WO2003004561A2 - Polyester / polycarbonate blend composition - Google Patents

Abstract

This invention relates to polyester / polycarbonate polymer blends with decreased polycarbonate content, an often eliminates the polycarbonate component of the blend. This invention is specifically useful in optical media applications, but additionally pertains to other applications where polycarbonate-containing polymers had been used previously, and for which the following polymer blend which comprises: (1) polyesters and copolyesters as well as blends thereof: with (2) polycarbonates as well as blends thereof, which exhibit exceptional clarity, stability, tensile strength, elongation, impact resistance, toughness, ductility, and processability, specifically including optical disks, water containers and automobile components including fascia.

Description

ι Polyester / Polycarbonate Blend Composition

2 Technical Field

3 The invention relates to polyester / polycarbonate blends useful as either a

4 complete replacement or a partial replacement for polycarbonate applications, and which

5 are particularly suitable for use in optical articles, particularly compact discs, plastic water

6 containers of any size or shape, and polymer fascia as used in car manufacturing, where it

7 is desirable to reduce the polycarbonate content. β Background of the Invention

9 Polycarbonates and other polymer materials are utilized in optical data storage o media, such as compact disks. In optical data storage media, it is critical that 1 polycarbonate resins have good performance characteristics such as transparency, low 2 water affinity, good processability, good heat resistance and low birefringence. High 3 birefringence is particularly undesirable in high density optical data storage media. 4 Improvements in optical data storage media, including increased data storage s density, are highly desirable, and achievement of such improvements is expected to 6 improve well established and new computer technology such as read only, write once, 7 rewritable, digital versatile and magneto-optical (MO) disks. s In the case of CD-ROM technology, the information to be read is imprinted directly 9 into a moldable, transparent plastic material, such as bisphenol A ("BPA") polycarbonate. 0 The information is stored in the form of shallow pits embossed in a polymer surface. The 1 surface is coated with a reflective metallic film, and the digital information, represented by 2 the position and length of the pits, is read optically with a focused low power (5 mW) laser 3 beam. The user can only extract information (digital data) from the disk without changing 4 or adding any data. Thus, it is possible to "read" but not to "write" or "erase" information. 5 The operating principle in a WORM drive is to use a focused laser beam (20-40 6 mW) to make a permanent mark on a thin film on a disk. The information is then read out 7 as a change in the optical properties of the disk, e.g., reflectivity or absorbance. These 8 changes can take various forms: "hole burning" is the removal of material, typically a thin 9 film of tellurium, by evaporation, melting or spalling (sometimes referred to as laser 0 ablation); bubble or pit formation involves deformation of the surface, usually of a polymer 1 overcoat of a metal reflector. 2 Although the CD-ROM and WORM formats have been successfully developed and 3 are well suited for particular applications, the computer industry is focusing on erasable 4 media for optical storage (EODs). There are two types of EODs: phase change (PC) and ι magneto-optic (MO). In MO storage, a bit of information is stored as an ~1 μ m diameter

2 magnetic domain, which has its magnetization either up or down. The information can be

3 read by monitoring the rotation of the plane polarization of light reflected from the surface

4 of the magnetic film. This rotation, called the Magneto-Optic Kerr Effect (MOKE) is typically

5 less than 0.5 degrees. The materials for MO storage are generally amorphous alloys of the

6 rare earth and transition metals.

7 Amorphous materials have a distinct advantage in MO storage as they do not suffer β from "grain noise", spurious variations in the plane of polarization of reflected light caused

9 by randomness in the orientation of grains in a polycrystalline film. Bits are written by ιo heating above the Curie point, T_c, and cooling in the presence of a magnetic field, a ιι process known as thermomagnetic writing. In the phase-change technology, information is

12 stored in regions that are different phases, typically amorphous and crystalline. These

13 films are usually alloys or compounds of tellurium which can be quenched into the

14 amoφhous state by melting and rapidly cooling. The film is initially crystallized by heating it is above the crystallization temperature. In most of these materials, the crystallization

16 temperature is close to the glass transition temperature. When the film is heated with a

17 short, high power focused laser pulse, the film can be melted and quenched to the is amorphous state. The amorphized spot can represent a digital "1 " or a bit of information.

19 The information is read by scanning it with the same laser, set at a lower power, and

20 monitoring the reflectivity.

21 In the case of WORM and EOD technology, the recording layer is separated from

22 the environment by a transparent, non-interfering shielding layer. Materials selected for

23 such "read through" optical data storage applications must have outstanding physical

24 properties, such as moldability, ductility, a level of robustness compatible with popular use,

25 resistance to deformation when exposed to high heat or high humidity, either alone or in

26 combination. The materials should also interfere minimally with the passage of laser light

27 through the medium when information is being retrieved from or added to the storage

28 device.

29 As data storage densities are increased in optical data storage media to

30 accommodate newer technologies, such as digital versatile disks (DVD) and higher

31 density data disks for short or long term data archives, the design requirements for the

32 transparent plastic component of the optical data storage devices have become

33 increasingly stringent. In many of these applications, previously employed polycarbonate ι materials, such as BPA (bisphenol A) polycarbonate materials, are inadequate. Materials

2 displaying lower birefringence at current, and in the future progressively shorter "reading

3 and writing" wavelengths have been the object of intense efforts in the field of optical data

4 storage devices. However it is a goal of the optical recording industry to move away from

5 polycarbonate-based materials, or to at least decrease the polycarbonate content in any

6 blend.

7 Additionally, polycarbonate has been used in the manufacture of water receptacles, β but suffers from a lack of durability. The compositions of this invention are equally

9 applicable for use in water containers of any size and shape where polycarbonate o containers had been used previously. 1 Summary of the Invention 2 In accordance with the present invention, there is provided polymer blend of 3 polymers which comprises: (1 ) polyesters and copolyesters as well as blends thereof; with 4 (2) polycarbonates as well as blends thereof, which exhibit exceptional clarity, stability, s tensile strength, elongation, impact resistance, toughness, ductility, and processability. 6 The formulation of the blends may contain other additives, such as ABS (acrylonitrile- 7 butadiene-styrene), nylons, stabilizers (e.g., phosphates, phosphites, phenols, amines, 8 halogens, phenols, amines, and UV absorbers), process and internal lubricants in all forms 9 (including glycols and fatty acids), colorants in all forms, as well as fillers, and 0 reinforcements (including carbons, talc, clays, oxides, metals, fibers, fabrics, micas, 1 conductives, and other organic and inorganic reinforcements and fillers). 2 It is an object of this invention to provide a composition which is less costly from a 3 raw materials standpoint and/or enhances physical properties, processing or productivity. 4 It is yet another object of this invention to provide a polyester and/or copolyester 5 blend which possesses similar and superior physical properties to polycarbonates used in 6 the prior art. 7 It is still yet another object of this invention to provide a polyester and/or copolyester 8 blend which surpasses the durability of polycarbonate when used as a water container. 9 It is an additional object of this invention to overcome the problems associated with 0 using only bisphenol A as the aromatic dihydroxy compound which has a large 1 photoelasticity constant and relatively poor melt flowability and, hence, gives moldings 2 having enhanced birefringence. In addition, this polycarbonate has an Abbe number as 3 small as 30, although its refractive index is as high as 1.58. Because of this, bisphenol A polycarboante does not always have performance sufficient for applications such as optical recording materials and optical lenses.

These and other objects of this invention will be evident when viewed in light of the detailed description and the pending claims. Detailed Description of the Invention

The invention builds in the recognition that blends of polycarbonates and polyesters, as well as specialized copolyesters can produce exceptionally good optical media capable of use in the optical recording industry. In one embodiment of this invention, the polycarbonate component is completely eliminated.

Polycarbonates have been used in the optical recording industry for many years. In general, polycarbonates will have at least the following repeat unit.

and wherein R is an alkylaryl or arylalkyl group (the nomenclature depending on whether the aryl properties or the alkyl properties of the chemical moiety predominates) of C_15-36 comprising at least one aryl ring.

One exemplary specific polycarbonate is a synthetic thermoplastic resin derived from bisphenol A and phosgene, a linear polyester of carbonic acid, e.g.,

Polycarbonates can be formed from any dihydroxy compound and any carbonate diester, or by ester interchange. Polymerization may be in aqueous emulsion or in non-aqueous solution. The polymers are transparent (90% light transmission), noncorrosive, weather and ozone-resistant, non-toxic, stain-resistant, low water absorption, high impact strength, heat-resistant, high dielectric strength, and dimensionally stable. It is their link to phosgene that has spurred the search for non-polycarbonate materials with similar properties, or at least to minimize the amount of polycarbonates used in any blend material. In an effort to improve performance characteristics of the polycarbonates, new compositions have been developed, which contain novel structures selected from the group consisting of: (a) carbonate structural units corresponding to structure (I)

(I) where

Ri, R2, R₃, and R are independently selected from the group consisting of

H, and C₁ - C₆ alkyls, R₅ is C1 - C₃ alkyl, n is an integral value from 0 to 2 inclusive; and (b) carbonate structural units corresponding to structure (II)

(II) where

Re, R7, R1₀ and Rn are independently selected from the group consisting of

H, and C-i - C_& alkyls, Re and R₉ are independently H or C₁ - C₅ alkyl, Rι₂ is H or C-i -C₃ alkyl; and n is an integral value from 0 to 2 inclusive; and (c) carbonate structural units selected from the group consisting of (1 ) carbonate structural units corresponding to structure (III)

(III) where

R-i₃, R-_I4 and Rιβ independently represent H, and C-i - Cβ alkyls, R-_I5 is H or Ci - C₃ alkyl and n is an integral value from 0 to 2 inclusive, R-_I7 is H or Ci - C₅ alkyl; and (2) carbonate structural units corresponding to structure (IV)

(IV) wherein

Ri₈ is independently selected from the group consisting of halogen, hydrogen, monovalent C-i - Cι₀ alkyls, monovalent d - C_& alkoxy radicals, aryl groups having from Cβ - C-io carbon atoms, aralkyl groups having from C₇ - C₁₀ carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof;

Rig is independently selected from the group consisting of halogen, hydrogen, monovalent C-i - Cι₀ alkyls, monovalent d - Cβ alkoxy radicals, aryl groups having from C₆ - C₁₀ carbon atoms, aralkyl groups having from C₇ - do carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof; W is selected from the group consisting of a covalent bond, substituted or unsubstituted divalent Ci -Cβ hydrocarbon radicals, alkylidene groups having from C2 - C10 carbon atoms, cycloalkylene group having C_δ - Cio carbon atoms, cycloalkylidene groups having from C₆ - C10 carbon atoms, alkylene-arylene-alkylene groups having Cβ - C15 carbon atoms, -S-, ~S(R₂₇)₂~, --S--S--, -0-, -N(R₂₈)-, -SO-, - S0₂~, -CO-; b is O or l ; wherein R₂7 and R₂β are substituents selected independently from the group consisting of H, halogen, phenyl, substituted phenyl, alkyl, substituted alkyl, alkoxy, and substituted alkoxy of from C-i to C_2u carbons; and each n is independently selected from integers having a value of from 0 to 4 inclusive; and (3) carbonate structural units corresponding to structures (III) and (IV) wherein the polycarbonate has a glass transition temperature of from about 120°C to about 185°C and a water absorption of less than about 0.33%. In a preferred blend embodiment, the polycarbonate will be an aromatic polycarbonate, which is a thermoplastic polycarbonate comprising a carbonic acid ester of an aromatic diol compound as the main recurring unit. This recurring unit is represented by the following formula (IV) and blends thereof

(IV) where ι Rιβ is independently selected from the group consisting of halogen, hydrogen,

2 monovalent Ci - C10 alkyls, monovalent d - Cβ alkoxy radicals, aryl groups

3 having from C₆ - C10 carbon atoms, aralkyl groups having from C₇ - Cι₀

4 carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and

5 combinations thereof;

6 R₁₉ is independently selected from the group consisting of halogen, hydrogen,

7 monovalent C-i - do alkyls, monovalent d - C₆ alkoxy radicals, aryl groups

8 having from C₆ - C₁₀ carbon atoms, aralkyl groups having from C₇ - Cι₀

9 carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and ιo combinations thereof; ιι W is selected from the group consisting of a covalent bond, substituted or

12 unsubstituted divalent Ci -Cβ hydrocarbon radicals, alkylidene groups having

13 from C₂ - do carbon atoms, cycloalkylene group having Cβ - C1₀ carbon

14 atoms, cycloalkylidene groups having from Cβ - C₁₀ carbon atoms, alkylene-

15 arylene-alkylene groups having C₈ - C1₅ carbon atoms, -S-, ~S(R₃₃)₂~, -

16 S-S-, -O-, -N(R₃₄)~, -SO-, -SO2-, -CO—,

17

18 R₃₃ and R^ are substituents selected independently from the group consisting of H,

19 halogen, phenyl, substituted phenyl, alkyl, substituted alkyl, alkoxy, and

20 substituted alkoxy of from Ci to C2₀ carbons; and

21 R₄₄ and R ₅ are selected from the group consisting of H, d - C₄ alkyls;

22 z is an integral value ranging from 4 to 9 inclusive;

23 b is 0 or 1 ; and wherein

24 each n is independently selected from integers having a value of from 0 to 4

25 inclusive. 1 The alkyl group having 1 to 10 carbon atoms may be linear or branched. Examples

2 of the alkyl group include methyl, ethyl, propyl, butyl, octyl, decyl and the like. Examples of

3 the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, cumyl, naphthyl and the

4 like. Examples of the aralkyl group having 7 to 10 carbon atoms include benzyl, 2-

5 phenethyl, 2-methyl, 2-phenylethyl and the like. Riβ and R19 are preferably independently

6 a hydrogen atom, methyl group or t-butyl group, particularly preferably a hydrogen atom.

7 The alkylene group having 1 to 10 carbon atoms may be linear or branched. Examples of β the alkylene group include methylene, 1 ,2-ethylene, 2,2-propylene, 2,2-butylene, 1 ,1 -

9 decylene and the like. Examples of the alkylidene group having 2 to 10 carbon atoms o include ethylidene, propylidene, butylidene, hexylidene and the like. Examples of the 1 cycloalkylene group having 6 to 10 carbon atoms include 1 ,4-cyclohexylene, 2-isopropyl- 2 1 ,4-cyclohexylene and the like. Examples of the cycloalkylidene group having 6 to 10 3 carbon atoms include cyclohexylidene, isopropylcyclohexylidene and the like. Examples 4 of the alkylene-arylene-alkylene group having 8 to 15 carbon atoms include m- 5 diisopropylphenylene group and the like. W is preferably a cyclohexylidene group or 2,2- 6 propylidene group, particularly preferably 2,2-propylidene group. 7 In one embodiment, the aromatic polycarbonate resin used in the present invention 8 is obtained by melt polymerization in which a dihydric phenol and a carbonate precursor 9 are subjected to ester interchange reaction. As typical examples of the dihydric phenol 0 used herein, there can be mentioned hydroquinone, resorcinol, 1 ,6-dihydroxynaphthalene, 1 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane, 1 ,1- 2 bis(4-hydroxyphenyl)-1 -phenylmethane, bis{(4-hydroxy-3,5-dimethyl)phenyl}methane, 1 ,1- 3 bis(4-hydroxyphenyl)ethane, 1 ,2-bis(4-hydroxyphenyl)ethane, 1 ,1-bis(4-hydroxyphenyl)-1 - 4 phenylethane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-1 - 5 naphthylmethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as: bisphenol A), 6 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, 2,2-bis{(4-hydroxy-3- 7 methyl)phenyl}propane, 2,2-bis{(4-hydroxy-3,5-dimethyl)phenyl}propane, 2,2-bis{(3,5- β dibromo-4-hydroxy)phenyl}propane, 2,2-bis{(3,5-dichloro-4-hydroxy)phenyl}propane, 2,2- 9 bis{(3-bromo-4-hydroxy)phenyl}propane, 2,2-bis{(3-chloro-4-hydroxy)phenyl}propane, 4- 0 bromoresorcinol, 2,2-bis{(3-isopropyl-4-hydroxy)phenyl}propane, 2,2-bis{(3-phenyl-4- 1 hydroxy)phenyl}propane, 2,2-bis{(3-ethyl-4-hydroxy)phenyl}propane, 2,2-bis{(3-n-propyl-4- 2 hydroxy)phenyl}propane, 2,2-bis{(3-sec-butyl-4-hydroxy)phenyl}propane, 2,2-bis{(3-tert- 3 butyl-4-hydroxy)phenyl}propane, 2,2-bis{(3-cyclohexyl-4-hydroxy)phenyl}propane, 2,2- bis{(3-methoxy-4-hydroxy)phenyl}propane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1 ,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene, 1,1-dichloro-2,2-bis{(3-phenoxy-4- hydroxy)phenyl}ethylene, ethylene glycol bis(4 -hydroxyphenyl) ether, 2,2-bis(4- hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4- hydroxyphenyl)-3,3-dimethylbutane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1 ,1-bis(4- hydroxyphenyl)isobutane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-4- methylpentane, 3,3-bis(4-hydroxyphenyl)pentane, 1 ,1-bis(4-hydroxyphenyl)cyclohexane, 1 ,1 -bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 1 ,1 -bis(4-hydroxyphenyl)-3,3,5- trimethylcyclohexane, 1 ,1-bis(4-hydroxyphenyl)cyclododecane, 9,9-bis(4- hydroxyphenyl)fluorene, 9,9-bis{(4-hydroxy-3-methyl)phenyl}fluorene, α,α'-bis(4- hydroxyphenyl)-o-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 1 ,3-bis(4-hydroxyphenyl)-5,7- dimethyladamanthane, 4,4'-dihydroxydiphenylsulfone, bis{(3,5-dimethyl-4- hydroxy)phenyl}sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxydiphenyl ester. These compounds can be used singly or in admixture of two or more kinds. Of these, preferably used is a homopolymer or copolymer obtained from at least one kind of bisphenol selected from the group consisting of bisphenol A, 2,2-bis{(4- hydroxy-3-methyl)phenyl}propane, 2,2-bis{(3,5-dibromo-4-hydroxy)phenyl}propane, ethylene glycol bis(4-hydroxyphenyl) ether, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxyphenyl)butane, 1 ,1-bis(4-hydroxyphenyl)cyclohexane, 1 ,1-bis(4- hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenylsulfone, bis{(3,5- dimethyl-4-hydroxy)phenyl}sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'- dihydroxydiphenyl sulfide and 4,4'-dihydroxydiphenyl ketone. Particularly preferable is a homopolymer of bisphenol A. As the carbonate precursor, there is used a carbonate ester or a haloformate. As specific examples, there are mentioned diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and dicyclohexyl carbonate; however, the carbonate precursor is not restricted thereto. Diphenyl carbonate, a dihaloformate of a dihydric phenol, or the like is preferably used, and diphenyl carbonate is more preferably used. These carbonate esters can be used singly or in combination of two or more kinds. ι In reacting a dihydric phenol with a carbonate precursor by melt polymerization to

2 produce a polycarbonate resin, it is possible to as necessary use a catalyst, a terminal-

3 blocking agent, an antioxidant for dihydric phenol, etc. The polycarbonate resin may be a

4 branched polycarbonate resin containing a polyfunctional aromatic compound having

5 three or more functional groups as a comonomer component, or a polyester carbonate

6 resin containing an aromatic or aliphatic difunctional carboxylic acid as a comonomer

7 component. Or, a mixture of two or more polycarbonate resins may be used as the β polycarbonate resin.

9 As the aromatic compound having three or more functional groups, there can be o mentioned fluoroglucine; fluoroglucide; trisphenols such as 4,6-dimethyl-2,4,6-tris(4- 1 hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1 ,3,5-tris(4- 2 hydroxyphenyl)benzene, 1 ,1 ,1-tris(4-hydroxyphenyl)ethane, 1 ,1 ,1-tris(3,5-dimethyl-4- 3 hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1 ,1-bis(4- 4 hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol and the like; tetra(4- 5 hydroxyphenyl)methane; bis(2,4-dihydroxyphenyl) ketone; 1 ,4-bis(4,4- 6 dihydroxytriphenylmethyl)benzene; trimellitic acid; pyromellitic acid; 7 benzophenonetetracarboxylic acid; chlorides of these acids; 2-(4-hydroxyphenyl)-2-(3'- 8 phenoxycarbonyl-4'-hydroxyphenyl)propane; 2-(4-hydroxyphenyl)-2-(3'-carboxy-4'- 9 hydroxyphenyl)propane; etc. Of these, preferred are 1 ,1 ,1-tris(4-hydroxyphenyl)ethane 0 and 1 ,1 ,1 -tris(3,5-dimethyl-4-hydroxyphenyl)ethane, and particularly preferred is 1 ,1 ,1 - 1 tris(4-hydroxyphenyl)ethane. 2 The reaction by melt polymerization is an ester interchange reaction between 3 dihydric phenol and carbonate ester, and is conducted by mixing, with heating, a dihydric 4 phenol and a carbonate ester in the presence of an inert gas and distilling the formed 5 alcohol or phenol. The reaction temperature is ordinarily in a range of 120 to 350°C, 6 although it differs depending upon, for example, the boiling point of formed alcohol or 7 phenol. In the latter stage of the reaction, the reaction system is made vacuum about 10 to 8 0.1 Torr (1 ,333 to 13.3 Pa) to make easy the distillation of the formed alcohol or phenol. 9 The reaction time is ordinarily about 1 to 4 hours. 0 In the melt polymerization, a polymerization catalyst may be used for accelerating 1 the polymerization speed. As the polymerization catalyst, there can be used, for example, 2 a catalyst consisting of (i) an alkali metal compound and/or (ii) a nitrogen-containing basic 3 compound; and condensation is conducted. As the alkali metal compound used as the catalyst, there can be mentioned, for example, hydroxides, hydrogencarbonates, carbonates, acetates, nitrates, nitrites, sulfites, cyanates, thiocyanates, stearates, boron hydrides, benzoates, hydrogenphosphates, bisphenol salts and phenol salts of alkali metals. As specific examples of the alkali metal compound, there can be mentioned sodium hydroxide; potassium hydroxide; lithium hydroxide; sodium hydrogencarbonate; potassium hydrogencarbonate; lithium hydrogencarbonate; sodium carbonate; potassium carbonate; lithium carbonate; sodium acetate; potassium acetate; lithium acetate; sodium nitrate; potassium nitrate; lithium nitrate; sodium nitrite; potassium nitrite; lithium nitrite; sodium sulfite; potassium sulfite; lithium sulfite; sodium cyanate; potassium cyanate; lithium cyanate; sodium thiocyanate; potassium thiocyanate; lithium thiocyanate; sodium stearate; potassium stearate; lithium stearate; sodium boronhydroxide; lithium boronhydroxide; potassium boronhydride; sodium phenylborate; sodium benzoate; potassium benzoate; lithium benzoate; disodium hydrogenphosphate; dipotassium hydrogenphosphate; dilithium hydrogenphosphate; disodium salt, dipotassium salt and dilithium salt of bisphenol A; and sodium salt, potassium salt and lithium salt of phenol. The alkali metal compound as the catalyst can be used in an amount of 10^"9 to 10^"4 moles, preferably 10^"8 to 10^"5 moles per mole of the dihydric phenol. An amount deviating from the above range is not preferred because it adversely affects the properties of the polycarbonate obtained or the ester interchange does not proceed sufficiently, making impossible the production of a polycarbonate of high molecular weight. As the nitrogen-containing basic compound as the catalyst, there can be mentioned, for example, ammonium hydroxides having an alkyl group, aryl group, alkylaryl group or the like, such as tetramethylammonium hydroxide (Me NOH), tetraethylammonium hydroxide (E NOH), tetrabutylammonium hydroxide (Bu NOH), benzyltrimethylammonium hydroxide (Φ-CH₂(Me)₃NOH), hexadecyltrimethylammonium hydroxide and the like; tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, hexadecyldimethylamine and the like; and basic salts such as tetramethylammonium borohydride (Me₄NBH₄), tetrabutylammonium borohydride (Bu NBH₄), tetrabutylammonium tetraphenylborate (Bu NBPh₄), tetramethylammonium tetraphenylborate (Me NBPh ) and the like. Of these, preferred are tetramethylammonium hydroxide (Me NOH), tetraethylammonium hydroxide (E NOH) and tetrabutylammonium hydroxide (Bu₄NOH), and particularly preferred is tetramethylammonium hydroxide (Me₄NOH). The above nitrogen-containing basic compound is used preferably in such an amount that the ammonium nitrogen atom in nitrogen-containing basic compound comes to be 1 x10^'5 to 1 x10^"3 equivalent per mole of the dihydric phenol. The amount is more preferably 2x10^"5 to 7x10^"4 equivalent on the same basis. The amount is particularly preferably 5x10^'5 to 5x10^"4 equivalent on the same basis. In the present invention, there can be used, as necessary, a catalyst generally used in esterification or ester interchange reaction, such as alkoxides of alkali metal or alkaline earth metal, organic acid salts of alkali metal or alkaline earth metal, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds, or the like. These catalysts may be used singly or in combination of two or more kinds. The use amount of such a polymerization catalyst is selected in a range of preferably 1x10^"9 to 1x10^"5 equivalent, more preferably 1 x10^"8 to 5x10^"6 equivalent per mole of the raw material dihydric phenol. In such polymerization, in order to reduce the phenolic terminal groups, it is preferred to add, in the latter stage of polycondensation reaction or after the completion of the reaction, a compound such as phenol, p-tert-butyl phenol, p-tert-butylphenylphenyl carbonate, p-tert-butylphenyl carbonate, p-cumylphenol, p-cumylphenylphenyl carbonate, p-cumylphenyl carbonate, bis(chlorophenyl) carbonate, bis(bromophenyl) carbonate, bis(nitrophenyl) carbonate, bis(phenylphenyl) carbonate, chlorophenylphenyl carbonate, bromophenylphenyl carbonate, nitrophenylphenyl carbonate, diphenyl carbonate, methoxycarbonylphenylphenyl carbonate, 2,2,4-trimethyl-4-(4-hydroxyphenyl)chroman, 2,4,4-trimethyl-2-(4-hydroxyphenyl)chroman, ethoxycarbonylphenylphenyl carbonate or the like. Of these, preferred are 2-chlorophenylphenyl carbonate, 2- methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate, and particularly preferred is 2-methoxycarbonylphenylphenyl carbonate. In the present invention, it is preferred to block the terminals of the aromatic polycarbonate with a terminal-blocking agent. It is also preferred to control the terminal hydroxyl group concentration of the aromatic polycarbonate resin before blocking the terminal with a terminal-blocking agent, to 20 mole % or more, preferably 30 mole % or more, further preferably 40 mole % or more, based on the total terminals. Thereby, a specified terminal group can be introduced at a high proportion and the aromatic polycarbonate resin can be improved at a high level. Generally, it is advantageous to apply a terminal-blocking agent to an aromatic polycarbonate resin whose terminal hydroxyl group concentration is 30 to 95 mole % of the total terminals. The proportion of terminal hydroxyl group in aromatic polycarbonate resin before blocking the terminal with terminal blocking agent can be controlled by the ratio of raw materials fed, i.e. dihydric phenol and diphenyl carbonate. Here, the terminal hydroxyl group concentration (moles) of a determined amount of aromatic polycarbonate resin can be determined by an ordinary method, i.e., ¹H-NMR. The terminal hydroxyl group concentration in the aromatic polycarbonate resin of the present invention is preferably 0 to 40 mole %, more preferably 0 to 18 mole %, further preferably 0 to 9 mole %, most preferably 0 to 7 mole % of the total terminals. Here, "0 mole %" indicates "not detectable" when the measurement was made by ¹ H-NMR. When the terminal hydroxyl group concentration is in the above range, further improvement in wet heat fatigue and impact resistance of flat can be obtained. In the present invention, it is preferred that the catalytic activity of the aromatic polycarbonate resin is neutralized by using a deactivator. As specific examples of the deactivator, there can be mentioned benzenesulfonic acid; p-toluenesulfonic acid; sulfonic acid esters such as methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p- toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p- toluenesulfonate, phenyl p-toluenesulfonate and the like; trifluoromethanesulfonic acid; naphthalenesulfonic acid; sulfonated polystyrene; methyl acrylate-sulfonated styrene copolymer; 2-phenyl-2-propyl dodecylbenzenesulfonate; 2-phenyl-2-butyl dodecylbenzenesulfonate; tetrabutylphosphonium octylsulfonate; tetrabutylphosphonium decylsulfonate; tetrabutylphosphonium benzenesulfonate; tetraethylphosphonium dodecylbenzenesulfonate; tetrabutylphosphonium dodecylbenzenesulfonate; tetrahexylphosphonium dodecylbenzenesulfonate; tetraoctylphosphonium dodecylbenzenesulfonate; decylammonium butylsulfate; decylammonium decylsulfate; dodecylammonium methylsulfate; dodecylammonium ethylsulfate; dodecylmethylammonium methylsulfate; dodecyldimethylammonium tetradecylsulfate; tetradecyldimethylammonium methylsulfate; tetramethylammonium hexylsulfate; ι decyltrimethylammonium hexadecylsulfate; tetrabutylammonium dodecylbenzylsulfate;

2 tetraethylammonium dodecylbenzylsulfate; and tetramethylammonium

3 dodecylbenzylsulfate. However, the deactivator is not restricted thereto. These

4 compounds may be used in combination of two or more kinds.

5 Of the deactivators, a phosphonium or ammonium salt-based deactivator is

6 particularly stable per se even at 200°O, or higher. The deactivator, when added to an

7 aromatic polycarbonate resin, quickly neutralizes the polymerization catalyst present in the β resin, whereby a stable aromatic polycarbonate resin can be obtained. The deactivator is

9 used in an amount of preferably 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, o particularly preferably 0.01 to 100 ppm relative to the polycarbonate formed after i polymerization. 2 Such a deactivator is used in an amount of preferably 0.5 to 50 moles per mole of 3 the polymerization catalyst. There is no particular restriction as to the method of adding the 4 deactivator to the aromatic polycarbonate resin after polymerization. For example, the s deactivator may be added while the reaction product, i.e. the aromatic polycarbonate 6 resin, is in a molten state; or, the deactivator may be added after the aromatic 7 polycarbonate resin is once pelletized and then remelted. In the former case, it is possible s that while the reaction product, i.e. the aromatic polycarbonate resin, in the reactor or 9 extruder is in a molten state, the deactivator is added thereto to form an aromatic 0 polycarbonate resin and then, the resin is passed through an extruder for pelletization; or, 1 the addition of the deactivator and subsequent kneading may be conducted while the 2 aromatic polycarbonate resin after polymerization is passed through an extruder for 3 pelletization, to obtain an aromatic polycarbonate resin. 4 In production of an aromatic polycarbonate resin by melt polymerization, when a 5 polymerization catalyst is used for acceleration of the polymerization, the polymerization 6 catalyst often remains in the aromatic polycarbonate resin after polymerization. If the 7 residual catalyst is allowed to stand as it is, the aromatic polycarbonate resin causes 8 trouble such as decomposition or post-reaction owing to the catalytic activity of the 9 residual catalyst. Further, in a composition between such an aromatic polycarbonate resin 0 having a residual catalytic activity and a filler, the adverse effect of the residual catalyst is 1 increased and, moreover, new problem such as reduction in impact resistance of flat and 2 the like may arise. Therefore, it is preferred to control the residual catalytic activity. "Residual catalytic activity index" is used as a yardstick for controlling the residual catalytic activity, and the index is measured as follows. As a tester, there is used a rotary rheometer which can measure the range of the melt viscosity of a sample resin to be tested; the sample resin is placed in a sufficient nitrogen current so as to prevent the sample resin from being oxidized by external oxygen and is rotated in a given direction at a given angular velocity under the condition of a given temperature at which the sample resin is melted, and the change of the melt viscosity of the sample resin during the rotation is measured. As a jig for rheometer, used in the measurement, the one having a cone- circular plate shape is used so that the strain of the whole sample becomes constant, that is, the shear speed of the sample becomes constant. The change of melt viscosity per minute, calculated from the following formula (i), is used as residual catalytic activity index. Residual catalytic activity index (%)=[(melt viscosity after 30 minutes-melt viscosity after 5 minutes) divided by ((melt viscosity after 5 minutes) x 25)] x 100 (i) The residual catalytic activity index is preferably 2% or less, more preferably 1 % or less, further preferably 0.5% or less, most preferably 0.2% or less. A residual catalytic activity index of this range is preferred because the aromatic polycarbonate resin shows little property change with time. In a most preferred embodiment, the polycarbonate will be a branched polycarbonate. The branched polycarbonate resin can be obtained by the same process for production as conventional processes for production according to a phosgene process except the steps comprising forming a reaction mixture while adding phosgene in bisphenol and trihydric or above phenol and after the completion of addition of phosgene, adding a tetraammonium salt to the reaction mixture to perform polycondensation reaction, then adding both monohydric phenol and a tertiary amine catalyst to the reaction mixture, further preforming polycondensation reaction, thereby obtaining a branched polycarbonate resin wherein number of dichloromethane insoluble gel-like particles with a particle diameter more than 50 μm is preferably 10 or below per 100 g of the resin. Examples of bisphenols as a raw material to derive the branched polycarbonate resin include 4,4'-biphenyldiol, 1 ,1'-bi-2-naphthol, bis(4-hydroxyphenyl) methane, bis(4- hydroxphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4- hydroxyphenyl)sulfιde, bis(4-hydroxyphenyl)ketone, 1 ,1 -bis(4-hydroxyphenyl)ethane, 2,2- bis(4-hydroxyphenyl) propane(bisphenol A; BPA), 2,2-bis(4-hydroxyphenyl) butane, 1 ,1 - bis(4-hydroxyphenyl)cyclohexane(bisphenol Z; BPZ), 2,2-bis(4-hydroxy-3,5- dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy- 3-bromophenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3- methylphenyl) propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1 ,1-bis(4- hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4- hydroxyphenyl) hexafluoropropane, α,ω-bis[2-(p-hydroxyphenyl)ethyl] polydimethylsiloxane, α,ω-bis[3-(o-hydroxyphenyl) propyl] polydimethylsiloxane, 9,9-bis(4- hydroxyphenyl) fluorene, 2,2-bis(4-hydroxy-3-allylphenyl)propane, 4,4'-[1 ,4- phenylenebis(1 -methylethylidene)]bisphenol, 4,4'-[1 ,3-phenylenebis(1 - methylethylidene)]bisphenol, 1 ,1 ,3-trimethyl-3-[(4-hydroxy)phenyl]-5-hydroxyindan, S.S.S'.S'-tetramethyl^.S^'.S'-tetrahydro^l .l '-spirobiindenJ-θ.δ'-diol, etc., and mixtures thereof. Examples of the branching agents include phloroglucin, 2,4,4'- trihydroxybenzophenone, 2,4,4'-trihydroxydiphenylether, 2,2-bis(2,4-dihydroxyphenyl) propane, 2,2',4,4'-tetrahydroxydiphenylmethane, 2,4,4'-trihydroxydiphenylmethane, 2,6- dimethyl-2,4,6-tri(4-hydroxyphenyl)-heptene-3, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)- heptane-2, 2,6-bis(2-hydroxy-5-methylbezil)-4-methylphenol, 2,6-bis(2-hydroxy-5- isopropylbenzil)-4-isopropylphenol, tetrakis(4-hydroxyphenyl)methane, α.α',α"-tris(4- hydroxyphenyl)-1 ,3,5-triisopropylbenzene, 1 ,1-bis(4-hydroxyphenyl)-1-[4-(4- hydroxyphenyl)isopropylphenyl]ethane and 1 ,1 ,1-tris(4-hydroxyaryl)alkanes. Examples of 1 ,1 ,1 -tris(4-hydroxyaryl)alkanes include 1 ,1 ,1 -tris(4- hydroxyphenyl)methane, 1 ,1 ,1 -tris(4-hydroxyphenyl)ethane, 1 ,1 ,1-tris(4-hydroxyphenyl) propane, 1 ,1 ,1 -tris(2-methyl-4-hydroxyphenyl)methane, 1 ,1 ,1-tris(2-methyl-4- hydroxyphenyl)ethane, 1 ,1 ,1 -tris(3-methyl-4-hydroxyphenyl)methane, 1 ,1 ,1-tris(3-methyl- 4-hydroxyphenyl)ethane, 1 ,1 ,1 -tris(3,5-dimethyl-4-hydroxyphenyl)methane, 1 ,1 ,1-tris(3,5- dimethyl-4-hydroxyphenyl)ethane, 1 ,1 ,1-tris(3-chloro-4-hydroxyphenyl)methane, 1 ,1 ,1- tris(3-chloro-4-hydroxyphenyl)ethane, 1 ,1 ,1 -tris(3,5-dichloro-4-hydroxyphenyl)methane, 1 ,1 ,1-tris(3,5-dichloro-4-hydroxyphenyl)ethane, 1 ,1 ,1-tris(3-bromo-4- hydroxyphenyl)methane, 1 ,1 ,1 -tris(3-bromo-4-hydroxyphenyl)ethane, 1 ,1 ,1-tris(3,5- dibromo-4-hydroxyphenyl)methane, 1 ,1 ,1-tris(3,5-dibromo-4-hydroxyphenyl)ethane, 1 ,1 ,1 - tris(3-fluoro-4-hydroxyphenyl)methane, 1 ,1 ,1-tris(3-fluoro-4-hydroxyphenyl)ethane, 1 ,1 ,1 - tris(3,5-difluoro-4-hydroxyphenyl)methane, 1 ,1 ,1-tris(3,5-difluoro-4-hydroxyphenyl)ethane, 1 ,1 ,1 -tris(4-hydroxyphenyl)-1 -phenylmethane, etc., among which 1 ,1 ,1 -tris(4- hydroxyphenyl)ethane is most preferable from the viewpoint of reactivity and easy handling. The amount of branching agent to be used for the branched polycarbonate resin is optionally selected within the range able to maintain characteristics of the branched polycarbonate resin. Considering the range to depress production of solvent insoluble three dimensional polymer and to exhibit good non-Newtonian characteristic, it is preferable that the amount is 0.1 to 3.0 mole % to bisphenol. Examples of monohydric phenols as molecular weight modifier include phenol, alkyl phenols including p-t-butylphenol, cumyl phenol, tribromophenol, p-n-octyl phenol and p-n- stearylphenol, alkylether phenols including p-n-butoxyphenols and p-n-octyloxyphenol and alkyl hydroxybenzoates including n-butyl p-hydroxybenzoate, n-octyl p-hydroxybenzoate and n-stearyl p-hydroxybenzoate. The monohydric phenol to be used as molecular weight modifier is added so as to able to maintain the molecular weight of the branched polycarbonate resin to preferable molecular weight range as molding material. The amount of monohydric phenol to be added is 0.5 to 10 mole % and preferably 1 to 5 mole % to bisphenol. Phosgene is used usually in the range of 100 to 140 mole and preferably 105 to 120 mole per 100 mole of bisphenol. The injection time of phosgene is usually 10 to 120 minutes and preferably 15 to 60 minutes. In conventional phosgene process, acid bonding agent such as pyridine, alkali metal hydroxides including sodium hydroxide and potassium hydroxide, etch, is used, among which preferably sodium hydroxide is used. It is preferable that the molar ratio of sodium hydroxides to bisphenol(s) is 2.0/1 to 3.5/1. Sodium hydroxide is used in the state of an aqueous solution. It is preferable that the concentration of sodium hydroxide in the aqueous solution is 6 to 10 (weight/volume) %. Water to be used herein is distilled water, ion exchange water or water recovered in the production of polycarbonate resin. Further, if necessary, a small amount of oxidation inhibitor such as sodium sulfite, hydrosulfite, etc., may be added. Examples of the tetraammonium salts to be added after the completion of injection of phosgene include tetramethylammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetraethylammonium bromide, tetra-n-butylammonium iodide, etc., among which trimethylbenzylammonium chloride and triethylbenzyl ammonium chloride are preferable. The tetraammonium salt is used usually in 0.0005 to 5 mole % to bisphenol. The tetraammonium salt is added in the state of an aqueous solution so as to be dispersed sufficiently over the whole of the reaction system. It is preferable that the concentration of tetraammonium salt in the aqueous solution is 0.1 to 20 (weight/volume) %. The aqueous solution is added to the reaction mixture, preferably together with sodium hydroxide, after the completion of injection of phosgene. The time at which a viscosity average molecular weight (Mv) of the reaction mixture reaches to 3,000 or above and less than 6,000 after the completion of addition of the tetraammonium salt is 3 to 20 minutes, depending upon the reaction temperature and stirring conditions. All the amount of the acid bonding agent to be used may be initially charged or 70 to 96% of the amount of the acid bonding agent to be used may be initially charged and then 2 to 28% of the acid bonding agent at the time of addition of tetraammonium and 2 to 28% of the acid bonding agent at the time of addition of monohydric phenol may be further added. At the time of addition of the monohydric phenol, it is possible to add a small amount of sodium hydroxide and the polymerization catalyst at the same time, Further, after adding the monohydric phenol to the reaction mixture, it is preferable to complete the polymerization with stirring for 30 to 120 minutes. Examples of the polymerization catalysts include tertiary amines such as triethylamine, tertiary phosphine, tetraphosphonium salts, nitrogen-containing heterocyclic compounds and salts thereof, imino ethers and salts thereof, and compounds having an amido group(s), among which tertiary amines such as triethylamine are preferable. The amount of the polymerization catalyst to be added is 0.01 to 1 mole % to bisphenol. The organic solvent is an organic compound which is insoluble in water and inert for the reaction and furthermore can dissolve polycarbonate produced by the reaction Examples of the organic solvents include chlorinated aliphatic hydrocarbons including dichloromethane, tetrachloroethane, chloroform, 1 ,2-dichloroethane, trichloroethane and dichloroethane, chlorimated aromatic hydrocarbons including chlorobenzene, dichlorobenzene and chlorotoluene, acetophenone, cyclohexane, anisole, etc, and a mixture thereof, among which dichloromethane is most preferably used. 0.1 to 2 L of the above-mentioned solvent(s) per 1 mole of bisphenol is used. In addition to the method described above for the synthesis of branched polycarbonates, it is possible to use a tetrahydric phenol having the following structure:

wherein A represents single bond, an alkylene or alkylidene group having from 1 to 20 carbon atoms, a polymethylene group having from 3 to 20 carbon atoms, a cycloakylene or cycloalkylidene group having from 5 to 20 carbon atoms, an arylene or arylalkylene group having from 6 to 20 carbon atoms, -O-, -CO-, -S-, -SO-, or -SO₂~; R₃₅ represents H, an alkyl group having from 1 to 8 carbon atoms, an aryl group having from 6 to 20 carbon atoms, or an arylalkyl group having from 7 to 20 carbon atoms; R₃₆ represents a halogen atom, an alkyl group having from 1 to 8 carbon atoms, an aryl group having from 6 to 20 carbon atoms, or an arylalkyl group having from 7 to 20 carbon atoms; and p is an integral value of from 0 to 4 inclusive. Alternatively, tetraphenols can be used in the preparation of branched polycarbonates which may be produced from any suitable dihydroxy compounds. The tetraphenols will have the following generic structure:

Still other methods of producing branched polycarbonates include the use of a tri- to hexahydric aliphatic alcohol of the following formula

wherein

R₃₇ and R₃₉ are independently selected from the group consisting of H, a linear Ci - C₃₀ alkyl, a branched C₃ - C₃₆ alkyl or R₄₀ — OH; and wherein

R₄o is selected from the group consisting of linear Ci - C₃₆ alkylene and branched C₃ - C₃₆ branched alkylene; and p is an integral value ranging from 2 to 5 inclusive; and R₃₈ is selected from the group consisting of a single bond, a linear Ci - C₃₆ alkylene or a branched C₃ - C₃₆ alkylene. Still yet other methods for producing branched polycarbonates will utilize the branching agent shown below

wherein

R ι, R ₂, and Rj₃ are independently selected from the group consisting of H,

C-i - C₅ alkyls and halogens; and q, r, and s are independently an integral value ranging from 0 to 4 inclusive. Still alternatively, branched polycarbonate resins may be prepared using interfacial polymerization processes wherein, typically, a polyhydric phenol having more than two hydroxy groups in the molecule is reacted with an aromatic dihydroxy compound and carbonic acid derivative in the presence of a chain terminating or molecular weight controlling agent Suitable polyhydric phenols are disclosed in the references cited above and include, for example, 1 ,1 ,1-tris-(4-hydroxyphenyl)-ethane (THPE), 1 ,3,5 tris-(4- hydroxyphenyl)-benzene, 1 ,4 bis-(4', 4"-dihydroxy-triphenylmethyl)-benzene and the like. Other examples of suitable branching agents include cyanuric chloride, branched dihydric phenols, 3,3-bis-(4-hydroxyaryl)oxindoles, and aromatic polycarbonates end-capped with branched alkyl acyl halides and/or acids. Another suitable branching agent is trimellitic triacid chloride. The aromatic dihydroxy compounds, carbonate precursors, and chain terminating or molecular weight controlling agents recited previously herein for use in the preparation of linear aromatic polycarbonates are also suitable for preparation of the branched aromatic polycarbonate starting material. Linear aromatic polycarbonate resin to branched chain polycarbonate is effected by contacting the resin with a polyhydric branching agent having more than two hydroxy groups per molecule in the presence of a catalytic amount of a suitable carbonate equilibration catalyst. In the same way, the branched polycarbonate resins of this invention may also be prepared from the commercially available aromatic branched polycarbonate resins described above by contacting the conventional resin with a polyhydric branching agent having more than two hydroxy groups per molecule in the presence of a catalytic amount of a suitable carbonate equilibration catalyst. Without intending to limit the scope of the present invention to any theory or reaction mechanism, it is believed that the reaction is initiated by the formation in-situ of a reactive phenoxide from reaction of the equilibration catalyst with the polyhydric branching agent which can thereafter readily undergo an addition reaction with electrophilic carbonate carbon atoms on the linear polycarbonate backbone causing chain scission to form a lower molecular weight fragment and a branched aromatic polycarbonate. It is further believed that the reaction continues until equilibration is attained and a product having a new molecular weight distribution and which has shorter branched chains than the linear aromatic or branched aromatic polycarbonate substrate is formed. Polyhydric phenols suitable as branching agents in the present invention include any triol or tetrol or higher hydroxy substituted polyhydric phenol, for example, 1 , 1 , 1 -tris- (4- hydroxyphenyl)ethane (or 4,4', 4"-ethylidyne trisphenol or THPE); 1 ,3,5-tris-(2- hydroxyethyl) cyanuric acid ([1 ,3,5-tris-(2-hydroxyethyl)-1 ,3,5-triazine-2,4,6-(1 H, 3H, 5H)- trione]; 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane-2; 2,2-bis-4,4-(4,4"- dihydroxyphenyl)-cyclohexyl propane; 1 ,3,5-trihydroxybenzene (phloroglucinol)); 1 ,2,3- trihydroxybenzene (pyrogallol); and 1 ,4-bis-(4'4"-dihydroxytriphenyl-methyl)-benzene. Other commercially available polyhydric phenols useful herein include, for example, 2', 3', 4'-trihydroxyacetophenone; 2,3,4-trihydroxybenzoic acid; 2,3,4- trihydroxybenzophenone; 2,4,4'-trihydroxybenzophenone; 2', 4', 6'-trihydroxy-3-((4- hydroxyphenyl)propiophenone; (phloretin); pentahydroxyflavone; 3,4,5- trihydroxyphenylethylamine (5-hydroxydopanine); 3,4-trihydroxyphenethyl alcohol; 2,4,5- trihydroxypyrimidine (isobarbituric acid); tetrahydroxy-1 , 4-quinone hydrate (tetrahydroxy- 1 ,4'-benzoquinone); 2,2', 4,4'-tetrahydroxybenzophenone; and 1 ,2,5,8- tetrahydroxyanthraquinone (quinalizarin). Of course, a mixture of two or more of such polyhydric phenols may be employed to achieve particularly desired properties of branched polycarbonate. Suitable carbonate equilibration catalysts include various bases and Lewis acids, and in general, any of those catalysts known for effecting polymerization of cyclic polycarbonate oligomers. Illustrative examples of bases include lithium 2,2,2- trifluoroethoxide, n-butyllithium, tetramethyl-ammonium hydroxide, and various weakly basic salts such as sodium benzoate and lithium stearate. Examples of useful Lewis acids include dioctyltin. oxide, triethanolamine titanium isopropoxide, tetra(2-ethylhexyl) titanate and polyvalent metal chelates such as aluminum acetylacetonate, bisisopropoxy titanium bisacetylacetonate, and the bisisopropoxy aluminum salt of ethyl acetoacetate. Also useful as carbonate equilibration catalysts herein are coordination compounds as employed as polycarbonate formation catalysts. Such a class of basic catalyst compounds is preferred in the practice of the present invention as they are able to generate phenoxides upon contact with the polyhydric phenol branching agents thus providing strong nucleophiles which can readily undergo an addition reaction with the substrate electrophillic carbon atoms. Illustrative examples of such preferred catalysts include tetrabutylammonium tetraphenylborate, tetramethylammonium tetraphenylborate, lithium tetraphenylborate, sodium tetraphenylborate, sodium bis-2,2'-biphenyleneborate, potassium tetraphenylborate, tetramethylphosphonium tetraphenylborate, tetra-n-butylphosphonium tetraphenylborate and tetraphenylphosphonium tetraphenylborate. The choice of any particular catalyst selected is not critical and the use herein of such catalysts described above or similar catalysts may depend upon such factors as their ι thermal stability, the desired rate of reaction and the chemical nature of the particular

2 linear polycarbonate and branching agents employed.

3 Preparation of the branched aryl polycarbonates can be effected by dry mixing the

4 above-described reagents prior to their reaction, for example, by melt condensation in a

5 Helicone at temperatures ranging from about 250°C to about 350°C, for approximately 5 to

6 30 minutes, or by dry mixing the reagents and continuously feeding the mixture through an

7 extrusion device at temperatures ranging from about 200°C to about 350°C. The β thermoplastic branched-chain polycarbonate is prepared by melt condensation at a

9 temperature of from about 200°C to about 350°C for about 1 to about 30 minutes. o In general equilibration is permitted to proceed for a period of time sufficient to i achieve the desired melt properties in the product branched resin. Generally, the level of 2 polyhydric branching agent is not critical to the practice of the present invention as varying 3 the level of branching agent will effect the number of branching sites and the average 4 branched polycarbonate chain length. For example, low levels of branching agents will s produce few branching points with relatively long chains, and higher levels will increase 6 the number of branching points, but will decrease the average length of the chains. The 7 amount of branching agent, therefore, will depend upon the various properties of particular s branched polycarbonates desired and end uses contemplated. 9 The above listing of processes used to synthesize branched polycarbonates is not 0 exhaustive and is provided as merely illustrative of one of a number of methods which may 1 be used to synthesize the desired product. 2 The polyesters as used in this invention, particularly PCTG, have a dicarboxylic 3 acid component and a glycol component, the dicarboxylic acid component comprising 4 repeat units from at least 90 mole % terephthalic acid and the glycol component 5 comprising repeat units from about 10-95 mole % 1 ,4-cyclohexanedimethanol and from 6 about 90-5 mole % ethylene glycol, the process comprising reacting the dicarboxylic acid 7 component and the glycol component at temperatures sufficient to effect esterification or 8 ester exchange and polycondensing the reaction product under an absolute pressure of 9 less than 10 mm Hg for a time of more than about 2 hours in the presence of a catalyst 0 and inhibitor system consisting essentially of about 0-75 ppm Mn, about 25-100 ppm Zn, 1 about 0.5-15 ppm Ti, about 5-80 ppm P, and 0 to about 60 ppm Co all parts by weight 2 based on the weight of the copolyester. In particular, PCTG polymers will have the 3 following formula:

wherein x ranges from 0.10 to 0.60 inclusive, preferably 0.20 to 0.50, most preferably

0.30 to 0.40 inclusive; and y is 1 -x. The PCTG polymer, a poly(1 ,4-cyclohexanedimethylene terephthalate-co-ethylene terephthalate) polymer has a number average molecular weight of about 26,000. Specifically, PCTG 5445 (CAS No. 25640-14-6) is a poly(cyclohexylenedimethlene terephthalate) modified with 34 mole percent ethylene glycol) and PCTG 10179 is a poly(cyclohexylenedimethylene terephthalate) modified with 19 mole percent ethylene glycol.

More generically, a PCTG-like polymer will be of the following formula:

wherein

R₂₂ is selected from the group consisting of a covalent bond, substituted or unsubstituted divalent C-i -Cβ hydrocarbon radicals, alkylidene groups having from C₂ - C₁₀ carbon atoms, cycloalkylene group having C₆ - do carbon atoms, cycloalkylidene groups having from Cβ - C₁₀ carbon atoms;

R₂₃ is selected independently from the group consisting of R₂₂;

R₂₄ is selected independently from the group consisting of R₂₃;

R₂sand R2₆ are independently selected from the group consisting of halogen, hydrogen, monovalent C-i - C₁₀ alkyls, monovalent Ci - C-₆ alkoxy radicals, aryl groups having from C₆ - do carbon atoms, aralkyl groups having from C₇ - C₁₀ carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof; m an n are integral values ranging from 0 to 4 inclusive; and x and y are as defined previously. Additionally, PCTA is another example of a polyester suitable for use in this invention. PCTA polymers will have the following formula.

PCTA 6761 (CAS No. 36487-02-2) is a poly(cyclohexylenedimethylene terephthalate) modified with 5 mole percent isophthalic acid and wherein v ranges from 0.01 to 0.40 inclusive, preferably 0.03 to 0.30, most preferably

0.04 to 0.10 inclusive; and w is 1 -v. More generically, a PCTA-like polymer will be of the following formula:

wherein

R₂7 is selected from the group consisting of a covalent bond, substituted or unsubstituted divalent Ci -C₈ hydrocarbon radicals, alkylidene groups having from C₂ - C₁₀ carbon atoms, cycloalkylene group having Cβ - do carbon atoms, cycloalkylidene groups having from C₆ - do carbon atoms;

R₂β is selected independently from the group consisting of R₂₇;

R₂g is selected independently from the group consisting of R₂β;

R₃o is selected independently from the group consisting of R₂₉; R31 and R₃₂ are independently selected from the group consisting of halogen, hydrogen, monovalent Ci - do alkyls, monovalent d - C₆ alkoxy radicals, aryl groups having from Cβ - do carbon atoms, aralkyl groups having from C7 - C10 carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof; m and n are as previously defined; and v and w are as previously defined. Either dimethyl terephthalate (or other lower dialkyl terephthalate ester) or terephthalic acid can be used in producing the copolyester. These materials are commercially available. The glycols used in the copolyester according to the present invention are CHDM and ethylene glycol. Both of these glycols are commercially available. The copolyesters used in making the articles of this invention have 100 mole % of a dicarboxylic acid portion and 100 mole % of a glycol portion. The dicarboxylic acid portion of the copolyesters comprises repeat units from at least 90 mole % terephthalic acid. Up to about 10 mole % of the dicarboxylic acid repeat units may be from other conventional acids such as those selected from succinic, glutaric, adipic, azelaic, sebacic, fumaric, maleic, itaconic, 1 ,4-cyclohexanedicarboxylic, phthalic, isophthalic, and naphthalene dicarboxylic acid. The glycol component of the copolyesters contains repeat units from about 10-95 mole % 1 ,4-cyclohexanedimethanol and about 90-5 mole % ethylene glycol. The glycol component may include up to about 10 mole % of conventional glycols such as propylene glycol, 1 ,3-propanediol; 2,4-dimethyl-2-ethylhexane-1 ,3-diol, 2,2-dimethyl-l,3-propanediol, 2-ethyl-2-butyl-1 ,3-propanediol, 2-ethyl-2-isobutyl-1 ,3-propanediol, 1 ,3-butanediol, 1 ,4- butanediol, neopentyl glycol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,8-octanediol, 2,2,4- trimethyl-1 ,6-hexanediol, thiodiethanol, 1 ,2-cyclohexanedimethanol, 1 ,3- cyclohexanedimethanol, 2,2,4,4-tetramethyl-l ,3-cyclobutanediol and the like. Branching agents such as, but not limited to, trimellitic acid, trimellitic anhydride, pentaerythritol, may be added for desired properties. In one aspect of the invention, the diacid component of the polyester includes aromatic groups and wherein the diol component of the polyester comprises at least a portion of a non-cyclic aliphatic diol. The diacid component will be considered to be aromatic if at least about 50 mole percent of the diacid is aromatic. As is well known in the polyester art, mixtures of diacids can be used. Useful diacid or diesters result in repeating units represented by the following formulas:

wherein a is an integer from 0 to 4 inclusive and each R₂₀ is independently selected from the group consisting of hydrogen, alkyl groups having from 1 to about 4 carbons and halogens.

The second component of the polyester is a diol component which can include cyclic components. Useful diol components result in repeating units which have the following structure:

and wherein R₂₁ represents a straight or branched alkylene group of from to about 1 to 10 carbons. Other diols resulting in repeating units having the formula:

-(OCH₂CH₂)_z- OCH₂ — ( )— CH₂O— (CH₂CH₂O)_z

(^R2θ)a and wherein z is an integer from 0 to 2 inclusive and R₂o and a are as defined previously.

Generally, the copolyesters may be produced using conventional polyesterification procedures described, for example, in U.S. Pat. Nos. 3,305,604 and 2,901 ,460. Of course, esters of the acids (e.g., dimethyl terephthalate) may be used in producing the polyesters. Either the cis or trans isomer of CHDM, or mixture thereof, may be used in accordance with the present invention.

In producing the copolyester according to this invention, a reaction mix of the dicarboxylic acids (or esters as described herein) and glycols is prepared. Mn and/or Zn and Ti are added at the beginning of the process (ester exchange reaction). P and Co (if used) are added after ester exchange. The catalysts and inhibitors can be mixed or added separately. Preferably, P is added after Co. ι In the preparation of polyesters by means of the ester interchange reaction, the

2 process comprises two steps. In the first step, glycol and diester such as dimethyl

3 terephthalate are reacted at elevated temperatures. Thereafter, the reaction product is

4 heated under still higher temperatures and under reduced pressure to form polyester with

5 the elimination of glycol, which is readily volatilized under these conditions and removed

6 from the system. The second step, or polycondensation step, is continued under higher

7 vacuum until a polymer having the desired degree of polymerization, determined by β inherent viscosity, is obtained. Without the aid of a suitable catalyst, the above reactions

9 do not proceed at a noticeable rate. o In the preparation of polyester by direct esterification, polyesters are produced by i reacting a free dicarboxylic acid with a glycol at a pressure of from about 1 to about 1000 2 pounds per square inch gauge pressure to produce a low molecular weight linear or 3 branched polyester product having an average degree of polymerization of from about 1.4 4 to about 10. This low molecular weight polymer can then be polymerized by s polycondensation reaction. 6 The present process can be advantageously operated as a continuous process. 7 High molecular weight linear or branched polyesters can be produced continuously by s continuously adding free dicarboxylic acid and glycol to molten low molecular weight linear 9 or branched polyester resin and reacting them while continuously withdrawing low 0 molecular weight resin and introducing the resin withdrawn into a polymerization 1 apparatus and continuously polymerizing it to high molecular weight resin and withdrawing 2 high molecular weight linear or branched polyester resin from the polymerization 3 apparatus. 4 If used, manganese is preferably used as a salt. Examples of suitable manganese 5 salts are manganous benzoate tetrahydrate, manganese oxide, manganese acetate, 6 manganese acetylacetonate, manganese succinate, manganese glycolate, manganese 7 naphthanate and manganese salicyl salicylate. 8 The zinc portion of the catalyst system is preferably added as a salt. Examples of 9 suitable salts include zinc acetate, zinc citrate, zinc lactate, zinc nitrate, zinc glycolate, etc. 0 The titanium is preferably added as titanium tetraalkoxide, e.g., titanium 1 tetraisopropoxide, titanium tetraethoxide or titanium tetrabutoxide. 2 The phosphorus is preferably added as trialkyl phosphate, triphenyl phosphate, or 3 phosphoric acid. The blue toner is preferably cobalt, and is preferably added as a salt. Examples of suitable cobalt salts are cobaltous acetate tetrahydrate, cobaltous nitrate, cobaltous chloride, cobalt acetylacetonate, cobalt naphthanate and cobalt salicyl salicylate. The levels of the catalysts and inhibitors used with dimethyl terephthalate based copolymers are as follows: Mn, from 0 to 75 ppm, preferably from 20 to 50 ppm, (catalyst); Zn, from 25 to 100 ppm, preferably from 50 to 80 ppm, (catalyst); Ti, from 0.5 to 15 ppm, preferably from 1 to 6 ppm (catalyst); and P, from 5 to 80 ppm, (inhibitor), preferably 10 to 30 ppm. Other mild catalysts, such as Ge, can be added but are not necessary. Co from 0 to 60 ppm or an organic blue toning agent at the proper level to control the color. The levels of the catalysts for terephthalic acid based copolymers are as follows: Zn, from 25 to 100 ppm, preferably from 50 to 80 ppm, (catalyst); Ti from 0.5-15 ppm, preferably from 1 to 6 ppm; P, from 5 to 80 ppm, (inhibitor), preferably from 10 to 30 ppm; Co from 0 to 60 ppm or an organic blue toning agent at the proper level to control the color. Other mild catalysts, such as germanium, can be added but are not necessary. The following examples are submitted for a better understanding of the blended polymers of this invention.

Table I

Material Weight percent Range CAS #

Polycarbonate 0.01-99.99% 25766-59-0

PCTG Copolyester 5445 0.01-99.99% 25640-14-6

Tinuvin 329 0-35% 003147-75-9

Doverphos S-9228 0-35% 154862-43-8

Glycolube P 0-35% 8045-34-9

Violet 14 0-35% 632-99-5

Tetrabromobisphenol 0-35% 79-94-7

ABS 0-50% 9003-56-9

Nylon 0-50% 63428-83-1

MBS 0-50% 102-77-2

Irganox 0-35% 2082-79-3

Naugard 0-35% 10081-67-1

INT-33UDK (fatty acid) 0-35% 57-11-4

Triphenylphosphate 0-35% 115-86-6

SAN 0-50% 9003-54-7

PET polyester 0-50% 25038-59-9

PETG polyester 0-50% 63407-54-5

PCTA polyester 0-50% 36487-02-2

Compact discs have been made from alloys of polycarbonate and PCTG clear plastics. Specific ranges in the composition used include 50% PC / 50% PCTG as well as 20% PC / 80% PCTG. These CD's show significant improvements in durability, ductility, impact, chemical resistance, and processability.

Example #1

The following PC/polyester blends were made and tested as illustrated in the Table

Table

Polycarbonate % Polyester % Melt Index HTD @66 PSI HTD @ 264 PSI

Makrolon 1239 PCTG 5445 (X) ASTM 648 (°C) ASTM 648 (°C)

10% 90% 72 75 68

20% 80% 55 88 78

30% 70% 46 93 84

40% 60% 35 98 87

50% 50% 27 101 93

Example #2

A 10% polycarbonate (Makrolon 1239) / 90% polyester (PCTG 5445) was molded an extruder with the following physical properties illustrated in Table III.

Table III

Test Result

Tensile strength (ASTM D-638) 7641 yield

(Type I Bar 27min) 7632 break

Tensile elongation (ASTM D-638) 317% yield

817% break

HDT @ 66 PSI (ASTM D-648) 88°C

(127mm x 12.7mm x 3.2mm)

HDT @ 264 PSI (ASTM D-648) 78°C

Specific Gravity (ASTM D-792) 1.224

Notched Izod (ASTM D-256) 0.5 in/lb. Example #3

The 20% blend of Table II was tested as illustrated in the Table IV.

Table IV

Property Conditions ASTM # Units Value

Melt Flow Rate G - 200°C @ 5 Kg D 1238 G/10 minutes 3

1 - 230°C @ 3.8 Kg 12

O - 300°C @ 1.2 Kg 78

Density D 792 g/cm³ 1.21

Water Absoφtion 24 hours @ 23°C D 570 % 0.15 Equilibrium @ 23°C 0.35

Tensile strength at yield Type 1 Bar (3.2 mm) D 638 Psi 8000

Tensile elongation at break Type 1 Bar (3.2 mm) D 638 % 350

Flexural modulus 3.2 mm D 790 Psi 300000

Heat Deflection temperature 66 psi D 648 °C 90 0.46 Mpa

Light Transmission D 1003 % 90

Haze D 1003 % 1

Refractive index D 542 1.584

Example #4 The injection molding conditions for molding the specimens were as follows in Table V.

Table V

Location T (°C) Comment

Rear 204-238 Injection pressure 8000-16000 psi

Middle 227-246 Hold 25-75% of injection pressure

Front 232-260 Back pressure 0-25 psi

Nozzle 232-260 Moderate screw speed

Melt temperature 232-266 Injection speed low to high

Mold temperature 21-66 Clamp 2 ton/in² Example # 5

A quality control chart from EMI Records is provided for a 20% PC / 80% PCTG 5445 polyester blend as tested as a CD. The test involved a CD-Digital Audio test involving 18 tracks with a total playing time of 74.22 minutes.

Table VI

Discs manufactured have passed current production quality control in all aspects, for the manufacture of CD audio as illustrated in Table VI, a quality control chart from EMI Records for an -80% PCTG / 20% PC alloy.

The ability to process at lower temperatures saves energy, slows degradation, reduces optical black specs and enables the incorporation of thermally unstable dyes, inks and other chemicals for new innovation in CDR, CDRW and other inked discs. The improvement in impact and ductility add service life to the optical medial which is significant in storage. It is now possible to sit on a CD made of the blends of this invention and not break the CD. ι The discs may contain various ratios of PC to PCTG and various melt index or

2 molecular weights of PC and PCTG to achieve significant desired changes in its thermal

3 and physical properties as illustrated in the Figures. The variation of these properties and

4 ratios will be useful in optimizing the desired properties in all forms of digital optics.

5 In a preferred embodiment of the optical media invention, the ratio of polycarbonate e / copolyester will be from ~100% PCTG / 0% PC to -5% PCTG / 95% PC. It is more

7 preferred that the amount of PCTG exceed the amount of PC. It is known in the art that β the ratios of the two polymers will change relative to each other based on various

9 molecular weights used of the respective polymers, as well as the desired final properties o of the blend. In one application, it is believed to be possible to completely eliminate all PC 1 in the manufacture of a CD. 2 One of the important aspects of this invention is the utilization of a copolyester 3 blend which is amorphous and wherein the blends are partially miscible. It is also believed 4 to be important that the refractive index match that of polycarbonate when polycarbonate s is used. 6 This same principle is used in the manufacture of automotive interior parts for 7 instrument panels. The improvement of impact will increase head impact safety and allow 8 interior panels to be manufactured without energy absorbent skins to pass government 9 regulations for head impact. The clarity (current systems are opaque due to impact 0 constraints) will allow the design changes including the elimination of paint and the 1 incorporation of molded-in-color which will add desired surface appearance over vehicle 2 life since there is no paint to scratch off.

Material 808C PC PC/ABS ABS

Izod Impact NB(25) 15 9 4

Elongation 320% 100% 120% 120%

Clarity 90 90 Opaque Opaque

Painted/Coated No Yes Yes Yes 3 4 The improved elongation and impact permit these interior parts to be unpainted or 5 coated while becoming safer and more durable with less manufacturing. 6 The same remains true for extruded sheets with respect to clarity, impact ductility, 7 improved chemical resistance and environmental aging. These sheets may be used as 8 glazing, panels, signs, displays, booths, stalls, cubicles, etc. ι In one particular embodiment of the invention, five (5) gallon water bottles

2 comprising 25% PC / 75% PCTG were molded using typical extrusion blow molding

3 equipment used in the production of polycarbonate water bottles. A typical extrusion blow

4 molding line set at approximately about 254°C was used with the key modification that the

5 temperature set up was lowered about 21-24°C. The advantages of this new bottle made

6 from this alloy include:

7 (a) greatly extended life cycle (as long as 10 times longer); β (b) higher strength (the impact strength of the PC/PCTG alloy was 29 ft. lbs.

9 Notched Izod whereas the same measurement for polycarbonate is typically o about 16 ft. lbs.; i (c) higher elasticity (the PC/PCTG alloy elongation was 300% whereas the 2 corresponding PC elongation is about 110% - the higher elasticity yielding a 3 bottle that is higher in puncture resistance and less susceptible to 4 destruction from freezing and splitting; s (d) better low temperature impact (the PC/PCTG has a 3 Izod at -40°C and 6 better low temperature elongation; and 7 (e) better chemical resistance (in wash tests, the bottle is expected to last up to 8 3 to 10 times longer than bottles made with PC alone due to the chemical 9 resistance of the PC/PCTG alloy). 0 Both linear and branched polycarbonates are useful in this invention. One of the keys to 1 this invention is the ability to raise the heat distortion temperature of the polyester by the 2 addition of polycarbonate. 3 Polymer blending is an excellent way of upgrading the physical properties over 4 either polymer individually as well as improving the economics for the blend. In addition, 5 heterogeneous materials are superior to homogeneous ones, as far as mechanical 6 properties. A critical factor in such heterogeneous systems is the interfacial adhesion 7 created at interfaces, which has to be strong enough to ensure stress transmission 8 between constituents at loading up o the fracture. Partial miscibility of components in 9 polymer blends represents the simplest way of achieving this desirable situation. In 0 practice, heterogeneous blends of partially miscible polymers are regarded as materials of 1 particular importance. 2 Polycarbonate attracts much attention because of its outstanding mechanical 3 properties. Through blending with the identified polyesters, and similar homologs or ι equivalents thereof, good adhesion is created at interfaces, due to the partial miscibility of

2 the polycarbonate with the polyesters. At least some of this desirable adhesion may be

3 attributable to alcoholysis and midchain transreactions. The midchain transreaction will

4 typically be effected between a carbonyl moiety of the polyester and the carbonate moiety

5 of the polycarbonate while the alcoholysis transreaction will be effected by alcoholysis of β the polycarbonate by a hydroxyl end group of the polyester. Transesterification can occur

7 between polyesters and polycarbonates during processing unless a transesterification β inhibitor such as Irganox 1098, from Ciba-Geigy, is incorporated with the polymer pellets.

9 The transesterification reaction may generate some block copolymers of polyester and o polycarbonate in the interfaces of the blends and these copolymers may be functioning as i a compatibilizer to improve the interfacial bonding for the phase-separated 2 polyester/polycarbonate blends. 3 The copolyester and/or copolyester/polycarbonate blends are useful in the following 4 applications: 5 Optical media, e.g., CD, DVD, CDR, CDRW, minidisc, VCD, and all other forms of 6 digital optical media; eyewear including glasses, lenses, sunglasses, safety glasses, 7 screens; transportation including interiors, e.g., instrument panels, bolsters, bezels, boxes, 8 covers, holders, knobs, pedals, rests, ducts, lenses, glazing and trim as well as exterior 9 applications, e.g., hubcaps, body parts, bumpers, panels, doors, hoods, fenders, lights, 0 and trim; appliances including housings, panels, displays, bins, trays, covers, boards, 1 bases, bezels, fans, coffee makers, computer housings, etc.; electronics including 2 housings, covers, displays, bezels, boxes, storage, memory, optics, trays, keyboards, 3 mice, conductors, insulators, diodes, capacitors, cords, wiring, etc.; housewares including 4 cutlery, handles, boards, boxes, glasses, dishes, utensils, bins, aquariums, terrariums, 5 bowls, pitchers, etc.; construction including coatings, paints, films, tanks, plumbing fixtures, 6 sinks, glazing, cabinets, doors, flooring, bathrooms, fixtures, showers, roofing gutters, 7 siding, decking, lighting, skylights, atriums, booths, blocks, structural supports, facades, 8 cladding, signs, trim, shelving, racking, piping, pipe, tubes, junction boxes, connectors, 9 insulators, insulation, foams, etc.; safety including glasses, shields, apparel, padding, 0 helmets, barricades, lenses, lights, bumpers, delineators, braces, signs, reflectors, cones, 1 helmets, barrels, etc.; agricultural and farming including housings, trays, films, 2 greenhouse, pots, seed trays, tools, blades, silos, grain storage, storage vessels, tanks, 3 dairy tanks, troughs, cow feeders, pens, dividers, enclosures, etc.; apparel including buttons, bangles, beads, bands, belting, boots, jewelry, rings, shoes, sandals, straps, belts, fibers, flocking, insulation, rood, sheet, tube, bullet proof vests, face shields, visors, eyewear, goggles, orthopedics, prosthetics, diapers, hairclips, hats, fake nails, dental, helmets, pads, etc.; toys including balls, guns, dolls, cars, Legos, blocks, games, pieces, dice, cubes, Frisbees, disks, flying apparatii, rattles, trains, trucks, planes, models, riding toys, bicycles, baby seats, car seats, basketball backboards, action toys, Nintendo game housings, swings, seats, sliding boards, playgrounds, toy housings, toy animals, pet toys, figurines, toy boats, floats, pools, tanks, padding, displays, doll houses, boards, slip-n- slides, etc.; lawn and garden including rakes, shovels, chairs, trowels, tillers, blades, lawn mowers, housings, weed whackers, hoses, sprinklers, tables, furniture, decking, enclosures, light holders, picnic tables, umbrellas, etc.; military including shielding, firearms, housings, vessels, helmets, boots, apparel, armor, displays, shelters, canopies, aircraft bullets, skins, sonar coverings, cables, etc.; medical including tubing, catheters, valves, prosthetics, needles, syringes, pans, packaging, piping, pumps, displays, implants, casts, machines, etc.; furniture including tables, chairs, counters, stands, planters, lanterns, stools, desks, lamps, lighting, chandeliers, couches, ladders, stairs, vases, etc.; marine including boats, canoes, kayaks, hulls, skins, seats, supports, steering wheels, dash boards, windows, buoys, bumpers, rope netting, patches, hatches, arks singhies, motor housings, displays, housing sails, hooks, pulleys, galleys, heads, paneling, interior flooring, wall covering mast, cleats, etc.; sporting goods, including fishing lures, backboards, billiard balls, pool tables, ping pong tables, rackets, paddles, balls, strings, pools, bows, guns, tents, poles, chairs, cleats, skis, hockey pucks, ski goggles, poles, skates, boats, rollers, wheels, roller blades, scooters, pads, helmets, posts, rims, netting, bowling balls and pins, shafts, golf clubs, golf ball cover, tees, golf carts, golf bags, fins, goggles, snorkels, hockey sticks, Frisbees, fishing poles, horseshoes, vaulting poles, etc.; packaging including bottles, trays, films, boxes, foams, cans, jars, dispensers, toilet paper and paper towel dispensers, lids, etc.; tools including handles, flashlights, lighting, optics, mallets, power tools, housings, tables hoses, etc.; utilities including solar panels, windmill blades, wave baffles, turbine blades, hydraulic blades, impeller parts, batteries, housings, light piping, lenses, solar lenses, solar laser, giant lenses, etc.; communications including telephones, fiber optics, digital media, credit cards, smart cards, CD cards, phone cards, business cards, pens, speakers, faxes mail boxes, wires, cell phones, cables, wire relays, ι piping, conduits, satellite dishes, etc.; and textiles including woven and unwoven fiber,

2 reflective, illuminated, luminous, spun and drawn, etc.

3 Additionally, polycarbonate has been used in the manufacture of water receptacles,

4 but suffers from durability problems. The compositions of this invention are equally

5 applicable for use in water containers of any size and shape where polycarbonate

6 containers had been used previously.

7 The articles of this invention are characterized by improved physical properties, and β include in general, automotive, truck, military vehicle, and motorcycle exterior and interior

9 components, including panels, quarter panels, rocker panels, trim, fenders, doors, o decklids, trunk lids, hoods, bonnets, roofs, bumpers, fascia, grilles, mirror housings, pillar i appliques, cladding, body side moldings, wheel covers, hubcaps, door handles, spoilers, 2 window frames, headlamp bezels, headlamps, tail lamps, tail lamp housings, tail lamp 3 bezels, license plate enclosures, roof racks, and running boards; enclosures, housings, 4 panels, and parts for outdoor vehicles and devices; enclosures for electrical and s telecommunication devices; outdoor furniture; aircraft components; boats and marine 6 equipment, including trim, enclosures, and housings; outboard motor housings; depth 7 finder housings, personal water-craft; jet-skis; pools; spas; hot-tubs; steps; step coverings; 8 building and construction applications such as glazing, roofs, windows, floors, decorative 9 window furnishings or treatments; treated glass covers for pictures, paintings, posters, and 0 like display items; wall panels, and doors; protected graphics; outdoor and indoor signs; 1 enclosures, housings, panels, and parts for automatic teller machines (ATM); enclosures, 2 housings, panels, and parts for lawn and garden tractors, lawn mowers, and tools, 3 including lawn and garden tools; window and door trim; sports equipment and toys; 4 enclosures, housings, panels, and parts for snowmobiles; recreational vehicle panels and 5 components; playground equipment; articles made from plastic-wood combinations; golf 6 course markers; utility pit covers; computer housings; desk-top computer housings; 7 portable computer housings; lap-top computer housings; palm-held computer housings; 8 monitor housings; printer housings; keyboards; FAX machine housings; copier housings; 9 telephone housings; mobile phone housings; radio sender housings; radio receiver 0 housings; light fixtures; lighting appliances; network interface device housings; transformer 1 housings; air conditioner housings; cladding or seating for public transportation; cladding 2 or seating for trains, subways, or buses; meter housings; antenna housings; cladding for 3 satellite dishes; coated helmets and personal protective equipment; coated synthetic or ι natural textiles; coated photographic film and photographic prints; coated painted articles;

2 coated dyed articles; coated fluorescent articles; coated foam articles; and like

3 applications. The invention further contemplates additional fabrication operations on said

4 articles, such as, but not limited to, molding, in-mold decoration, baking in a paint oven,

5 lamination, and/or thermoforming.

6 This invention has been described in detail with reference to specific embodiments

7 thereof, including the respective best modes for carrying out each embodiment. It shall be β understood that these illustrations are by way of example and not by way of limitation.

Claims

What is Claimed Is:

1. A polymer blend comprising:

(a) a polycarbonate having the following repeating unit

wherein

Ri₈ is independently selected from the group consisting of halogen, hydrogen, monovalent Ci - do alkyls, monovalent d - Cβ alkoxy radicals, aryl groups having from Cβ - Cι₀ carbon atoms, aralkyl groups having from d - do carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof;

R₁₉ is independently selected from Rι₈;

W is selected from the group consisting of a covalent bond, substituted or unsubstituted divalent Ci -Cs hydrocarbon radicals, alkylidene groups having from C₂ - do carbon atoms, cycloalkylene group having C - C₁₀ carbon atoms, cycloalkylidene groups having from C - do carbon atoms, alkylene-arylene-alkylene groups having C₈ - C₁₅ carbon atoms, --S-, ~S(R₃₃)₂~, -S-S-, -O-, ~N(R₃4)~, -SO-, -SO2-, and -CO-,

R₃₃ and R₃₄ are substituents selected independently from the group consisting of H, halogen, phenyl, substituted phenyl, alkyl, substituted alkyl, alkoxy, and substituted alkoxy of from d to C₂₀ carbons; and

R _t and R₄₅ are selected from the group consisting of H, Ci - C alkyls; b is O or 1 ; z is an integral value ranging from 4 to 9 inclusive; and each n is independently selected from integers having a value of from 0 to 4 inclusive; and (b) a polyester selected from the group consisting of

(i) a polyester having the following repeating unit of formula (V):

wherein

R₂₂ is selected from the group consisting of a covalent bond, substituted or unsubstituted divalent d -Cβ hydrocarbon radicals, alkylidene groups having from C₂ - C10 carbon atoms, cycloalkylene group having C - C₁₀ carbon atoms, cycloalkylidene groups having from C - do carbon atoms;

R₂₃ is selected independently from the group consisting of R₂₂;

R₂₄ is selected independently from the group consisting of R₂₃;

R₂₅and R₂₆ are independently selected from the group consisting of halogen, hydrogen, monovalent d - C1₀ alkyls, monovalent Ci - C₆ alkoxy radicals, aryl groups having from C₆ - C₁₀ carbon atoms, aralkyl groups having from C7 - C10 carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof; m an n are integral values ranging from 0 to 4 inclusive; x ranges from 0.10 to 0.60 inclusive, preferably 0.20 to 0.50, most preferably

0.30 to 0.40 inclusive; and y is 1-x; and

(ϋ) a polyester having the following repeating unit of formula (VI):

(VI) wherein

R₂₇ is selected from the group consisting of a covalent bond, substituted or unsubstituted divalent d -Cβ hydrocarbon radicals, alkylidene groups having from C₂ - C₁₀ carbon atoms, cycloalkylene group having Cβ - C₁₀ carbon atoms, cycloalkylidene groups having from Cβ - Cι₀ carbon atoms;

R₂β is selected independently from the group consisting of R₂₇;

R₂g is selected independently from the group consisting of R₂β;

R₃o is selected independently from the group consisting of R₂g;

R₃₁ and R₃₂ are independently selected from the group consisting of halogen, hydrogen, monovalent Ci - do alkyls, monovalent Ci - Cβ alkoxy radicals, aryl groups having from Cβ - do carbon atoms, aralkyl groups having from C₇ - C₁₀ carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof; m an n are as previously defined; v ranges from 0.01 to 0.40 inclusive, preferably 0.03 to 0.30, most preferably 0.04 to 0.10 inclusive; and w is 1 -v.

2. The blend of claim 1 wherein

(a) x ranges from about 0.20 to about 0.50 inclusive; and

(b) v ranges from about 0.03 to about 0.30 inclusive.

3. The blend of claim 2 wherein

(a) x ranges from about 0.30 to 0.40 inclusive; and

(b) v ranges from about 0.04 to 0.10 inclusive.

4. The blend of claim 3 wherein

(a) the polyester of formula (V) is a poly(cyclohexylenedimethlene terephthalate) modified with 34 mole percent ethylene glycol; and

(b) the polyester of formula (VI) is a poly(cyclohexylenedimethylene terephthalate) modified with 5 mole percent isophthalic acid

The blend of claim 4 wherein

(a) the polyester of formula (V) is a poly(cyclohexylenedimethlene terephthalate) modified with 34 mole percent ethylene glycol

6. The blend of claim 4 wherein

(a) said polycarbonate is a branched polycarbonate.

7. The blend of claim 1 wherein said polycarbonate is selected from the group consisting of (a) carbonate structural units corresponding to structure (I)

where

Ri, R2, R₃, and t are independently selected from the group consisting of H, and Ci - C₆ alkyls, R₅ is C_T - C₃ alkyl, n is an integral value from 0 to 2 inclusive; and (b) carbonate structural units corresponding to structure (II)

(II) wherein

R₆, R₇, R₁₀ and Rn are independently selected from the group consisting of H, and C-i - Cβ alkyls, Re and R₉ are independently H or d - C₅ alkyl, R₁₂ is H or d -C₃ alkyl; and n is an integral value from 0 to 2 inclusive; and (c) carbonate structural units selected from the group consisting of (i) carbonate structural units corresponding to structure (III)

(lll) where

R₁₃, Rι and R-ie independently represent H, and d - Cβ alkyls,

R-_I5 is H or Ci - C₃ alkyl and n is an integral value from 0 to 2 inclusive,

R₁₇ is H or Ci - C₅ alkyl; and

(ii) carbonate structural units corresponding to structure (IV)

(IV) wherein

Riβ is independently selected from the group consisting of halogen, hydrogen, monovalent C-i - C10 alkyls, monovalent d - Cβ alkoxy radicals, aryl groups having from Cβ - do carbon atoms, aralkyl groups having from C₇ - do carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof;

R1₉ is independently selected from the group consisting of halogen, hydrogen, monovalent Ci - C₁₀ alkyls, monovalent Ci - Cβ alkoxy radicals, aryl groups having from Cβ - C₁₀ carbon atoms, aralkyl groups having from C₇ - do carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof; W is selected from the group consisting of a covalent bond, substituted or unsubstituted divalent d -C₈ hydrocarbon radicals, alkylidene groups having from C2 - C1₀ carbon atoms, cycloalkylene group having C₆ - C₁₀ carbon atoms, cycloalkylidene groups having from Cβ - C10 carbon atoms, alkylene-arylene-alkylene groups having C₈ - ds carbon atoms, -S-, -S(R₂₇)₂-, -S-S-, -0-, - N(R₂₈)~, -SO-, -SO₂~, -CO-; b is 0 or 1 ; wherein

R₂ and R₂β are substituents selected independently from the group consisting of H, halogen, phenyl, substituted phenyl, alkyl, substituted alkyl, alkoxy, and substituted alkoxy of from C-i to C₂o carbons; and each n is independently selected from integers having a value of from 0 to 4 inclusive; and (iii) carbonate structural units corresponding to structures (III) and (IV) wherein the polycarbonate has a glass transition temperature of from about 120°C to about 185°C and a water absorption of less than about 0.33%.

8. The blend of claim 1 wherein

(a) a weight percent of said polyester in said blend is greater than said weight percent of said polycarbonate.

9. A process to improve the impact strength and elasticity of polycarbonate by blending in an amount of polyester a polyester selected from the group consisting of

(a) a polyester having the following repeating unit of formula (V):

wherein R₂₂ is selected from the group consisting of a covalent bond, substituted or unsubstituted divalent d -Cβ hydrocarbon radicals, alkylidene groups having from C₂ - do carbon atoms, cycloalkylene group having C₆ - C₁₀ carbon atoms, cycloalkylidene groups having from Cβ - C₁₀ carbon atoms;

R₂₃ is selected independently from the group consisting of R₂₂;

R₂₄ is selected independently from the group consisting of R₂₃;

R₂βand R₂₆ are independently selected from the group consisting of halogen, hydrogen, monovalent d - C₁₀ alkyls, monovalent Ci - Cβ alkoxy radicals, aryl groups having from Cβ - do carbon atoms, aralkyl groups having from C₇ - C₁₀ carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof; m an n are integral values ranging from 0 to 4 inclusive; x ranges from 0.10 to 0.60 inclusive, preferably 0.20 to 0.50, most preferably 0.30 to 0.40 inclusive; and y is 1-x; and (b) a polyester having the following repeating unit of formula (VI):

(VI) wherein

R₂₇ is selected from the group consisting of a covalent bond, substituted or unsubstituted divalent Ci -C₈ hydrocarbon radicals, alkylidene groups having from C2 - do carbon atoms, cycloalkylene group having Cβ - C₁₀ carbon atoms, cycloalkylidene groups having from Cβ - C₁₀ carbon atoms;

R₂β is selected independently from the group consisting of R₂₇;

R₂g is selected independently from the group consisting of R₂β;

R₃₀ is selected independently from the group consisting of R₂₉;

R₃₁ and R₃₂ are independently selected from the group consisting of halogen, hydrogen, monovalent d - do alkyls, monovalent C-i - Cβ alkoxy radicals, aryl groups having from Cβ - o carbon atoms, aralkyl groups having from C₇ - C₁₀ carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof; m an n are as previously defined; v ranges from 0.01 to 0.40 inclusive, preferably 0.03 to 0.30, most preferably 0.04 to 0.10 inclusive; and w is 1-v.

10. The process of claim 9 wherein

(a) x ranges from about 0.20 to about 0.50 inclusive; and

(b) v ranges from about 0.03 to about 0.30 inclusive.

11. The process of claim 10 wherein

(a) x ranges from about 0.30 to 0.40 inclusive; and

(b) v ranges from about 0.04 to 0.10 inclusive.

12. The process of claim 11 wherein

(a) the polyester of formula (V) is a poly(cyclohexylenedimethlene terephthalate) modified with 34 mole percent ethylene glycol; and

(b) the polyester of formula (VI) is a poly(cyclohexylenedimethylene terephthalate) modified with 5 mole percent isophthalic acid

13. The process of claim 11 wherein

(a) the polyester of formula (V) is a poly(cyclohexylenedimethlene terephthalate) modified with 34 mole percent ethylene glycol

14. The process of claim 12 wherein

(a) said polycarbonate is a branched polycarbonate.

15. An article of manufacture comprising a polyester selected from the group consisting of (a) a polyester having the following repeating unit of formula (V):

wherein

R22 is selected from the group consisting of a covalent bond, substituted or unsubstituted divalent Ci -C₈ hydrocarbon radicals, alkylidene groups having from C2 - C1₀ carbon atoms, cycloalkylene group having Cβ - C₁₀ carbon atoms, cycloalkylidene groups having from Cβ - C1₀ carbon atoms;

R23 is selected independently from the group consisting of R₂₂; R₂₄ is selected independently from the group consisting of R₂₃;

R₂₅and R₂β are independently selected from the group consisting of halogen, hydrogen, monovalent d - do alkyls, monovalent Ci - Cβ alkoxy radicals, aryl groups having from Cβ - C₁₀ carbon atoms, aralkyl groups having from C₇ - C₁₀ carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof; m an n are integral values ranging from 0 to 4 inclusive; x ranges from 0.10 to 0.60 inclusive, preferably 0.20 to 0.50, most preferably 0.30 to 0.40 inclusive; and y is 1-x; and (b) a polyester having the following repeating unit of formula (VI)

(VI) wherein

R₂7 is selected from the group consisting of a covalent bond, substituted or unsubstituted divalent d -Cs hydrocarbon radicals, alkylidene groups having from C₂ - C₁₀ carbon atoms, cycloalkylene group having Cβ - C₁₀ carbon atoms, cycloalkylidene groups having from Cβ - C₁₀ carbon atoms; R28 is selected independently from the group consisting of R₂7; R₂g is selected independently from the group consisting of R₂β; R₃o is selected independently from the group consisting of R₂₉; R₃-i and R₃2 are independently selected from the group consisting of halogen, hydrogen, monovalent d - C₁₀ alkyls, monovalent Ci - C alkoxy radicals, aryl groups having from Cβ - C1₀ carbon atoms, aralkyl groups having from C₇ - C10 carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof; m an n are as previously defined; v ranges from 0.01 to 0.40 inclusive, preferably 0.03 to 0.30, most preferably 0.04 to 0.10 inclusive; and w is 1-v.

16. The article of claim 15 wherein

(a) x ranges from about 0.20 to about 0.50 inclusive; and

(b) v ranges from about 0.03 to about 0.30 inclusive.

17. The article of claim 16 wherein

(a) x ranges from about 0.30 to 0.40 inclusive; and

(b) v ranges from about 0.04 to 0.10 inclusive.

18. The article of claim 17 wherein

(a) the polyester of formula (V) is a poly(cyclohexylenedimethlene terephthalate) modified with 34 mole percent ethylene glycol; and

(b) the polyester of formula (VI) is a poly(cyclohexylenedimethylene terephthalate) modified with 5 mole percent isophthalic acid

19. The article of claim 18 wherein

(a) the polyester of formula (V) is a poly(cyclohexylenedimethlene terephthalate) modified with 34 mole percent ethylene glycol

20. The article of claim 15 which further comprises using a polymer blend comprising a polycarbonate having the following repeating unit

wherein

Riβ is independently selected from the group consisting of halogen, hydrogen, monovalent Ci - C₁₀ alkyls, monovalent C-i - Cβ alkoxy radicals, aryl groups having from Cβ - C1₀ carbon atoms, aralkyl groups having from d - C1₀ carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof;

R₁₉ is independently selected from R₁₈;

W is selected from the group consisting of a covalent bond, substituted or unsubstituted divalent d -Cβ hydrocarbon radicals, alkylidene groups having from C2 - do carbon atoms, cycloalkylene group having Cβ - C₁₀ carbon atoms, cycloalkylidene groups having from Cβ - C₁₀ carbon atoms, alkylene-arylene-alkylene groups having C₈ - C₁₅ carbon atoms, -S-, ~S(R₃₃)2~, -S-S-, -O-, -N(R₃₄)-, -SO-, -SO2-, and -CO-,

R₃₃ and R₃₄ are substituents selected independently from the group consisting of H, halogen, phenyl, substituted phenyl, alkyl, substituted alkyl, alkoxy, and substituted alkoxy of from d to C₂₀ carbons; and

R ₄ and R ₅ are selected from the group consisting of H, d - C alkyls; z is an integral value ranging from 4 to 9 inclusive; b is 0 or 1 ; and each n is independently selected from integers having a value of from 0 to 4 inclusive.