can be used as a catalyst. Specifically, for example, an antimony compound such as antimony trioxide; a germanium compound such as germanium dioxide and germanium tetroxide; a manganese compound; a zinc compound; a zirconium compound; a cobalt compound; And reaction aids such as phosphorus compounds such as esters and metal salts thereof.

[0092] Further, in order to prevent deactivation of the catalyst, 10% by weight or more of the titanium catalyst used in the esterification reaction (or transesterification reaction) is a reaction liquid independent of terephthalic acid (or dialkyl terephthalate). It is preferable to supply directly to the phase part. Here, the reaction liquid phase part means the liquid phase side of the gas-liquid interface in the esterification reaction tank or transesterification reaction tank. To supply directly to the reaction liquid phase part, use piping or the like. This means that the titanium catalyst is supplied directly to the liquid phase part without going through the gas phase part of the reactor. The proportion of the titanium catalyst added directly to the reaction liquid phase is preferably 30% by weight or more, more preferably 50% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more.

[0093] The titanium catalyst described above can be supplied directly to the reaction liquid phase part of the esterification reaction tank or the transesterification reaction tank with or without being dissolved in a solvent or the like, but the supply amount is stabilized. In order to reduce adverse effects such as heat denaturation due to the heat medium jacket of the reactor, it is preferable to dilute with a solvent such as 1,4 butanediol. The concentration at this time, as the concentration of the titanium catalyst to the total solution, usually 0.01 to 20 wt%, from 0.05 to 10 weight ^_0/0 Among, in particular 0.08 to 8 wt ^_0/0 Is preferred. [0094] From the viewpoint of reducing foreign matter, the water concentration in the solution is usually 0.05 to: L 0% by weight, and the temperature during the preparation of the solution is usually 20 to 20 from the viewpoint of preventing deactivation and aggregation. It is preferably 150 ° C, particularly 30 to 100 ° C, particularly 40 to 80 ° C. In addition, the catalyst solution is preferably mixed with separately supplied 1,4 butanediol through a pipe or the like and supplied to the esterification reaction tank or transesterification reaction tank from the viewpoint of preventing deterioration, preventing precipitation, and deactivation.

[0095] The Group 1 metal catalyst and the Z or Group 2 metal catalyst can be supplied to the esterification reaction tank or the transesterification reaction tank, but the supply position is not particularly limited. The reaction solution may be supplied to the upper surface of the reaction solution or directly to the reaction solution liquid phase portion. At this time, it may be supplied together with the raw material terephthalic acid or the titanium catalyst, or may be supplied independently.

[0096] Among these, from the viewpoint of catalyst stability, it is preferable to supply the reaction solution from the gas phase part to the upper surface of the reaction solution independently from the terephthalic acid or titanium catalyst. As a method for supplying the Group 2 metal catalyst, for example, when the Group 2 catalyst is solid at room temperature, it can be supplied to the reaction solution as a solid, but the supply amount is stabilized, and adverse effects such as heat denaturation are caused. To reduce this, it is preferable to dissolve in water or a solvent such as 1,4 butanediol and supply it as a solution. The concentration of the Group 2 metal catalyst in this solution is usually 0.01% by weight or more, preferably 0.05% by weight or more, and particularly preferably 0.08% by weight or more. Of these, the content is preferably 10% by weight or less, particularly preferably 8% by weight or less.

[0097] Further, the Group 1 metal catalyst and the Z or Group 2 metal catalyst may be added to a polycondensation reaction tank following the esterification reaction tank or the ester exchange reaction tank, or an oligomer piping attached thereto. The addition method in this case is also dissolved in a solvent such as water or 1,4 butanediol or a copolymer component such as polytetramethylene ether glycol in order to stabilize the supply amount and reduce adverse effects such as heat denaturation. The concentration at this time, which is preferably supplied as a solution, is the same as the above-mentioned solution concentration.

Next, an example of a continuous method employing a direct polymerization method will be described as a method for producing a polybutylene terephthalate resin. First, the dicarboxylic acid component having terephthalic acid as a main component and the diol component having 1,4 butanediol as a main component are mixed in a raw material mixing tank to form a slurry. In the presence of titanium catalyst, Always 180-260. C, preferably 200-245. C, more preferably 210-235. C temperature, usually 10 to 133 kPa, preferably 13 to: L01 kPa, more preferably 60 to 90 kPa (absolute pressure, the same shall apply hereinafter), usually 0.5 to 10 hours, preferably 1 In -6 hours, oligomers are obtained by continuous esterification reaction.

Next, this oligomer is transferred to a polycondensation reaction tank and polycondensed in the presence of a polycondensation catalyst in one or a plurality of polycondensation reaction tanks. In this case, it is preferably continuously, usually 210 to 280. C, preferably 220-260. C, more preferably 230-250. At least one polycondensation reaction tank at a temperature of C is usually 20 kPa or less, preferably 10 kPa or less, more preferably 5 kPa or less, with stirring, usually 2 to 15 hours, preferably 3 to : Perform polycondensation reaction in LO time. The polymer obtained by the polycondensation reaction is usually transferred to the bottom force polymer extraction die of the polycondensation reaction tank and extracted in the form of strands. After the water cooling or water cooling, it is cut with a cutter, pellets, chips It is made into granular bodies, such as a shape.

[0100] In the case of the direct polymerization method, the molar ratio of terephthalic acid to 1,4 butanediol preferably satisfies the following formula.

[0101] B / TPA = 1.1 to 5.0 (mol / mol)

[0102] However, in the above formula, B is the number of moles of 1,4 butanediol supplied to the esterification reaction tank per unit time, and TPA is the terephthalate supplied from the outside to the esterification reaction tank per unit time. The number of moles of acid.

[0103] The above "1,4 butanediol supplied from the outside to the esterification reaction tank" is a raw slurry or solution, in addition to 1,4 butanediol supplied together with terephthalic acid or dialkyl terephthalate, These are the total of 1,4 butanediol that enters the reaction tank from outside the reaction tank, such as 1,4 butanediol supplied independently and 1,4 butanediol used as the solvent for the catalyst.

[0104] If the above BZTPA value is less than 1.1, the conversion rate will be reduced and the catalyst will be deactivated. If it is greater than 5.0, the thermal efficiency will decrease and the by-products such as THF will increase. It tends to be. The value of B / TPA is preferably ί, preferably ί 1.5 to 4.5, and further to ί 2. 0 to 4.0, particularly 3.1 to 3.8.

[0105] An example of a continuous process employing the transesterification process is as follows. First, single or multiple The number of transesterification reaction vessel, in the presence of a titanium catalyst, usually 110 to 260 ° C, preferably rather ί or one hundred forty to two hundred and forty-five ^o C, further [this temperature [trowel preferably ί or 180 to 220 ^o C 10 to 133 kPa, preferably 13 to 120 kPa, more preferably 60 to: The transesterification reaction is carried out continuously under a pressure of LOlkPa, usually 0.5 to 5 hours, preferably 1 to 3 hours. An oligomer is obtained.

[0106] Next, the oligomer is transferred to a polycondensation reaction tank, and preferably continuously in the presence of a polycondensation reaction catalyst in one or a plurality of polycondensation reaction tanks, usually at 210 to 280 ° C. Is at a temperature of 220 to 260 ° C, more preferably 230 to 250 ° C, and at least one polycondensation reaction tank is usually stirred at a reduced pressure of 20 kPa or less, preferably 10 kPa or less, more preferably 5 kPa or less. The polycondensation reaction is usually carried out for 2 to 15 hours, preferably 3 to 10 hours.

[0107] In the transesterification method, the molar ratio of dialkyl terephthalate to 1,4 butanediol preferably satisfies the following formula.

[0108] B / DAT = 1.1-2.5 (mol / mol)

[0109] However, in the above equation, B is the number of moles of 1,4 butanediol supplied to the esterification reaction tank per unit time, and DAT is the external capacity of the esterification reaction tank per unit time. The number of moles of dialkyl terephthalate supplied by the company.

[0110] If the above B / DAT value is less than 1.1, the conversion rate and catalytic activity will decrease, and if it is greater than 2.5, the thermal efficiency will only decrease. There is a tendency for by-products to increase. The value of BZDAT is preferably 1.1 to 1.8, more preferably 1.2 to 1.5.

[0111] In the present invention, the esterification reaction or transesterification reaction is preferably performed at a temperature equal to or higher than the boiling point of 1,4 butanediol in order to shorten the reaction time. The boiling point of 1,4 butanediol depends on the reaction pressure, but it is 230 ° C at 101. lkPa (atmospheric pressure) and 205 ° C at 50 kPa.

[0112] As the esterification reaction tank or the transesterification reaction tank, any conventionally known one can be used. For example, any of a vertical stirring complete mixing tank, a vertical heat convection mixing tank, a tower continuous reaction tank, etc. The model of Also, a single tank may be a plurality of tanks in which the same or different tanks are connected in series or in parallel. Of these, a reaction vessel having a stirring device is preferred. In addition to the normal type consisting of a power unit, bearing, shaft, and stirring blade force, the type of agitation device may be a high-speed rotating type such as a turbine stator type high-speed rotary agitator, disk mill type agitator, or rotor mill type agitator. I can do it.

[0113] The form of stirring is not particularly limited. In addition to a normal stirring method in which the reaction solution in the reaction tank is directly stirred at the top, bottom, side, etc. It is also possible to circulate the reaction liquid by taking the part out of the reactor and stirring it with a line mixer. Known types of stirring blades can be selected, and specific examples include propeller blades, screw single blades, turbine blades, fan turbine blades, disk turbine blades, fiddler blades, full zone blades, and Max blend blades.

[0114] In the production of polybutylene terephthalate resin, usually, a multi-stage reaction vessel is used, preferably 2 to 5 reaction vessels, and the molecular weight is increased sequentially. Usually, a polycondensation reaction is performed following the initial esterification reaction or transesterification reaction.

[0115] In the polycondensation reaction step of the polybutylene terephthalate resin, a single reaction tank or a plurality of reaction tanks may be used, but a plurality of reaction tanks are preferably used. The form of the reaction tank may be any type such as a vertical stirring complete mixing tank, a vertical heat convection mixing tank, a tower type continuous reaction tank, or the like, and these may be combined. Among them, as a stirring device that is preferably a reaction tank having a stirring device, a turbine stator type high-speed rotating stirrer, a disk mill type stirrer, a rotor mill, in addition to a normal type including a power unit, a bearing, a shaft, and a stirring blade. A high-speed rotating type such as a mold stirrer can also be used.

[0116] The form of stirring is not particularly limited, and in addition to the normal stirring method in which the reaction solution in the reaction vessel is directly stirred from the top, bottom, side, etc. of the reaction vessel, It is also possible to circulate the reaction liquid by taking the part out of the reactor and stirring it with a line mixer. In particular, it is recommended that at least one of the polycondensation reactors use a horizontal reactor that has a horizontal axis of rotation and excellent surface renewal and self-cleaning properties.

[0117] Further, in order to suppress coloring and deterioration, and to suppress the increase of the end of vinyl group or the like, in at least one reaction tank, it is usually a high vacuum of 1.3 kPa or less, particularly 0.5 kPa or less, particularly 0.3 kPa or less. It is preferable to carry out below. The reaction temperature is usually 225 to 255 ° C, especially 230 to 250 ° C, especially 233 to 245 ° C. / ヽ. [0118] In addition, the polycondensation reaction step of the polybutylene terephthalate resin is a process in which a polybutylene terephthalate resin having a relatively low molecular weight, for example, an intrinsic viscosity of about 0.1 to 1.0 is obtained by melt polycondensation. After the production, it can be subsequently subjected to solid phase polycondensation (solid phase polymerization) at a temperature below the melting point of polybutylene terephthalate resin.

[0119] Hereinafter, preferred and preferred embodiments of the method for producing polybutylene terephthalate resin (B component) used in the present invention will be described with reference to the accompanying drawings. FIG. 1 is an explanatory diagram of an example of an esterification reaction step or transesterification reaction step employed in the present invention, and FIGS. 2 and 3 are explanatory diagrams of an example of a polycondensation step employed in the present invention.

[0120] In FIG. 1, the raw material terephthalic acid is usually mixed with 1,4-butanediol in a raw material mixing tank (not shown), and is transferred from the raw material supply line (1) to the reaction tank (A) in the form of slurry. If the raw material is dialkyl terephthalate, it is usually fed to the reaction tank (A) in a molten state. On the other hand, the titanium catalyst is preferably made into a solution of 1,4 butanediol in a catalyst adjusting tank (not shown) and then supplied from the catalyst supply line (3). Fig. 1 shows a mode in which the catalyst supply line (3) is connected to the recycle line for 1,4 butanediol (2) and mixed, and then supplied to the liquid phase part of the reaction tank (A). It was.

[0121] Gas that also distills from the reaction tank (A) is separated into a high-boiling component and a low-boiling component in the rectification column (C) via the distillation line (5). Usually, the main component of the high boiling point component is 1,4 butanediol, and the main component of the low boiling point component is water and THF in the case of the direct polymerization method, and in the case of the transesterification method, ananolone, _THF and water.

[0122] The high-boiling components separated in the rectification column (C) are extracted from the extraction line (6), passed through the pump (D), and partly from the recirculation line (2) to the reaction tank (A) Part of it is returned to the rectifying tower (C) from the circulation line (7). The surplus is extracted from the extraction line (8). On the other hand, the light boiling components separated in the rectification column (C) are extracted from the gas extraction line (9), condensed in the capacitor (G), and passed through the condensate line (10) and then into the tank (F). Is temporarily stored.

[0123] Tank) A part of the collected light boiling components is returned to the rectification tower (C) via the extraction line (11), the pump (E) and the circulation line (12). It is extracted outside through the extraction line (13). The condenser (G) is connected to an exhaust device (not shown) via a vent line (14). The oligomer produced in the reaction tank (A) is removed from the extraction pump (B) and the extraction line (4 ) Is extracted.

[0124] Although the catalyst supply line (3) is connected to the recirculation line (2) in the process shown in FIG. 1, both may be independent. The raw material supply line (1) may be connected to the liquid phase part of the reaction tank (A).

[0125] In FIG. 2, the oligomer supplied from the extraction line (4) shown in FIG. 1 is polycondensed under reduced pressure in the first polycondensation reaction tank (a) to become a prepolymer, and then extracted. It is supplied to the second polycondensation reaction tank (d) via the output gear pump (c) and the extraction line (L1).

[0126] When addition of Group 1 and Z or Group 2 metal catalysts is necessary, after diluting these catalysts with a solvent such as 1, 4 butanediol in a preparation tank (not shown) Then, it is connected to the 1,4 butanediol supply line (L8) via the line (L7), further diluted with 1,4 butanediol, and then supplied to the oligomer extraction line (4). The same applies to Fig. 3.

[0127] In the second polycondensation reactor (d), usually, polycondensation proceeds at a lower pressure than that of the first polycondensation reactor (a) to become a polymer. The obtained polymer is extracted in the form of a melted strand from the die head (g) through the extraction gear pump (e) and the extraction line (L3), cooled with water, etc., and then a rotary cutter ( Cut into pellets in h).

Further, in FIG. 3, the polymer obtained in the second polycondensation reactor (d) is passed through the extraction gear pump (e) and the extraction line (L3), and then passed through the third polycondensation reaction tank ( k). The third polycondensation reaction tank (k) is a horizontal reaction tank composed of a plurality of stirring blade blocks and equipped with a biaxial self-cleaning type stirring blade.

[0129] Usually, in the second polycondensation reaction tank (d), polycondensation proceeds at a lower pressure than in the first polycondensation reaction tank (a), and polycondensation occurs in the third polycondensation reaction tank (k). Going further, it becomes a polymer.

[0130] The polymer obtained in the third condensation reactor (k) is extracted in the form of a strand in which the die head (g) force is also melted through the extraction gear pump (m) and the extraction line (L5). After cooling with water, etc., it is cut into pellets by a rotary cutter (h).

[0131] Reference numerals (L2), (L4), and (L6) in FIGS. 2 and 3 are vent lines of the respective polycondensation reaction tanks (a), (d), and (k). [0132] “3Ί Rubber ί 本 (C5 ^):

The rubbery polymer used in the present invention has a glass transition temperature of 0 ° C or lower, particularly 20 ° C or lower, and is a polymer obtained by copolymerizing a rubbery polymer with a monomer component copolymerizable therewith. Including body. As the component C used in the present invention, any conventionally known component that can be generally combined with a polycarbonate resin composition or the like to improve its mechanical properties can be used.

[0133] Examples of component C include polybutadiene, polyisoprene, gen-based copolymers (styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, acrylic butadiene rubbers, etc.), ethylene and _α- olefin. Polymers (ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / otaten copolymer, etc.), ethylene / unsaturated carboxylic acid ester copolymer (ethylene / metatalylate copolymer, ethylene. Butyl phthalate copolymer), copolymer of ethylene and aliphatic vinyl compound, terpolymer of ethylene, propylene and non-conjugated gen, acrylic rubber (polybutyl acrylate, poly (2-ethylhexyl) Acrylate), butyl acrylate, 2-ethylhexyl acrylate copolymer), silico And rubbers (polyorganosiloxane rubber, polyorganosiloxane rubber and polyalkyl (meth) acrylate rubber and vertical composite rubber that also has power).

[0134] These may be used alone or in combination of two or more. Note that “(meth) acrylate” means “attalate” and “methacrylate”, and “(meth) acrylic acid” described later means “acrylic acid” and “methacrylic acid”.

[0135] As the C component used in the present invention, a copolymer obtained by polymerizing a monomer component to a rubber polymer may be used. Preferred examples of this monomer include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds. Examples of other monomer components include epoxy group-containing (meth) acrylic acid ester compounds such as glycidyl (meth) atalylate; maleimide compounds such as maleimide, Ν-methylmaleimide, Ν-malemaleimide; maleic acid, Examples thereof include α, β-unsaturated carboxylic acid compounds such as phthalic acid and itaconic acid, and anhydrides thereof (for example, maleic anhydride). These monomer components may be used alone or in combination of two or more.

[0136] The C component used in the present invention has a high impact resistance and a core-seal type graft copolymer tie. Are preferred. Among them, at least one selected from butadiene-containing rubber, butyl acrylate-containing rubber, and silicone rubber strength is used as a rubber polymer core layer, and acrylic acid ester, methacrylic acid ester, aromatic belief around it. A core Z shell type graft copolymer comprising a shell layer formed by copolymerizing at least one monomer component selected from a composite product is particularly preferred.

[0137] More specifically, methyl methacrylate-butadiene styrene polymer (MBS), methyl methacrylate-acrylonitrile-butadiene styrene polymer (MABS), methyl methacrylate-butadiene polymer (MB), methyl methacrylate-acrylic. Rubber polymer (MA), Methyl methacrylate-acrylic rubber Styrene polymer (MAS), Methyl methacrylate Acrylate / Butadiene rubber copolymer, Methyl methacrylate Acrylate / Butadiene rubber Styrene copolymer, Methyl methacrylate (Acrylic Examples include silicone IPN (interpenetrating polymer network) rubber. Such rubbery polymers may be used alone or in combination of two or more.

[0138] Specific examples of other rubbery polymers include polybutadiene rubber, styrene-butadiene copolymer (SBR), styrene butadiene styrene block copolymer (SBS), styrene ethylene Z butylene styrene block copolymer Polymer (SEBS), Styrene Ethylene Z Propylene / Styrene Block Copolymer (SEPS), Acrylonitrile / Butadiene / Styrene Polymer (ABS), Acrylonitrile-Styrene-Acrylic Rubber Polymer (ASA), Acrylonitrile-Tolyl / Ethylene Propylene Examples thereof include rubber-styrene polymer (AES).

[0139] In the aromatic polycarbonate resin composition of the present invention, the content ratio of the component A and the component B is preferably 51 to 99 parts by weight of the component A out of a total of 100 parts by weight of the component A and the component B. Is 55 to 90 parts by weight, more preferably 60 to 85 parts by weight, and component B is 1 to 49 parts by weight, preferably 10 to 45 parts by weight, more preferably 15 to 40 parts by weight.

[0140] When the A component is 51 parts by weight or more, impact resistance tends to be improved, and when it is less than 99 parts by weight, fluidity tends to improve chemical resistance.

[0141] The component C is preferably 0.5 to 40 parts by weight, more preferably 2 to 30 parts by weight, and particularly preferably 3 to 25 parts by weight with respect to 100 parts by weight of the total of the components A and B. When the C component is 0.5 parts by weight or more, impact resistance is improved, and when it is 40 parts by weight or less, rigidity, heat resistance, Fatigue properties tend to improve.

[0142] "41 inorganic filler (component D):

The inorganic filler which is the D component of the present invention (hereinafter sometimes abbreviated as “D component”) is a solid inorganic compound. The form (shape) of the solid is arbitrary. For example, it may be spherical, plate-like, needle-like, fiber-like, amorphous, etc. The finally obtained resin composition has dimensional stability and rigidity. In order to improve this, a plate shape, needle shape, or fiber shape is preferable.

[0143] The shape of the inorganic filler used in the present invention is distinguished from spherical, plate-like, needle-like and fiber-like as follows. A spherical shape includes a shape having an elliptical cross section or a substantially oval shape to a certain extent that is not limited to a true spherical shape, and preferably has an aspect ratio close to 1, with a specific aspect ratio exceeding 0.5. Indicates less than.

[0144] The plate shape indicates a plate shape and an aspect ratio (the length of the longest side of the plate-like surface of the plate-like powder, the thickness of the Z-plate body) in the range of 2 to: LOO. Needle-shaped refers to those with a length of 100 μm or less and an aspect ratio (particle length Z particle diameter) in the range of 2 to 20, and fibrous refers to those with a length exceeding 100 m . These shapes can be easily identified by an electron micrograph or the like.

[0145] Specific examples of the inorganic filler (D component) used in the present invention include, for example, magnesium silicate such as talc, kaolinite, clay, my strength, graphite, sericite, montmorillonite, and the like as a plate-like inorganic filler. Examples include plate-like calcium carbonate, plate-like alumina, and glass flakes.

[0146] Examples of acicular inorganic fillers include calcium silicates such as wollastonite, moss heidi, zonotrite, calcium titanate, aluminum borate, acicular calcium carbonate, acicular titanium oxide, and tetrapot type acid zinc oxide. Examples of the fibrous inorganic filler include glass fiber and carbon fiber.

[0147] When the inorganic filler (component D) used in the present invention is a plate-like or needle-like inorganic filler, the average particle diameter may be appropriately selected and determined, but is 0.1 to 25 µm. Is preferred. If the average particle size is too small, the reinforcing effect is insufficient, and if it is too large, the product appearance may be adversely affected and the impact resistance may be further insufficient. Therefore, the average particle size is preferably 0.3 to 15 / ζ πι, particularly 0.5 to LO / zm. Here, the average particle diameter means D measured by a liquid phase precipitation method by X-ray transmission. this

50

A device that can perform such measurements is the Sedigraph particle size analyzer (Micromeritics Instr

1111161 ^ 5 "Model 5100").

[0149] When the inorganic filler (component D) used in the present invention is a fibrous inorganic filler, the average fiber diameter may be appropriately selected and determined, but may be 1 to 20 / ζ πι. More preferably, it is 2 to 17 μm, particularly 3 to 15 μm. If the fiber diameter is less than 1 μm, the reinforcing effect is insufficient, and if it exceeds 15 m, the appearance of the product tends to be adversely affected. The fiber diameter of the fibrous filler can be easily measured with an electron micrograph.

[0150] Among the inorganic fillers used in the present invention, there are glass-based fillers selected from silicate compounds, Z, glass fibers, and glass flakes in terms of the balance of rigidity, fluidity, and impact resistance. A silicate compound is more preferable in terms of a preferable product appearance. A silicate compound is composed of at least a metal oxide component and an SiO component.

2

Any form such as a karate, disilicate, cyclic silicate, chain silicate, layered silicate, etc. may be used. In addition, the silicate composite used in the present invention is in a crystalline state, and any crystal form that the silicate composite can take may be a fiber, a plate What is necessary is just to select and determine suitably from various shapes, such as a shape. Furthermore, as the silicate compound used in the present invention, any of natural minerals and artificial synthetics can be used, and as the artificial synthetics, silicate compounds obtained with various conventionally known method powers are used. it can. The silicate compound can be used in a desired particle size and fiber length by pulverization and classification.

[0151] The silicate compound used as the component D in the present invention is a silicate compound represented by the following formula.

[0153] Here, χ and y represent natural numbers, z represents an integer of 0 or more, MO represents a metal oxide component, and MO may include a plurality of metal oxides.

[0154] The metal M in the metal oxide MO is potassium, sodium, lithium, barium, force russium, zinc, manganese, iron, connolto, magnesium, zirconium, aluminum, Examples include titanium. As the metal oxide MO, those substantially containing either CaO or MgO are preferable.

[0155] Specific examples of the silicate compound used as the D component in the present invention include wollastonite, talc, my strength, zonotolite, sepiolite, attabalgite, kaolinite, montmorillonite, bentonite, smectite and the like. I can do it. Of these, wollastonite, talc, and my strength are preferred in terms of rigidity, impact resistance, and appearance.

[0156] Wollastonite:

In the present invention, wollastonite used as the D component is a natural white mineral having needle-like crystals, and the chemical formula is represented by CaO′SiO. Usually, SiO is about 50% by weight, CaO is about 46

twenty two

It contains wt%, Fe O, Al 2 O, etc., and the specific gravity is 2.9. Also average

2 3 2 3

A pect ratio of 3 or more is preferred. Examples of such wollastonite include PH330 and PH450 manufactured by Kawatetsu Mining Co., Ltd., Nigros 4 and Niidaros 5 manufactured by Nyco Minerals, and SH1250 and SH1800 manufactured by Kinsey Matech.

[0157] Tanorek:

! Talc used as component D Te Contactヽthe present invention is a hydrous Kei acid magnesium © beam having a layered structure, chemical formula 4SiO - indicated by 3MgO-HO, the normal SiO 58 to 66 weight ^_0/0

2 2 2

, MgO 28-35% by weight, H 2 O about 5% by weight, Fe O force as other minor components ^

2 2 3

. 03~: L 2 Weight ^_0/0, Al O forces 0. 05~: L 5 weight ^_0/0, CaO force 0. 05~: L 2 Weight ^_0/0, K

2 3 2

O is 0.2% by weight or less, Na O is 0.2% by weight or less, and the specific gravity is about 2.7.

2

is there. The average particle diameter of talc is preferably 0.3 to 15 m, and more preferably 0.5 to LO / z m.

[0158] My strength:

In the present invention, the my strength used as the D component is a pulverized silicate salt containing aluminum, potassium, magnesium, sodium, iron and the like. Specifically, for example, muscovite (mascobite, chemical formula: K (AlSi O) (OH) Al (OH) (AlSi O) K), phlogopite

3 10 2 4 2 3 10

(Phlogopite, chemical formula: K (AlSi O) (OH) Mg (OH) (AlSi O) K), biotite (bar

3 10 2 6 2 3 10

Geotite, chemical formula: K (AlSi O) (OH) (Mg, Fe) (OH) (AlSi O) K), artificial clouds

3 10 2 6 2 3 10

Mother (fluorine phlogopite, chemical formula: K (AlSi O) (OH) F Mg F (AlSi O) K)

3 10 2 2 6 2 3 10 It is done. In the present invention, any conventionally known My force can be used, but among these, muscovite is preferably used. In addition, as a pulverization method for My power, either the dry pulverization method or the wet pulverization method is used, but the wet pulverization method is more effective for pulverizing the My power more thinly and finely. And, as a result, the reinforcing effect of the resin composition is higher, which is preferable.

[0159] The component D is 1 to 50 parts by weight, particularly 3 to 45 parts by weight, and particularly 5 to 40 parts by weight, with respect to the total 50 to 99 parts by weight of the components A and B. Preferred (the total of components A to D is 100 parts by weight). B component strength ^ If less than parts by weight, the rigidity is insufficient. On the other hand, if it exceeds 50 parts by weight, impact resistance and stagnant heat stability deteriorate.

[0160] "51 Phosphorus compounds:

The polycarbonate resin composition of the present invention preferably contains a phosphorus compound in order to improve heat resistance and residence heat stability within a range not impairing the effects of the present invention. As the phosphorus compound, any conventionally known compound can be used. Specifically, phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, phosphorous oxo acid such as phosphoric acid, acidic pyrophosphoric acid metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, acidic calcium pyrophosphate, phosphoric acid Examples include Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate, organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds.

Of these, organic phosphite compounds represented by the following general formula (I) and Z or organic phosphite compounds represented by the following general formula (下記) are preferred.

[0162] 0 = P (OH) (OR)… (I)

m 3— m

[0163] In general formula (I), R is an alkyl group or an aryl group, which may be the same or different. m is an integer of 0-2.

[0164] [Chemical 1]

In the formula, R ′ is an alkyl group or an aryl group, which may be the same or different. [0166] In the general formula (I), R is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, more preferably 2 to 25 carbon atoms. It is an alkyl group. M is preferably 1 and Z or 2.

[0167] In the general formula (Π), R 'is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Preferable specific examples of the phosphite ester represented by the above general formula (ジ) include distearyl pentaerythritol diphosphite, bis (2,4-di-tertbutylphenol) pentaerythritol diphosphite, bis Mention may be made of (2, 6 di-tert-butyl-4-methylphenol) pentaerythritol diphosphite.

[0168] The content of these phosphorus compounds is preferably from 0.001 to 1 wt.%, Preferably from 0.005 to 0.5 wt. ^ Particularly preferred is 0.01 to 0.3 parts by weight.

[0169] The polycarbonate resin composition of the present invention contains various resin additives other than the above-mentioned components A and B within the range that does not impair the object of the present invention, if necessary. Good

[0170] Examples of other resins include polyester resins other than polybutylene terephthalate resins such as polyethylene terephthalate resin and polytrimethylene terephthalate resin, Atari mouth nitrile styrene copolymer, acrylonitrile butadiene styrene. Copolymer, Polystyrene resin, Polystyrene resin such as Polystyrene resin, Polyolefin resin, Polypropylene resin such as Polypropylene resin, Polyamide resin, Polyimide resin, Polyetherimide resin, Polyurethane resin, Polyolefin resin Examples include lenether resin, polyphenylene sulfide resin, polysulfone resin, polymetatalylate resin, phenol resin, and epoxy resin.

[0171] In addition, various types of resin additives include antioxidants, mold release agents, dyes and pigments, heat stabilizers, reinforcing agents, flame retardants, impact resistance improvers, weather resistance improvers, antistatic agents, antistatic agents. Examples include clouding agents, lubricants, anti-blocking agents, fluidity improvers, plasticizers, dispersants, and antibacterial agents. These can be used alone or in combination of two or more.

[0172] In addition to the components A and B, the resin composition of the present invention can employ any of conventionally known methods, such as resin additives, as appropriate. [0173] Specifically, for example, the components A and B and additive components blended as necessary are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then mixed with a Banbury mixer, roll, A resin composition can be produced by melt-kneading with a lavender, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader or the like. In addition, the resin composition can be produced without mixing each component in advance, or by mixing only some components in advance and supplying them to an extruder using a feeder and melt-kneading them.

[0174] The power of the resin composition of the present invention The method for producing a molded product is not particularly limited. The molding method generally used for thermoplastic resin is a general injection molding method, an ultra-high speed injection molding method. Method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulation mold, molding method using rapid heating mold, foam molding (including supercritical fluid), Insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, etc. can be employed. A molding method using a hot runner method can also be selected.

[0175] Further, in the present invention, from the viewpoint of reducing environmental burden such as waste reduction and cost reduction, when manufacturing a molded product from a resin composition, non-conforming product, sprue, runner, used Recycling materials such as these products can be mixed with virgin materials for recycling, and V materials can be recycled. In this case, it is preferable to use the recycled raw material because it can be used after being pulverized, since it can reduce problems in producing a molded product.

[0176] The content ratio of the recycled material is preferably 70% by weight or less, more preferably 50% by weight or less, and even more preferably 30% by weight or less, out of the total 100% by weight of the recycled material and the virgin material. .

Example

[0177] The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the following examples and comparative examples, the blending amount means parts by weight.

[0178] In obtaining each of the resin compositions of Examples and Comparative Examples, the following raw materials were prepared.

[0179] <A component>

PC—1: Bisphenol A-type aromatic polycarbonate produced by interfacial polymerization (Mitsubishi ("Iupilon S-3000FN" manufactured by Engineering Plastics, Mv22500, terminal hydroxyl group concentration 150 ppm)

[0180] PC-2: Bisphenol A-type aromatic polycarbonate produced by interfacial polymerization (“Iupilon E-2000FN” manufactured by Mitsubishi Engineering Plastics, Mv28000, terminal hydroxyl group concentration 150 ppm)

[0181] PC-3: Bisphenol A-type aromatic polycarbonate produced by interfacial polymerization (“Iupilon H-4000FN” manufactured by Mitsubishi Engineering Plastics, viscosity average molecular weight 15 500, terminal hydroxyl group concentration = 150 ppm)

[0182] <B component>

Production Example 1 (Production of PBT-1):

Through the esterification step shown in FIG. 1 and the polycondensation step shown in FIG. 3, polybutylene terephthalate resin was produced in the following manner. First, a 60 ° C slurry mixed at a ratio of 1.80 moles of 1,4 butanediol to 1.00 moles of terephthalic acid is passed through the raw material supply line (1) from the slurry preparation tank in advance. In a reaction vessel (A) for ester cake having a screw type stirrer charged with 1% polybutylene terephthalate oligomer,

40. It was continuously supplied so as to be OkgZh.

[0183] At the same time, the bottom component of the rectification column (C) at 185 ° C was supplied at 18.4 kgZh from the recirculation line (2), and 65 ° C tetrabutyl was used as the catalyst from the catalyst supply line (3). A 6.0 wt% 1,4 butanediol solution of titanate was fed at 127 g / h (40 ppm relative to the theoretical polymer yield). The water in this solution is 0.20 weight ⁰ /. Met.

[0184] The internal temperature of the reaction vessel (A) is 230 ° C, the pressure is 78 kPa, and the produced water, THF and excess 1,4 butanediol are distilled from the distillation line (5), In (C), a high-boiling component and a low-boiling component were separated. The high-boiling component at the bottom of the tower after the system is stabilized is 98% by weight or more of 1,4 butanediol, so that the liquid level in the rectification tower (C) is constant, through the extraction line (8). Part of it was extracted outside. On the other hand, low-boiling components were extracted from the top of the column in the form of gas, condensed by the condenser (G), and extracted from the extraction line (13) to the outside so that the liquid level in the tank (F) was constant.

[0185] A certain amount of the oligomer produced in the reaction tank (A) was removed using the pump (B) and the extraction line (4) The liquid level was controlled so that the average residence time of the liquid in the reaction tank (A) was 3. Ohr. Extraction line 4 forces The extracted oligomer was continuously supplied to the first polycondensation reaction tank (a). After the system was stabilized, the ester ratio of the oligomer collected at the outlet of the reaction vessel (A) was 97.4%.

[0186] The internal temperature of the first polycondensation reaction tank (a) was 240 ° C, the pressure was 2.7 kPa, and the liquid level was controlled so that the residence time was 120 minutes. An initial polycondensation reaction was performed while extracting water, THF, and 1,4 butanediol from a vent line (L2) connected to a decompressor (not shown). The extracted reaction liquid was continuously supplied to the second polycondensation reaction tank (d).

[0187] The internal temperature of the second polycondensation reaction tank (d) was 245 ° C, the pressure was 140 Pa, the liquid level was controlled so that the residence time was 60 minutes, and connected to a decompressor (not shown). The polycondensation reaction was further carried out while extracting water, THF, and 1,4 butanediol from the vent line (L4). The obtained polymer was continuously supplied to the third polycondensation reaction tank (k) via the extraction line (L3) by the extraction gear pump (e). The internal temperature of the third polycondensation reaction tank (k) was 239 ° C, the pressure was 600 Pa, the residence time was 80 minutes, and the polycondensation reaction was advanced. The obtained polymer was continuously extracted in a strand form from the die head (g) and cut with a rotary cutter (h). Table 1 summarizes the analytical values of the resulting polybutylene terephthalate. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 1 is referred to as PBT-1.

[0188] The analytical value in Production Example 1 was measured by the following method.

[0189] (1) Esterification rate:

The acid value and Keny rating power were calculated by the following formula. The acid value was determined by titration using a 0.1 N KOHZ methanol solution after dissolving the oligomer in dimethylformamide. The saponification value was obtained by subjecting the oligomer to brine decomposition with 0.5N KOHZ ethanol solution and titrating with 0.5N hydrochloric acid.

[0190] Esterification Rate = ((Saponification Value—Acid Value) Z Saponification Value) X 100

[0191] (2) Concentration of titanium atom and group 1 and group 2 metal atoms in polybutylene terephthalate resin: High-resolution ICP (Inductively Coupled) Plasma) —Measured using MS (MassSpectrometer; manufactured by ThermoQuest). [0192] (3) Intrinsic viscosity of polybutylene terephthalate resin (IV):

It calculated | required in the following way using the Ubbelohde type viscometer. That is, a mixed solvent of phenol Z tetrachloroethane (weight ratio 1Z1) was used, and at 30 ° C., the polymer solution having a concentration of 1. OgZdL and the falling seconds of the solvent alone were measured and obtained from the following formula.

[0193] IV = ((1 + 4K 7) ° · 5 -? 1) / (2Κ C)

H sp H

[0194] where r? = N / n 1, r? Is the polymer solution fall seconds, r? Is the solvent fall seconds sp 0 0 number, C is the polymer solution concentration (gZdL), and K is the Huggins constant It was 0.33.

H

[0195] (4) Terminal carboxyl group concentration of polybutylene terephthalate resin:

In 25 mL of benzyl alcohol, 0.5 g of polybutylene terephthalate resin was dissolved, and titrated using a 0.01 mol ZL benzyl alcohol solution of sodium hydroxide.

[0196] (5) Concentration of terminal methoxycarbol group of polybutylene terephthalate resin:

Deuterated form Z Hexafluoroisopropanol = 7Z3 (volume ratio) Mixed solvent lm L About lOOmg of polybutylene terephthalate resin is dissolved, heavy pyridine 36 L is added, and 1H-NMR at 50 ° C Was measured and determined. As an NMR apparatus, “α-400” or “AL-400” manufactured by JEOL Ltd. was used.

[0197] Production Example 2 (Production of PBT-2):

The esterification process in the reactor (A) was performed in the same manner as PBT-1, and the polycondensation process was performed using the process shown in FIG. The reaction conditions in the first polycondensation reaction tank (a) were the same as in PBT-1, the second polycondensation reaction tank (d) had an internal temperature of 241 ° C, a pressure of 150 Pa, and a residence time of 70 minutes. Obtained. 50 kg of this PBT pellet was subjected to solid-phase polymerization at 195 ° C under reduced pressure (0.133 kPa or less) in a double-coal blender (100 L capacity), and taken out over time while checking its viscosity Then, the polymerization was stopped by cooling at a predetermined intrinsic viscosity. The analytical values of the obtained PBT are summarized in Table 1. Hereinafter, the poly (ethylene terephthalate) resin obtained in Production Example 2 is referred to as PBT-2.

[0198] Production Example 3 (Production of PBT-3):

In PBT-1, the slurry is supplied to 41 kgZh, the bottom component of the rectifying column (C) is supplied from the recirculation line (2) at 17.2 kgZh, and the catalyst is supplied from the catalyst supply line (3). as feed 65 ° 6. 0 weight ^_0/0 1 tetrabutyl titanate C, 4-butanediol solution in 97gZh The esterification reaction was carried out in the same manner as PBT-1, except that the yield was 30 ppm with respect to the theoretical polymer yield.

[0199] Further, the pressure of the first polycondensation reaction tank (a) is 2. lkPa, the pressure of the second polycondensation reaction tank (d) is 130 Pa, the residence time is 90 minutes, the third polycondensation reaction tank (k) The procedure was the same as PBT-1, except that the internal temperature was 240 ° C, the pressure was 130 Pa, and the residence time was 60 minutes. The analytical values of the obtained PBT are summarized in Table 1. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 3 is referred to as PBT-3.

[0200] Production Example 4 (Production of PBT-4):

The polycondensation process was carried out in the process shown in Fig. 2, and was performed in the same manner as PBT-3 except that the third polycondensation reaction tank (k) was used. The analytical values of the obtained PBT are summarized in Table 1. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 4 is referred to as PBT-4.

[0201] Production Example 5 (Production of PBT-5):

The esterification process in the reactor (A) was performed in the same manner as PBT-1. After magnesium acetate tetrahydrate is dissolved in pure water, 1, 4 butanediol is added, and magnesium acetate tetrahydrate, pure water, and 1,4 butanediol are 5% by weight and 20% by weight, respectively. And 75% by weight in a preparation tank (not shown). The temperature at this time was 25 ° C. This solution was supplied to the 1,4 butanediol line (L8) through the supply line (L7), and a predetermined amount was supplied to the oligomer extraction line (4) as a low-concentration solution.

[0202] The internal temperature of the first polycondensation reactor (a) is 246 ° C, the pressure is 2.4 kPa, the residence time is 120 minutes, the internal temperature of the second polycondensation reactor (d) is 239 ° C, and the pressure is 150 Pa. The residence time was 130 minutes, the internal temperature of the third polycondensation reactor (k) was 238 ° C, the pressure was 130 Pa, and the residence time was 70 minutes. The analytical values of the obtained PBT are summarized in Table 1. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 5 is referred to as PBT-5.

[0203] Production Example 6 (Production of PBT-6):

The esterification process in the reactor (A) was performed in the same manner as PBT-1, and the polycondensation process was performed using the process shown in FIG. The addition method of magnesium acetate tetrahydrate and the reaction conditions in the first polycondensation reaction tank (a) are the same as in PBT-5, the internal temperature of the second polycondensation reaction tank (d) is 238 ° C, the pressure is 200 Pa, Pellets were obtained with a residence time of 140 minutes. The analysis value of the obtained PBT is This is shown in Table 1. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 6 is referred to as PBT 6.

[0204] Production Example 7 (PBT-7 production):

The esterification process in the reactor (A) was carried out in the same manner as PBT-1. Instead of magnesium acetate tetrahydrate of PBT-5, lithium acetate dihydrate, pure water, and 1,4 butanediol are 2.5%, 20%, and 77.5% by weight, respectively. In this way, the solution is prepared in a preparation tank (not shown), and this solution is supplied to the 1, 4 butanediol line (L8) through the supply line (L7). A predetermined amount was supplied to (4). The conditions for the first polycondensation reactor (a) were the same as for PBT-5, the internal temperature of the second polycondensation reactor (d) was 241 ° C, and the internal temperature of the third polycondensation reactor (k). The polycondensation reaction was performed in the same way as PBT-5, except that the temperature was 242 ° C. The analytical values of the obtained PBT are summarized in Table 1. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 7 is referred to as PBT-7.

[0205] Production Example 8 (Production of PBT-8):

The esterification process in the reactor (A) and the initial polycondensation process in the first polycondensation reaction tank (a) were carried out in the same manner as PBT-1, and the pressure in the second polycondensation reactor (d) was 200 Pa, The procedure was the same as PBT-1, except that the pressure in the third polycondensation reactor (k) was 650 Pa and the residence time was 70 minutes. The analytical values of the obtained PBT are summarized in Table 1. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 8 is referred to as PBT-8.

[0206] Production Example 9 (Production of PBT-9):

The internal temperature of the first polycondensation reactor (a) is 247 ° C, the pressure is 6. OkPa, the pressure of the second polycondensation reactor (d) is 250 Pa, and the internal temperature of the third polycondensation reactor (k) is The procedure was the same as PBT-1, except that the residence time was 245 ° C and 70 minutes. The analytical values of the obtained PBT are summarized in Table 1. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 9 is referred to as PBT-9.

[0207] Production Example 10 (Production of PBT-10):

In a 200-liter stainless steel reaction vessel equipped with a turbine-type stirring blade, dimethyl terephthalate (DMT) 272.9 mol, 1,4 butanediol 327.5 mol, tetrabutyl titanate 0.126 mol (as the amount of titanium per theoretical yield polymer) lOOppm) was charged and the atmosphere was sufficiently replaced with nitrogen. Subsequently, the system was heated up, and after 60 minutes, the temperature was 210 ° C and atmospheric pressure under nitrogen. The resulting methanol, 1,4 butanediol, and THF were subjected to ester exchange reaction for 2 hours while distilling out of the system (the reaction start time was the time when the predetermined temperature was reached).

[0208] After the oligomer obtained above was transferred to a stainless steel reactor with an internal volume of 200 L having a vent pipe and a double helical stirring blade, it was allowed to reach a temperature of 245 ° C and a pressure of lOOPa over 60 minutes. The polycondensation reaction was performed in the state. When the predetermined power was reached, the reaction was terminated, and the polymer was extracted in the form of strands and cut into pellets. The analytical values of the obtained PBT are summarized in Table 1. Hereinafter, the polybutylene terephthalate resin obtained in Production Example 10 is referred to as PBT-10.

[0209] [Table 1]

[0210] <C component: Rubber polymer>

[0211] C1: Polybutadiene (core) Z Core alkyl acrylate 'alkyl methacrylate copolymer (shell) Z shell type graft copolymer (Rohm and Haas Japan)

"EXL2603")

[0212] C-2: Polyalkyl acrylate (core) Z alkyl acrylate 'alkyl methacrylate copolymer (shell) core Z-shell type graft copolymer (Rohm and Haas Japan made by Japan " EXL2315 ")

[0213] <D component: inorganic filler> D—l: Wollastonite (Nyda Minerals “Nidaros 4”, average particle size 3.4 / zm) [0214] D—2: Talc (Hayashi Kasei “UPN HSTO. 5”, primary average particle Diameter 2 / zm, deaeration compression

TO

[0215] <Other ingredients>

[0216] Phosphorus compounds:

Equation 0 = P (OH) (OC H) (n

3, = 1 and 2)), “18 37

ADK STAB AX—71 ”

[0217] [Preparation of rosin composition]

A component, B component, C component, D component and other components were uniformly mixed in a tumbler mixer in the ratios shown in Tables 2 to 9, and then a twin screw extruder (manufactured by Nippon Steel Works, TEX30XCT, L

/ D = 42, Nonore number 12)! /, And feed the pellets of the resin composition by feeding to the extruder from barrel 1 at a cylinder temperature of 270 ^° C and a screw speed of 200 rpm and melt-kneading. Produced. In Examples 30 and 31, pellets of the resin composition were prepared by further feeding the B component from the barrel 7 to the extruder at a ratio shown in Table 9 and melt-kneading it.

[0218] [Preparation of specimen]

After the pellets obtained by the above method were dried at 110 ° C for 4 hours or longer, using a M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho, the cylinder temperature was 270 ° C, the mold temperature was 80 ° C, ASTM test specimens (normally molded products) were prepared under conditions of a molding cycle of 55 seconds.

[0219] In addition, the stagnant molding was performed in 2.5 cycles for 1 cycle, and the stagnated molded products after the fifth shot were evaluated. Further, 30 parts by weight of ASTM test pieces obtained by continuous molding in the above molding cycle of 55 seconds (recycled raw material) and 70 parts by weight of pellets of rosin composition (virgin raw material) were tumbled. Mix evenly with a mixer and dry at 110 ° C for 4 hours or more. Then, using a Μ150ΑΠ—SJ type injection molding machine manufactured by Meiki Seisakusho, the cylinder temperature is 270 ° C and the mold temperature is 80 ° C. ASTM specimens were prepared under a cycle of 55 seconds. This operation was repeated twice to produce a recycled molded product (ASTM test piece).

[0220] [Evaluation method] (1) Fluidity (Q value):

Using a high-load flow tester, the flow rate Q value (unit: mlZs) of the composition per unit time was measured under the conditions of 280 ° C and a load of 160 kgfZcm ² to evaluate the fluidity. The orifice used was lmm in diameter x 10mm in length. The higher the Q value, the better the fluidity.

[0221] (2) Rigidity (flexural modulus)

In accordance with ASTM D790, measurement was performed at 23 ° C using a 6.4 mm thick test piece.

[0222] (3) Impact resistance

[0223] a. Izod impact strength:

According to ASTM D256, Izod impact strength (unit: j / m) was measured at 23 ° C using a notched specimen having a thickness of 3.2 mm.

[0224] b. Tensile elongation at break

In accordance with ASTM D638, a tensile test (unit:%) was performed by performing a tensile test (speed: 20 mmZmin.) At 23 ° C. using a specimen having a thickness of 3.2 mm.

[0225] (4) Chemical resistance (breaking elongation retention):

ASTM test specimen (thickness: 3.2 mm) is loaded with a test product with a deformation rate of 1%, and the retention of elongation at break after 48 hours (compared to that without test chemical) Rate). As the test chemical, di (2-ethylhexyl) phthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used. The chemical resistance was evaluated as 0 when the elongation at break was 75% or more, and X when the elongation at break was less than 75%.

[0226] (5) Fatigue properties (bending fatigue failure):

In accordance with ASTM D671, a Type A test piece was used and the test was performed at 23 ° C and an actual stress of 19 MPa.

[0227] (6) Heat resistance (thermal deformation temperature: DTUL):

Based on ASTM D648, the heat distortion temperature (unit: C) was measured at 0.45 MPa.

[0228] (7) Stability thermal stability (thermal deformation temperature and hue):

[0229] a. Thermal deformation temperature: In accordance with ASTM D648, the thermal deformation temperature of the retained molded product was measured at 0.45 MPa and evaluated.

[0230] b. Hue:

As compared with the above-mentioned normal molded product, the retained molded product was evaluated as ◯ when there was no or almost no hue change, and X when the hue change was observed.

[0231] c Appearance:

As compared with the above-mentioned normal molded product, visually evaluated as ◯ that the retained molded product had almost no hue change and rough skin due to silver streak, and X had a hue change or silver streak rough skin.

[0232] (8) Recycling characteristics (thermal deformation temperature and hue):

[0233] a. Thermal deformation temperature:

In accordance with ASTM D648, the thermal deformation temperature of the recycled molded product was measured at 0.45 MPa and evaluated.

[0234] b. Hue:

As compared with the above-mentioned normal molded product, the recycle molded product with almost no hue change was evaluated as ◯, and the one with hue change was evaluated as X.

[Examples 1 to 7 and Comparative Examples 1 to 3 (Examples regarding the aromatic polycarbonate resin composition described in the first aspect)]

Each of the resin compositions described in Tables 2 and 3 was produced and evaluated by the method described above. The results are shown in Tables 2 and 3.

[0236] [Table 2]

Example

Item Unit

1 2 3 4 5 6 7

PC-1 70 70 70-70-30

A component

PC-2 ― ― ― 70 ― 70 40

PBT-1 30 1----1

PBT-2-30--One--

PBT-3 Triple--30 15--Pair

PBT-4 heavy

Adult P B T One ― ― 15 ― ― ― Part

PBT-5----30 15

PBT-6-----15

PBT-7 1----30 Other Phosphorus

0.03 0.03 0.03 0.03 0.03 0.03 0.03 Component Compound

X 10 - ²

Fluidity Q value 20 19 15 10 15 10 13 ml / s

Izod

Impact resistance J / m 81 86 95 135 98 145 120 Impact strength

Elongation at break

Chemical resistance-o o o ○ o o o Rating Retention

Price

Bending fatigue

Fatigue properties Time 590000 640000 680000 720000 740000 770000 700000 Fracture

Fruit

Heat resistance Thermal deformation temperature ° C 121 117 125 123 124 122 122 Residence Thermal deformation temperature ° C 112 108 116 114 115 114 113 Thermal stability Hue Visual observation ○ o O ○ OOO Recycling Thermal deformation temperature V, 116 112 119 118 119 118 116 Characteristics Hue visual observation OOO 〇 OOO 3]

Comparative example

11th unit

one two Three

PC- 1 70 70 70

A component

PC-2---

PBT-8-

Heavy 30

Pair

PBT PBT-9 ― 30-part

PBT-10--30

Other Phosphorus

0.03 0.03 0.03

Component Compound

X 10 - ²

Fluidity Q value 21 19 20

ml / s

Izod

Impact resistance J / m 85 50 58

Impact strength

Elongation at break

Chemical resistance-X ○ ○

Retention rate

Price

Bending fatigue

Fatigue property times 640000 270000 330000

Destruction

Fruit

Heat resistance Thermal deformation temperature 106 125 123

Residence heat distortion temperature c 95 116 113

Thermal stability Hue Visual X 〇 X Recycle Heat distortion temperature ° c 99 118 1 17

Characteristics Hue Visual X 〇 X

[0238] From the results shown in Table 2, the following can be understood. The aromatic polycarbonate resin composition described in Example 17 of the present invention has an excellent balance of fluidity, impact resistance, chemical resistance, heat resistance, residence heat stability, and recycling characteristics. On the contrary, the composition in Comparative Example 1 has a titanium atom content of B component outside the scope of this patent, and compared with the compositions of Examples, fatigue properties, heat resistance, residence heat stability, recycling Inferior in characteristics.

[0239] Further, the composition of Comparative Example 2 has a terminal component carboxy concentration outside the range prescribed in this patent, and is inferior in impact resistance and fatigue properties as compared to the compositions of Examples. In the composition of Comparative Example 3, the titanium atom content of the B component and the terminal carboxy concentration are within the scope of this patent specification. It is outside the range, and is inferior in impact resistance, fatigue characteristics, residence heat stability, and recycling characteristics as compared with the compositions of the examples.

[Examples 8 to 18 and Comparative Examples 4 to 6 (Examples relating to the aromatic polycarbonate resin composition described in the second aspect)]

Each grease composition described in Tables 4 and 5 was produced and evaluated by the method described above. The results are shown in Tables 4 and 5.

[0241] [Table 4]

Example

Item Unit

8 9 10 11 12 13 14

PC-1 65 65 50 65 50 65 65

A

PC-2 ― ― 15-15 1-Minute

PC-3-------

PBT 1 35------

PBT-2-35 ― ―-One-

PBT-3-One 35 20---

PBT-4---15-

PBT-5 ― ― ―-35 20-Heavy

Pair P B T

PBT-6---One ― 15-

Part

PBT 7-One----35

PBT-8-------

PBT-9------One

PBT 10 ― ―----

C-l 4 4 4 4 4 4 4

C component

C-2 ―----―-Other Phosphorus

0.03 0.03 0.03 0.03 0.03 0.03 0.03 Component Compound

X 10 - ²

Fluidity Q value 14 14 12 13 12 13 11 ml / s

Rigid Flexural modulus MPa 2420 2410 2430 2430 2440 2440 2430 Review Izod

Impact resistance J / m 680 700 740 730 760 750 750 value Impact strength

Heat resistance Thermal deformation temperature ° C 117 111 120 119 119 118 118

Elongation at break

Chemical resistance ― O ○ ○ O ○ O ○ Retention rate

Bending fatigue

Fatigue properties Time 480000 520000 550000 560000 550000 550000 560000 Fracture 5] Example Comparative example Item Unit

15 16 17 18 4 5 6

PC-1 65 ―--65 65 6D

A

PC-2-70 30 30--Minute

PC-3--40 30---

PBT-1---― One

PBT-2-One---―

PBT-3-30----

PBT-4 4

. \ ― ― ―----

PBT 5 20-30 40--Heavy

Pair P B T

PBT-6 10-----

Part

PBT-7-One---―

PBT-8--―-35-

PBT 9---35-

PBT-10-----35

C-l 5 10 10 4 4 4

C component

C-2--10 ― ― Others Phosphorus

0.03 0.03 0.03 0.03 0.03 0.03 0.03 Component Compound

Fluidity Q value 11 17 26 30 14 13 14 Rigid Flexural modulus MPa 2360 2050 2070 2130 2430 2410 2440 Review Izod

Impact resistance J / m 780 720 690 680 690 200 260

Heat resistance Heat distortion temperature C 119 115 114 111 98 119 119 Fruit

Elongation at break

Chemical resistance ― ○ ○ ○ ○ X ○ ○ Retention rate

Bending fatigue

Fatigue properties Time 550000 450000 430000 380000 500000 220000 240000 Fracture

[0243] From the results shown in Tables 4 and 5, the following can be seen. The aromatic polycarbonate resin composition described in Examples 8 to 18 of the present invention has an excellent balance of fluidity, rigidity, impact resistance, heat resistance, chemical resistance, and fatigue characteristics. Conversely, the composition in Comparative Example 4 has a titanium atom content of component B that is outside the range specified in this patent, and is inferior in heat resistance and chemical resistance as compared to the compositions in Examples.

[0244] In the composition of Comparative Example 5, the terminal carboxy concentration of component B is outside the range specified in this patent. Yes, it is inferior in impact resistance and fatigue properties as compared with the compositions of the examples. The composition of Comparative Example 6 is inferior in impact resistance and fatigue properties as compared with the compositions of Examples, in which the content of titanium atom of the B component and the terminal carboxy concentration are outside the ranges specified in this patent.

[Examples 19 to 31, Comparative Examples 7 to 12 (Examples of the aromatic polycarbonate resin composition described in the third aspect of the present invention)]

Each greave composition described in Tables 6-8 was produced and evaluated by the method described above. The results are shown in Tables 6-8.

[0246] [Table 6]

Example Comparative example Item Unit

1 9 2 0 7 8 9

PC- 1 63 63 63 63 63

Component A PC-2---

PC-3--One-

PBT-1 27

PBT-2-27--

PBT-3

PBT-4---

PBT 5----

P B T

PBT-6 a ―-One-Pair

PBT-7 1--

Part

PBT- 8 27-

PBT 9 1-27

PBT-10-27

C-l-

C component

C 2 ― ―

D 1 10 10 10 10 10

D component

D-2 1--Phosphorus compounds 0.1 0.1 0.1 0.1 0.1 Other components

PET - - - flowability Q value ^{X 10- 2 ml / s 18 19} 19 18 18 flexural rigidity modulus MPa 3570 3540 3530 3550 3570

Izod impact strength J / m 55 51 50 38 42

Tensile strength at break% 120 110 103 51 60 Heat resistance Heat distortion temperature C 127 122 104 128 128

Fatigue properties Bending fatigue properties Times 840000 860000 810000 390000 430000 Appearance Visual ○ ○ X ○ X Stability of heat retention

Thermal deformation temperature ° c 113 108 92 116 115 7] Example

Item Unit

2 1 2 2 2 3 2 4

PC- 1--14 59

Component A PC-2 59 59 45-

PC- 3-1--

PBT-1 31---

PBT-2-31-One

PBT-3--31 18

PBT-4 ―-13

PBT-5-One--

P B T

PBT-6 Single--Single

Pair

PBT-7---

Part

PBT-8----

PBT-9 ―--One

PBT-10 ― ― One-

C-l 5 5 5 5

C component

C-2---―

D-l 10 10 10 10

D component

D-2 ―--― Phosphorus compounds 0.1 0.1 0.1 0.1 Other components

PET ― One ―-Fluidity Q value X 10_ ² ml / s 12 12 11 10 Rigid Flexural modulus MPa 3420 3490 3430 3410

Izod impact strength J / m 150 140 160 169

Tensile strength at break% 118 101 122 120 Heat resistance Heat distortion temperature ° C 126 120 128 127

Fatigue property Bending fatigue property Time 780000 780000 820000 840000 Appearance Visual ○ ○ ○ O Stability of heat retention

Thermal deformation temperature ° C 113 107 115 115 8] Example

Item Unit

2 5 2 6 2 7 2 8

PC- 1 14--

Component A PC-2 45 59 59 66

PC-3 one one one-

PBT-1--― ―

PBT-2 ― ―

PBT-3-― ―

PBT 4----

PBT- 5 31 18 15

P B T

PBT-6 _£ ― 13 ― 8 pairs

PBT-7 ― ― 31

Part

PBT-8--

PBT-9--One ―

PBT-10----c-i 5 5 5 6

C component

C-2 One--

D-l 10 10 10 1 1

D component

D-2 1 ―-Phosphorus compounds 0.1 0.1 0.1 0.1 Other components

PET ― 6 Fluidity Q value X 10 ~ ² ml / s 11 10 9.2 8.5 Rigidity Flexural modulus MPa 3440 3400 3420 3440

Izod impact strength J / m 163 172 175 177

Tensile strength at break% 121 120 119 119 Resulting heat resistance Heat distortion temperature ° C 127 126 128 132

Fatigue properties Bending fatigue properties Times 840000 860000 850000 870000 Appearance Visual ○ ○ ○ ○ Stability of stagnant heat

Thermal deformation temperature ° C 114 114 115 122 9] Example Comparative example Item Unit

2 9 3 0 3 1 1 0 1 1 1 2

PC 1--31--―

Component A PC-2 52 65 One 59 59 59

PC- 3--32 1--

PBT-1---One--

PBT-2--One--One

PBT-3-24---

PBT-4-One ―--―

PBT-5 28 ― 25-―-

P B T

PBT-6---―--Pair

PBT-7-One 31--Growth

Part

PBT-8---31--

PBT-9--One ― 31 One

PBT-10---― One 31

C 1 10 5-5 5 o

C component

C-2-― 10---

D-l 20 ―-10 10 10

D component

D-2-11 8 ―--Other Phosphorus compounds 0.1 0.1 0.1 0.1 0.1 0.1 Component PET-5----

X 10- ²

Fluidity Q value 6.7 10.3 35 12 12 12 ml / s

Rigid Flexural modulus MPa 4630 3490 2700 3430 3400 3440 Rating Izod Impact strength J / m 101 175 110 135 90 98 Value Impact resistance

Tensile strength at break% 35 135 100 102 52 58

Result Heat resistance Thermal deformation temperature ° C 128 131 121 104 127 126 Fatigue property Bending fatigue property Time 920000 850000 610000 750000 400000 460000 Retention heat appearance Appearance ○ ○ OXOX Qualitative heat deformation temperature C 114 120 109 92 115 115 Shown in Table 6 8 From the results, the following can be understood. The aromatic polycarbonate resin composition described in Example 1931 of the present invention has an excellent balance of fluidity, rigidity, impact resistance, heat resistance, fatigue characteristics, and residence heat stability. [0251] Conversely, in the compositions of Comparative Examples 7 and 10, the titanium atom content of the B component is outside the range specified in this patent, and compared with the compositions of the examples, heat resistance and residence heat stability Inferior to

[0252] In addition, the compositions of Comparative Examples 8 and 11 have a terminal component carboxy concentration outside the range specified in this patent, and are inferior in impact resistance and fatigue properties as compared to the compositions of Examples. In the compositions of Comparative Examples 9 and 12, the titanium atom content of the B component and the terminal carboxy concentration are outside the scope of this patent, and compared with the compositions of the Examples, the impact resistance, fatigue characteristics, residence heat Inferior in stability.

Claims

The scope of the claims

[1] Aromatic polycarbonate resin composition comprising aromatic polycarbonate resin (component A) and polybutylene terephthalate resin (component B), and comprising aromatic polycarbonate resin (component A) and polybutylene terephthalate resin Of the total 100 parts by weight of fat (component B), 51 to 99 parts by weight of aromatic polycarbonate resin (component A) and 1 to 49 parts by weight of polybutylene terephthalate resin (B component) Aromatic polycarbonate resin composition characterized in that in terephthalate resin (component B), the titanium compound content is more than 1 ppm as titanium atom and 75 ppm or less and the terminal carboxyl group is 39 μeqZg or less. Adult.

[2] Further, 0.5 to 40 parts by weight of a rubbery polymer (component C) is added to 100 parts by weight of the total amount of aromatic polycarbonate resin (wax component) and polybutylene terephthalate resin (sulphur component). The aromatic polycarbonate resin composition according to claim 1.

[3] The aromatic polycarbonate resin composition according to claim 2, which is a rubber-based polymer (component C) force core-shell type graft copolymer.

[4] The content of the rubber-like polymer (component C) is 2 to 30 parts by weight with respect to 100 parts by weight as a total of the polycarbonate rosin (component)) and the polybutylene terephthalate resin (component Β). 2. The aromatic polycarbonate resin composition according to 2 or 3.

[5] Furthermore, the inorganic filler (component D) is contained in an amount of 1 to 50 parts by weight with respect to a total of 50 to 99 parts by weight of the aromatic polycarbonate resin (a component) and polybutylene terephthalate resin (a component). The aromatic polycarbonate resin composition according to any one of claims 1 to 4.

[6] The aromatic polycarbonate resin composition according to claim 5, wherein the inorganic filler (component D) is a silicate compound and a glass or glass-based filler.

7. The aromatic polycarbonate resin composition according to claim 6, wherein the inorganic filler (component D) is at least one selected from the group consisting of wollastonite, talc, my strength, and kaolinite.

[8] The polybutylene terephthalate resin (component B) further contains a Group 1 metal compound and a Z or Group 2 metal compound, and the content of the Group 1 metal compound and the Z or Group 2 metal compound is converted to its metal atom In any one of claims 1 to 7, wherein the concentration is more than lppm and not more than 50ppm. Aromatic polycarbonate resin composition.

The aromatic polycarbonate resin composition according to any one of claims 1 to 8, wherein the terminal methoxycarbonyl group concentration of polybutylene terephthalate resin (component B) is 0.5 µeqZg or less.

10. The aromatic polycarbonate power resin composition according to claim 1, wherein the content power of the titanium compound of the polybutylene terephthalate resin (component B) is more than 20 ppm and not more than 50 ppm as a titanium atom.

The aromatic polycarbonate resin composition according to any one of claims 1 to 10, wherein the terminal carboxyl group of polybutylene terephthalate resin (component B) is 10 to 30 µeq / g.

12. The aromatic polycarbonate resin composition according to any one of claims 8 to 11, wherein the polybutylene terephthalate resin (component B) contains a magnesium compound as a group 2 metal compound. The aromatic polycarbonate bottle according to any one of claims 1 to 12, which contains 10 to 45 parts by weight of polybutylene terephthalate resin (component B) with respect to 55 to 90 parts by weight of polycarbonate resin (A component). Fat composition.

A resin molded product obtained by molding the aromatic polycarbonate resin composition according to any one of claims 1 to 13.

15. The resin molded product according to claim 14, wherein a part of the molding material is a recycled material.