RU2291876C2 - Polymer composition and heat-resistant parts (variants) - Google Patents

Abstract

FIELD: polymer materials.

SUBSTANCE: group of inventions relates to structural polycarbonate-based plastics and items molded therefrom. A heat-resistant part is provided consisting of polycarbonate copolymer, which gas 5 to 95 mol % of repetitive units (component "a") described by general formula I:

(I) and 95 to 5 mol % of repetitive units (component "b") described by general formula II:

(II), where each of R^a-R^d independently represents hydrogen atom, hydrocarbon group optionally substituted with aromatic radical having 1 to 9 carbon atoms, or halogen atom, an W is alkyl group optionally substituted with aromatic radical having 1 to 9 carbon atoms. Provided are also a part for solder-fusion soldering, a part for light beam trajectory transformation, optical disk, plastic mirror, conductive polymer composition and electronic part transportation pan containing the latter.

EFFECT: increased heat resistance and dimension-retention capability.

34 cl, 2 dwg, 9 tbl, 36 ex

Description

FIELD OF TECHNOLOGY

The present invention relates to a polycarbonate copolymer and to heat-resistant parts containing a copolymer. More specifically, the present invention relates to a polycarbonate copolymer containing repeating units including 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and to heat-resistant parts containing a copolymer. In addition, the present invention also relates to a polymer composition comprising a copolymer.

BACKGROUND

The polycarbonate obtained by the reaction between 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as "bisphenol A") and a carbonate precursor is used as a structural plastic in various fields. However, molded products made using polycarbonate containing bisphenol A units exhibit poor heat resistance, transparency, formability, and dimensional stability depending on the application, so that the molded products may undergo deformation, melting, and the like.

Therefore, a variety of proposals were made aimed at improving heat resistance (reference to patent publications 1, 2, 3, 4, 5, and 6).

In addition, for use in optics, a polycarbonate copolymer having a fluorene structure was proposed, a typical representative of which is 9,9-bis (4-hydroxyphenyl) fluorene (reference to patent publications 7, 8, 9, 10, 11, 12 and 13) .

Prior Art Publications

Patent Publication 1 JP-A 6-25401 Patent Publication 2 JP-A 7-52270 Patent Publication 3 JP-A 6-192411 Patent Publication 4 JP-A 11-306823 Patent Publication 5 JP-A 11-35815 Patent Publication 6 JP-A 7-268197 Patent Publication 7 JP-A 6-25398 Patent Publication 8 JP-A 6-172508 Patent Publication 9 JP-A 2000-319375 Patent Publication 10 JP-A 2000-319376 Patent Publication 11 JP-A 2000-319377 Patent Publication 12 JP-A 2001-55435 Patent Publication 13 JP-A 2001-55436

The tasks solved by the invention

An object of the present invention is to provide a polycarbonate copolymer having excellent heat resistance and dimensional stability, a polymer composition containing a copolymer and a variety of molded articles.

Description of the invention

The present invention is a polycarbonate copolymer containing from 5 to 95 mol% of repeating units (component a) described by the following general formula (I):

and from 95 to 5 mol% of the repeating units (component b) described by the following general formula (II):

where R ^a -R ^d each independently represents a hydrogen atom, a hydrocarbon group that may contain an aromatic group having from 1 to 9 carbon atoms, or a halogen atom, a W represents a single bond, a hydrocarbon group that may contain an aromatic group, having from 1 to 20 carbon atoms, or the group O, S, SO, SO ₂ , CO or COO.

In addition, the present invention relates to a heat-resistant part containing a polycarbonate copolymer, wherein the polycarbonate copolymer contains from 5 to 95 mol% of repeating units (component a) described by the following general formula (I):

and from 95 to 5 mol% of the repeating units (component b) described by the following general formula (II):

where R ^a —R ^d each independently represents a hydrogen atom, a hydrocarbon group that may contain an aromatic group having from 1 to 9 carbon atoms, or a halogen atom, and W represents a single bond, a hydrocarbon group that may contain an aromatic group having from 1 to 20 carbon atoms, or the group O, S, SO, SO ₂ , CO or COO.

The first aspect of the present invention is a part for reflow soldering consisting of a polycarbonate copolymer, the polycarbonate copolymer containing from 60 to 95 mol% of repeating units (component a) described by the following general formula (I):

and from 40 to 5 mol% of repeating units (component b) described by the following general formula (II-1):

The second aspect of the present invention is a part for converting the trajectory of a light beam, consisting of a polycarbonate copolymer, the polycarbonate copolymer containing from 50 to 95 mol% of repeating units (component a) described by the following general formula (I):

and from 50 to 5 mol% of repeating units (component b) described by the following general formula (II):

where R ^a -R ^d each independently represents a hydrogen atom, a hydrocarbon group that may contain an aromatic group having from 1 to 9 carbon atoms, or a halogen atom, a W represents a single bond, a hydrocarbon group that may contain an aromatic group, having from 1 to 20 carbon atoms, or the group O, S, SO, SO ₂ , CO or COO.

A third aspect of the present invention is an optical disk that includes a substrate with a thickness in the range of 0.3 to 1.2 mm, on which there are embossed recesses, or guide grooves, a reflective layer formed on the substrate, and a transparent protective layer with a thickness of a range from 3 to 200 μm, which is formed on a reflective layer and which reproduces the recorded data on the mechanism for changing the light intensity of the reflected light obtained by illuminating the disk with a beam of light from the transparent side of the protective layer,

the substrate essentially consists of a polycarbonate copolymer,

the polycarbonate copolymer contains from 20 to 95 mol% of repeating units (component a) described by the following general formula (I):

and from 80 to 5 mol.% repeating units (component b) described by the following general formula (II):

where R ^a -R ^d each independently represents a hydrogen atom, a hydrocarbon group that may contain an aromatic group having from 1 to 9 carbon atoms, or a halogen atom, a W represents a single bond, a hydrocarbon group that may contain an aromatic group, having from 1 to 20 carbon atoms, or the group O, S, SO, SO ₂ , CO or COO,

the substrate is characterized

(A) a modulus of elasticity in bending from 2800 to 4000 MPa,

(B) water absorption equal to 0.3 wt.% Or less upon reaching saturation,

(C) a tanδ value measured at 40 ° C and 18 Hz in accordance with ISO 6721-4 of at least 0.020, and

(D) deformation resistance, measured under a load of 1.81 MPa in accordance with ISO 75-1, -2, equal to 110 ° C or more.

A fourth aspect of the present invention is a plastic mirror consisting of a polycarbonate substrate and a metal reflective film,

the polycarbonate substrate contains a polycarbonate copolymer,

the polycarbonate copolymer contains from 20 to 70 mol.% repeating units (component a) described by the following general formula (I):

and from 80 to 30 mol.% repeating units (component b) described by the following general formulas (II-1) and / or (II-2):

polycarbonate substrate is characterized

(A) glass transition temperature from 120 to 230 ° C,

(B) water absorption equal to 0.2 wt.% Or less after immersion in water at 23 ° C for 24 hours, and

(C) the modulus of elasticity in bending from 2500 to 4000 MPa.

A fifth aspect of the present invention is a conductive polymer composition comprising a polycarbonate copolymer and a carbon-based filler, wherein the polycarbonate copolymer contains from 5 to 95 mol% of repeating units (component a) described by the following general formula (I):

and from 95 to 5 mol% of the repeating units (component b) described by the following general formula (II):

where R ^a -R ^d each independently represents a hydrogen atom, a hydrocarbon group that may contain an aromatic group having from 1 to 9 carbon atoms, or a halogen atom, a W represents a single bond, a hydrocarbon group that may contain an aromatic group, having from 1 to 20 carbon atoms, or the group O, S, SO, SO ₂ , CO or COO.

A sixth aspect includes a tray for transporting an electronic component, the tray consisting of a polycarbonate copolymer and a carbon-based filler, wherein the polycarbonate copolymer contains from 5 to 95 mol% of repeating units (component a) described by the following general formula (I):

and from 95 to 5 mol% of the repeating units (component b) described by the following general formula (II):

where R ^a -R ^d each independently represents a hydrogen atom, a hydrocarbon group that may contain an aromatic group having from 1 to 9 carbon atoms, or a halogen atom, a W represents a single bond, a hydrocarbon group that may contain an aromatic group, having from 1 to 20 carbon atoms, or the group O, S, SO, SO ₂ , CO or COO.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a part of a schematic representation of a vertical cross section of a disk in one embodiment of the optical disk of the present invention.

Figure 2 is a part of a schematic vertical cross section of a disk in one embodiment of the optical disk of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Polycarbonate copolymer

Component a

The polycarbonate copolymer of the present invention is obtained by using 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as “biscresolfluorene”) as the aromatic dihydroxy component, described by the following formula (1):

Component b

The polycarbonate copolymer of the present invention is obtained by using an aromatic dihydroxy component as the copolymerizable component described by the following formula (2):

where R ^a -R ^d each independently represents a hydrogen atom, a hydrocarbon group that may contain an aromatic group having from 1 to 9 carbon atoms, or a halogen atom, a W represents a single bond, a hydrocarbon group that may contain an aromatic group, having from 1 to 20 carbon atoms, or the group O, S, SO, SO ₂ , CO or COO.

As such an aromatic dihydroxy component, it is possible to use any component that is generally used as the dihydroxy component of a polycarbonate. Illustrative examples of the component include 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2- bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-tert-butyl-4- hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis ( 3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bi (3,5-Dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1 bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (4-hydroxyphenyl) cyclopentane, 4 4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy- 3,3'-dimethyldiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxy-3,3 '-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyl diphenyl sulfone, 4,4'-dihydroxy-3,3'-diphenyl diphenyl sulfide, 4,4'-dihydroxy-3,3'-diphenyl diphenyl sulfoxide, 1,3- bis {2- (4-hydroxyphenyl) propyl} benzene (bisphenol M) and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene.

Of these, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), described by the following formula (2-1), 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene ("bisphenol M "), described by the following formula (2-2), and 2,2-bis (4-hydroxy-3-methylphenyl) propane (" bisphenol C "), described by the following formula (2-3).

Other copolymerizable components

In addition, the polycarbonate copolymer of the present invention can be a branched polycarbonate copolymer obtained by copolymerization with a phenolic compound having three or more functional groups.

Illustrative examples of a phenolic compound having three or more functional groups include phloroglucinol, phloroglucid, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2,4,6-dimethyl-2,4,6 tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 2,2-bis (4,4-bis (4 -hydroxyphenyl) cyclohexyl) propane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2,6-bis (2-hydroxy-5-isopropylbenzyl) -4-isopropylphenol, bis (2-hydroxy -3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl) methane, tetrakis (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) phenylmethane, tr sfenol, 2,2-bis (2,4-hydroxyphenyl) propane, bis (2,4-dihydroxyphenyl) ketone and 1,4-bis (4,4-digidroksitrifenilmetil) benzene. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane is preferred. They can be used individually or as a combination of two or more. A phenolic compound having three or more functional groups is preferably used in an amount of from 0.01 to 5 mol%, more preferably from 0.1 to 3 mol%, based on the total amount of aromatic dihydroxy components and a branched polycarbonate copolymer is obtained, characterized in excellent rigidity.

The present invention relates to heat-resistant parts consisting of the above copolymer. Illustrative examples of heat-resistant parts include parts for reflow soldering, parts for converting the path of a light beam, optical discs, plastic mirrors, and trays for transporting electronic parts.

First aspect: parts for reflow soldering

The first aspect of the present invention relates to a part for reflow soldering with good transparency, which does not undergo deformation during brazing in a furnace for reflow solder.

In the field of technology related to electronic components, along with reducing the size and improving the performance of electronic devices, and improving productivity, surface mounting technology (SMT) is becoming popular as a way to install various electronic parts on substrates, which allows for high density installation of parts and is highly efficient.

Surface mounting technology means the technology of fixing electronic parts on a printed circuit board by placing electronic parts on a circuit board using a creamy consistency solder, and then passing the printed circuit board through a heating furnace (solder reflow oven) to melt the solder.

Illustrative examples of methods that are primarily used as a method of heating a substrate in a solder reflow oven include a conventional heat transfer method using hot air, including passing the board through hot air, which is forced circulation, a method using far infrared radiation, including heating the board under the action of far infrared radiation from the upper side of the board or both from the upper and lower sides of the board, and a method comprising heating the board under the action of a combination of hot air and far infrared radiation. When soldering, the temperature of the printed circuit board and electronic parts introduced into the furnace for reflowing the solder reaches high values in the range from 220 to 270 ° C.

Among electronic parts, there are parts that should be characterized by the presence of transparency, such as lenses, prisms and transparent caps. Despite the fact that at present, given the existence of the problem of heat resistance, these parts are made of glass or thermosetting polymer, there is a problem in that they take some time to form. Accordingly, thermoplastic polymers exhibiting heat resistance during flash brazing and easy formability are desirable. However, such materials for which there would be a balance of heat resistance during fusion soldering of solder and optical properties are still unknown.

An object of the first aspect of the present invention is to provide a reflow solder part exhibiting heat resistance during reflow soldering and excellent transparency and formability.

Polycarbonate copolymer

The polycarbonate copolymer constituting the reflow solder part of the first aspect of the present invention contains repeating units (component a) described by the general formula (I) in an amount of from 60 to 95 mol%, preferably from 65 to 90 mol%, more preferably from 70 to 85 mol%, and repeating units (component b) described by the general formula (II-1), in an amount of from 40 to 5 mol%, preferably from 35 to 10 mol%, more preferably from 30 to 15 mol.%.

If the amount of component a is less than 60 mol.%, Then the heat resistance of the part for reflow soldering may be unsatisfactory. Meanwhile, if the amount of component a is greater than 95 mol%, the copolymer will exhibit poor melt flow and will be difficult to mold, and the product formed from it will exhibit poor transparency.

Specific viscosity

The polycarbonate copolymer is preferably characterized by a specific viscosity of from 0.17 to 0.55, more preferably from 0.21 to 0.45, when measured at 20 ° C. for a solution of 0.7 g of the copolymer in 100 ml of methylene chloride.

Glass transition temperature

The polycarbonate copolymer is preferably characterized by a glass transition temperature (Tg) of 200 to 250 ° C. as measured at a temperature increase rate of 20 ° C./min. Tg is more preferably in the range from 205 to 245 ° C. If Tg is below 200 ° C, then during the reflow soldering, the heat resistance of the optical part molded using the copolymer will be unsatisfactory, while if the temperature is higher than 250 ° C, the copolymer will have a high melt viscosity, and in some cases, it may turn out to be difficult to work with.

Volumetric melt flow rate

The polycarbonate copolymer preferably shows a melt volume flow rate (MVR), measured at 320 ° C under a load of 1.2 kg in accordance with JIS K-7210 of at least 0.2 cm ^3/10 min, more preferably 0.5 cm ^3/10 min.

Specific examples of reflow solder parts of the present invention include lenses and caps for various indicator lights; camera lenses and lens mounts for mobile phones with integrated cameras; lenses and caps for light emitting elements such as diodes; caps and sealants for various devices, such as transistors and rectifiers; caps and sealants for sensors, ICs (integrated circuits) and the like, and spectral separation / summing devices, such as optical waveguides and fiber optic cables, for example, prisms. The parts for reflow soldering of the present invention are particularly suitable for lenses, lens frames and prisms.

Parts for reflow soldering are molded by any method, such as injection molding method, direct compression method, injection molding method, extrusion method and solution casting method.

Optical parts require transparency for different wavelengths according to the application. For example, caps and sealants require transparency for visible light (400 to 700 nm). For lenses and caps for light-emitting elements, such as diodes, transparency is required for the wavelengths of light emitted by the elements. In addition, wavelengths from 1300 to 1600 nm are used for fiber-optic communications, and transparency for these wavelengths is required for spectral separation devices, such as prisms for spectral separation in the case of fiber-optic cable.

The polycarbonate copolymer used in the present invention exhibits good transparency at any of these wavelengths. A test sample with a thickness of 1.0 mm, which was molded from a polycarbonate copolymer, preferably had a transmittance of 60% or more, more preferably 70% or more, at each of the following wavelengths, i.e. at 400 nm, 500 nm , 600 nm, 700 nm, 1300 nm, 1400 nm, 1500 nm and 1600 nm.

The reflow solder of the solder of the present invention does not deform even after processing in the solder reflow oven with such a preset that the peak temperature of 250 ° C. continues for 5 seconds.

Second aspect: detail for transforming the path of a ray of light

A second aspect of the present invention relates to a part for converting a path of a light beam exhibiting good heat resistance and thermal stability, very little birefringence and excellent transparency.

To date, several polymethyl methacrylate polymers have been used as optical materials, such as materials for manufacturing lenses, optical fiber plates, and the like, since they exhibit good transparency and low birefringence. However, given the increase in recent years, the need to improve the heat resistance of polymers from the point of view of increasing the compactness of electronic equipment and safety can hardly be said that the polymethylmethacrylate polymer has sufficient heat resistance.

Meanwhile, in various applications, including optical materials, polycarbonate polymers are used, which is caused by high transparency and the ability to maintain dimensions. However, taking into account the properties necessary for optical elements requiring optical accuracy, such as lenses, prisms, optical fiber plates, and optical fibers, it is currently difficult to develop an option for using polycarbonate polymers in optical elements, since polycarbonate polymers belong to the group of ordinary plastics, which demonstrate quite pronounced birefringence due to the orientation of the molecular chain, and which are characterized by the presence of significant deformation caused by molding.

As a way to improve the birefringence of a polycarbonate polymer, a method for grafting the copolymerization of a polycarbonate polymer and a styrene-based polymer is proposed (JP-A 61-19630 and 63-15822). However, a grafted copolymer containing a polycarbonate polymer and a styrene-based polymer has low mechanical strength, it is very fragile, and it is difficult to form due to poor thermal stability, and in order to improve its mechanical strength, its molecular weight must be increased. However, simultaneously with an increase in molecular weight, its formability and surface accuracy deteriorate, so that lenses that are useful in practice cannot be obtained.

As an improved method without causing the above-mentioned problem of the above-mentioned method, a method for mixing a polycarbonate polymer containing an aromatic dihydroxy component, such as bis (4-hydroxy-3,5-dimethylphenyl) propane, with an acrylonitrile styrene copolymer (JP-A 5- 027101). However, despite the fact that this polymer composition is characterized by improved transparency and birefringence, it has a problem in that it has low thermal stability and is very difficult to form.

In addition, it was reported (JP-A 6-018701) about a lens with improved heat resistance and a high refractive index, which contains a polycarbonate copolymer containing an aromatic dihydroxy component with a fluorenone scaffold inserted therein. However, this publication describes improvements in heat resistance and refractive index, but does not mention a specific improvement in the birefringence situation.

The second aspect of the present invention is the creation of an optical molded product, characterized by the presence of very little birefringence and excellent transparency.

The inventor of the present invention has found that a polycarbonate copolymer obtained using a specific diatomic phenol in a specific amount is characterized by very little birefringence, and that the part molded from the polycarbonate copolymer has suitable optical properties.

Polycarbonate copolymer

The polycarbonate copolymer constituting the part for converting the light path of the second aspect of the present invention contains repeating units (component a) described by general formula (I) in an amount of from 50 to 95 mol%, preferably from 65 to 75 mol%, and repeating units (component b) described by the general formula (II) in an amount of from 50 to 5 mol%, preferably from 35 to 25 mol%.

Particularly preferred is a polycarbonate copolymer containing repeating units (component a) described by the general formula (I) in an amount of from 50 to 95 mol% and repeating units (component b) described by the general formulas (II-1) and / or ( II-2), in an amount of from 50 to 5 mol.%.

Re ₅₅₀

The molded plate polycarbonate copolymer is preferably characterized by a transmission at 550 nm of 80% or more, and preferably its characteristics satisfy the following expression:

Re ₅₅₀ / d≤10,

if the delay at 550 nm is denoted by Re ₅₅₀ (nm), and the thickness of the section on which the transmission and delay are measured, indicate d (mm).

An optical element containing a polycarbonate polymer, similar in type to a conventional polymer from bisphenol A, generally exhibits a high delay, and in some cases its value can be reduced by changing the molding conditions. However, the range of conditions is generally very small, so molding is very difficult to carry out, and the characteristics of a conventional polycarbonate polymer often cannot satisfy the above expression. Meanwhile, the polycarbonate copolymer used in the present invention is characterized by a low delay caused by orientation in the polymer and a low degree of deformation caused by molding, so that a good optical element can be obtained from it without strictly specifying the molding conditions.

Skipping

The molded plate is preferably characterized by a transmission (T ₅₅₀ ) at 550 nm of 80% or more, more preferably 85% or more. Transmission is measured using a U-4001 type spectrophotometer from Hitachi, Ltd.

Specific viscosity

The polycarbonate copolymer is preferably characterized by a specific viscosity of from 0.17 to 0.55, more preferably from 0.21 to 0.45, when measured at 20 ° C. after dissolving 0.7 g of the polymer in 100 ml of methylene chloride.

Glass transition temperature

The polycarbonate copolymer is preferably characterized by a glass transition temperature (Tg) of from 150 to 250 ° C. as measured at a temperature increase rate of 20 ° C./min. Tg is more preferably in the range from 160 to 245 ° C.

5% weight reduction temperature

The polycarbonate copolymer is preferably characterized by a mass reduction temperature of 5% (Td), used as an indicator of heat resistance of 450 ° C or more, more preferably 480 ° C or more, when measured at a temperature increase rate of 20 ° C / min. If the temperature of reducing the mass by 5% is less than 450 ° C, then during the molding, intense thermal decomposition will occur, and therefore it will be difficult to obtain a good molded product, which is disadvantageous.

Photoelasticity coefficient

The polycarbonate copolymer is preferably characterized by a photoelasticity coefficient of 50 × 10 ¹³ cm ² / dyn or less, more preferably 45 × 10 ¹³ cm ² / dyn or less. If the photoelasticity coefficient is greater than 50 × 10 ¹³ cm ² / dyn, then the deformation caused by molding will be large, and therefore, in some cases it may be difficult to use the resulting molded product as a part for converting the path of the light beam.

Volumetric melt flow rate

The polycarbonate copolymer preferably has a melt flow volume rate (MVR), measured at 340 ° C under a load of 1.2 kg in accordance with JIS K-7210, at least equal to 1.0 cm ^3/10 min, more preferably at least equal to 1.5 cm ^3/10 min.

A detail for converting the trajectory of a light beam denotes a lens, a prism, plates of optical fibers and a optical fiber, which are optical elements used as parts for optical equipment. More specifically, a lens means any lens that has two spherical or non-spherical refractive surfaces and through which light has the ability to pass. Illustrative examples of lenses include spherical lenses, non-spherical lenses, Fresnel lenses and micro-raster lenses.

Meanwhile, a prism means any molded product having at least two polished surfaces that are at least non-parallel to each other and are at some angle to each other. Illustrative examples of a prism include a rectangular prism, a Porro prism, a direct prism prism, a pentagonal prism, a Dobress prism, a Henzolt prism, a Spreng prism, a Moler prism, a Wollaston prism, an inclined prism and an Abbe prism.

A part for converting the trajectory of the light beam is formed by any method, such as an injection molding method, a direct compression method, an injection molding method, an extrusion method, and a solution casting method. From the point of view of ease of molding and cost, the part for converting the trajectory of the light ray is particularly preferably molded by injection molding or injection molding.

A component for converting the path of a light beam, such as a molded plate, is preferably characterized by a transmission at 550 nm of 80% or more, more preferably 85% or more.

Since the light beam converting part of the present invention has the good optical properties described above, it can suitably be used as an optical element for electrical and electronic equipment such as a camera, digital camera, liquid crystal display, liquid crystal projector, copy machine and equipment associated with working with optical disks, and as a part for converting the trajectory of a ray of light, such as a splitter and and integrator, it can be used in optical communication equipment.

The detail for converting the path of the light beam is preferably a sensor lens, a camera lens, a micro-raster lens, a projector lens, or a prism.

The beam converting part of the light beam of the present invention is characterized by good heat resistance and thermal stability, very little birefringence and excellent transparency.

Third aspect: optical disk

A third aspect of the present invention relates to an optical disk characterized by excellent stiffness and resistance to water absorption.

In conventional optical discs (hereinafter abbreviated as "CDs"), such as CD (compact disc) and CD-ROM (read-only memory on CD), on one surface of a transparent substrate with a thickness of 1.2 mm form embossed recesses corresponding to the recorded data, and, in addition, a reflective film made of Al and the like is formed on this surface. The data recorded on such a CD-ROM is reproduced as a result of illumination by a focused beam of another surface of a transparent substrate on which a reflective film is not formed.

In contrast, DVDs (digital video discs) and DVD-ROMs (read-only memory on digital video discs) (hereinafter abbreviated as "DVDs"), characterized by higher recording densities, on one surface of a transparent substrate with a thickness of 0 , 6 mm form a more miniature embossed recesses in comparison with the recesses for the CD, and, in addition, a reflective film made of Al and the like is formed on this surface. As with a CD, data recorded on the recording surface of such a DVD is reproduced when the focused beam illuminates another surface of a transparent substrate on which no reflective film is formed.

As a substrate material with a thickness of 0.6 mm, PC (polycarbonate), which is a transparent polymeric material, is generally used. A PC substrate with a thickness of 0.6 mm is itself characterized by insufficient mechanical properties and undergoes warpage. Therefore, joint lamination of two PC substrates with a thickness of 0.6 mm is made so that their recording surfaces are in contact with each other. In this way, mechanical properties are ensured since the total thickness of the disc becomes 1.2 mm.

The reason why the thickness of the substrate of the DVD is 0.6 mm is to ensure the maximum angular deviation. As the pitch between the tracks and the density of the recesses increase, the limit for the angular deviation at the disc decreases. The value of the limiting angular deviation can be guaranteed by reducing the thickness of the substrate from 1.2 mm to 0.6 mm. However, since the elastic modulus of the substrate is proportional to the cube of its thickness from the point of view of the strength of the materials, it is impossible to avoid the deterioration in the angular deviation that occurs during the manufacture of the substrate.

Meanwhile, in order to increase, in addition to the density increase mentioned above, in optical disks the data transfer speed during their writing and reading, rotation of the disk substrate with an increased speed can no longer be avoided.

However, in the case of the structure of the optical disks mentioned above, it is difficult to avoid distortion for the following reasons (1-4):

(1) In injection molding: under the action of shear stress, stress arises when the polymer flows into the mold cavity (distortion of the orientation of the molecules).

(2) Completion of filling: when the polymer fills the mold cavity, the flow of the polymer will immediately end, since the movement of the screw will stop quickly, as a result, the inertia of the polymer and the screw will affect the substrate.

(3) Pressure retention: since until the injection gate is closed during injection of the polymer, the pressure is applied to the polymer to prevent the polymer from flowing back and to prevent runoff caused by volume reduction in the substrate mass pressure distribution.

(4) Cooling: due to thermal shrinkage, a voltage corresponding to the temperature distribution occurs.

Accordingly, in order to improve the structure of the optical discs mentioned above, an “optical recording medium is proposed in which at least a recording layer and a transparent protective layer are sequentially formed on a substrate, and to which light is supplied from the transparent protective side a layer for recording and / or reproducing data signals, wherein the aforementioned substrate includes a first polymer layer that forms a surface on which the aforementioned recording layer is formed, and a second polymer layer which is laminated to the aforementioned first polymer layer and which includes a polymer material having a higher flexural modulus compared to a polymer material forming the first polymer layer mentioned above (JP-A 11-242829).

Meanwhile, even if the problem of mechanical properties is solved using the above-mentioned improvements, optical disks that use only one side surface for recording and reproducing signals will undergo deformation due to water absorption caused by changes in temperature and humidity in the environment.

In the case of DVDs, a conventional polycarbonate substrate is used, characterized by a water absorption of 0.3 wt.% Or more. However, since 0.6 mm thick discs are connected to each other so that their signal sides are in contact with each other, a good balance of water absorption is achieved even when water absorption is large, so that the resulting DVD whether it will be deformed. However, since in the case of high density disks with a high numerical aperture (N.A.), the signals are on one side of the surface layer, the balance of water absorption changes, so that the problem of deformation due to moisture absorption remains. In particular, there is the possibility of a sharp change during the operation of the drive, because due to the operation of the drive the temperature in the device will be high and the humidity in it will be low, and it is likely that a focusing error will occur in which the signals cannot be read due to deformation of the disk.

In order to suppress the occurrence of such deformation caused by water absorption, a “disc-shaped recording medium that includes a substrate, a recording layer formed on the substrate to record data signals, and a transparent protective layer laminated to the recording layer are proposed. , and in which data signals are recorded and reproduced as a result of the light coming from the transparent protective layer, the substrate including a middle layer obtained from a polymer and a surface obtained from a polymer a distinct layer, while the surface layer is integrated with the middle layer, having recesses and protrusions on one surface corresponding to the data signals of the recording layer, and characterized by higher fluidity in comparison with the middle layer ", while using in the surface layer of the substrate a polymer characterized by water absorption equal to 0.3 wt.% or less (JP-A 2000-11449). The proposal recommends solving the problem when using a complicated configuration of the substrate, formed by the methods of two-color molding, or sandwich molding.

Thus, in order to increase the recording density, to guarantee a sufficient limiting angular deviation and mechanical strength and to prevent the occurrence of deformation due to water absorption caused by changes in temperature and humidity in the environment, the configuration of the substrate has become very complicated.

A potential reason for this is the lack of available polymers having the satisfactory properties required for the polymer used as a substrate material in the development of an optical disk, i.e., rigidity, damping, heat resistance, and water absorption capacity. In particular, in the case of research projects in the field of polycarbonate-based polymers, which are widely used as materials for optical disks, in order to improve the optical properties of the most widely used polycarbonate polymer, in which 4,4'-dihydroxyphenylpropane is bound by carbonate bonds, A wide range of polycarbonate-based polymers has been developed (e.g., JP-A 2000-327767).

However, as described above, the development of polycarbonate polymers, characterized by improved stiffness, water absorption, damping and heat resistance, is still unsatisfactory, and the creation of an optical disc with a simpler design and high recording density when using a polymer is most urgently desired. , which will simplify the layout of the substrate for recording, including also characterized by formability.

An object of the third aspect of the present invention is to provide an optical disk characterized by a simple structure and excellent rigidity, damping, heat resistance and water absorption capacity.

Structure

The optical disk of the present invention is an optical disk that includes a substrate with a thickness in the range of 0.3 to 1.2 mm, on which there are embossed recesses or guide grooves, a reflective layer formed on the substrate, and a transparent protective layer with a thickness of 3 up to 200 μm, which is formed on the reflective layer and which reproduces the recorded data on the mechanism of changing the light intensity of the reflected light obtained by illuminating the disk by starting the light from the side of the transparent protective layer.

For example, the optical disk of the present invention shown in FIG. 1 is formed by successively laminating a reflective layer 3, a recording layer 4 and a transparent protective layer 5 on a substrate 2 having guide grooves (optical disk 1). Phase depressions are formed on the upper surface of the substrate 2 for recording data and tracking servo signals and guide grooves forming a pattern with a given uneven arrangement of elements, such as miniature depressions and protrusions, for example, pre-marked grooves.

In addition, the optical disk 2 shown in FIG. 2 is characterized by such a multilayer structure that the recording film or the reflective layer and the transparent protective layer are laminated several times on the substrate 2 having guide grooves. For the manufacture of substrates, reflective layer, layers for recording and transparent protective layers forming these discs, you can use materials that have the same or similar properties.

The optical disc preferably has a recording layer located between the reflective layer and the transparent protective layer. In addition, the embossed recesses or guide grooves are preferably formed on both surfaces of the substrate of the optical disk; a reflective layer, a recording layer and / or a transparent protective layer are also formed on both of its surfaces. In addition to this, the optical disk is preferably characterized by the presence of a multilayer structure, so that the lamination layer for recording or reflective layer is performed several times. In addition, the transparent protective layer of the optical disk of the present invention preferably forms the same polycarbonate copolymer as the polycarbonate copolymer forming the substrate.

Polycarbonate copolymer

The polycarbonate copolymer used as the material of the optical disk of the present invention contains from 20 to 95 mol%, preferably from 25 to 70 mol%, more preferably from 30 to 60 mol%, repeating units (component a) described by the general formula (I).

Another component of the copolymer comprises from 80 to 5 mol.%, Preferably from 75 to 30 mol.%, More preferably from 70 to 40 mol.%, Repeating units (component b) described by the general formula (II).

If the proportion of repeating units described by the general formula (I) is less than 20 mol%, then an optical disk can be obtained that is characterized by poor transparency, heat resistance, mechanical physical properties, birefringence for an irregularly incident light beam, water absorption, stiffness, and ability to data transfer or warping.

In order to obtain the desired fluidity, stiffness and resistance to water absorption, the polycarbonate copolymer used in the present invention must contain a certain number of repeating units (component a) described by the general formula (I), and also contain repeating units as another component (component b) described by the general formula (II).

A polycarbonate copolymer containing from 20 to 95 mol% of the repeating units described by the formula (I) and from 80 to 5 mol.% Of the repeating units described by the general formula (II-2) and / or the repeating units described is particularly preferred general formula (II-3).

A polycarbonate copolymer containing from 20 to 70 mol%, preferably from 30 to 60 mol%, repeating units described by the general formula (I), and from 80 to 30 mol%, preferably from 70 to 40 mol, is particularly preferred. .%, repeating units described by the general formula (II-2).

In addition, a polycarbonate copolymer containing from 20 to 70 mol.%, Preferably from 30 to 60 mol.%, Repeating units described by the general formula (I), and from 80 to 30 mol.%, Preferably from 70 to 40, is preferred. mol.%, repeating units described by the general formula (II-3).

In the optical disk of the present invention, the substrate is characterized

(A) a modulus of elasticity in bending from 2800 to 4000 MPa,

(B) water absorption equal to 0.3 wt.% Or less upon reaching saturation,

(C) a tanδ value measured at 40 ° C and 18 Hz in accordance with ISO 6721-4 of at least 0.020, and

(D) deformation resistance, measured under a load of 1.81 MPa in accordance with ISO 75-1, -2, equal to 110 ° C or more.

Flexural modulus

A polycarbonate copolymer is characterized by a bending modulus measured in accordance with ISO 178, ranging from 2800 to 4000 MPa, more preferably from 2900 to 3900 MPa, much more preferably from 3100 to 3900 MPa. If the bending elastic modulus is less than 2800 MPa, then during the rotation of the formed optical disk with high speed, the surface will oscillate with a significant amplitude, which is undesirable for an optical disk with a storage capacity with a high recording density. Meanwhile, if the bending elastic modulus exceeds 4000 MPa, a brittle optical disk will be obtained, and it may turn out to be difficult to form.

Water absorption

The polycarbonate copolymer is characterized by water absorption, measured in accordance with ISO 62 when saturation at 23 ° C is achieved, equal to 0.3 wt.% Or less, preferably 0.28 wt.% Or less. If the water absorption exceeds 0.3 wt.%, Then the probability of warping due to water absorption of the optical disk with a metal film formed on the surface of the substrate of the optical disk will appear, and therefore, tracking errors will become likely. Particularly preferably, water absorption equal to 0.27 wt.% Or less.

tanδ

The polycarbonate copolymer is characterized by a tanδ measured at 40 ° C. and 18 Hz in accordance with ISO 6721-4, at least equal to 0.020, more preferably at least equal to 0.025, much more preferably at least equal to 0.027. If the tanδ value is less than 0.020, then the damping of the polymer will be insignificant, so that when the formed optical disk rotates at high speed, the surface will oscillate with a significant amplitude, which is disadvantageous.

Deformation resistance

The polycarbonate copolymer exhibits a deformation resistance resistance measured under a load of 1.81 MPa in accordance with ISO 75-1, -2, equal to 110 ° C or more, preferably 115 ° C or more, more preferably 120 ° C or more. If the deformation resistance is low, then the temperature resistance of the disk will be unsatisfactory. The deformation resistance is generally 150 ° C. or less, preferably 140 ° C. or less, if the polycarbonate copolymer is used in conventional injection molding.

Specific viscosity

The polycarbonate copolymer preferably exhibits a specific viscosity of from 0.1 to 0.5, more preferably from 0.15 to 0.4, when measured at 20 ° C. after dissolving 0.7 g of the copolymer in 100 ml of methylene chloride. If specific viscosity falls within the above range, the polycarbonate copolymer will have good melt flow and excellent formability.

Warping

To measure the warping of the optical disk during the processes of water absorption and drying, the following measurement method was used. Namely, after the disk was exposed to the environment (environment A), where the temperature was 30 ° C and the humidity corresponded to 90% relative humidity, until the saturation by water absorption was reached, the disk was transferred to the environment (environment B), where the temperature was 23 ° C and the humidity corresponded to 50% relative humidity, over time, we measured the change in angular deviation at a distance of 58 mm from the center, which arose as a result of changes in the environment, and the maximum Ichin change the angular deviation and the value at which the change of the angular deviation reaches the steady-state values were compared with each other to determine the difference (ΔTilt). In this case, the ΔTilt of the optical disc is within 1.00 degrees, preferably within 0.75 degrees, more preferably within 0.60 degrees.

In addition, since in the case of the optical disc of the present invention, data signals are recorded and reproduced when light comes from the transparent protective layer 5, the substrate 2 does not affect the characteristics of the optical recording and reproduction, and it does not require transparency. Despite the fact that the mixture material formed from at least two polymers, characterized by significantly different refractive indices, it was still not easy to use as a substrate material for CD, DVD, or the like, for which conventional optical properties, since the mixture material is characterized by the presence of turbidity due to light scattering, even such a mixture material as described above can be used in the substrate 2 of the present invention.

Other thermoplastic polymers and additives, such as a stabilizer, a dye, an antistatic agent and a lubricant, can be added to the substrate of the optical disk of the present invention in such quantities that do not impair the ability to transmit data and the effect of reducing the degree of warpage in the processes of water absorption and drying of the formed disk.

As a mixing method, for example, for a polymer solution, first of all, it is possible to imagine the use of a container equipped with a mixer, and for a molded product, such as powder or granules, the method of mixing using a drum mixer, a V-shaped mixer, a Noether mixer, a Banbury mixer, a plasticizing roll, an extruder, and the like. In any case, you can use any method. However, taking into account the ease of removal of foreign material mixed during the implementation of the mixing method, a method is preferred that involves passing the resulting mixture after mixing in the state of the polymer solution through a filter having suitable openings.

In addition, in the extrusion stage (granulation stage) during the preparation of the polymer composition in the form of granules for injection molding, in order to remove foreign material, the molten polymer is preferably passed through a sintered filter with a filter fineness of 50 μm or less. If necessary, the addition of an additive such as a phosphorus-based antioxidant is also preferred. In any case, the content of foreign materials, impurities and solvents in polymer raw materials must be reduced to a minimum before injection molding.

The method of obtaining an optical disk

Next, a method for producing an optical disc will be described.

The substrate of the optical disk is obtained from the polycarbonate copolymer mentioned above by the injection molding method using an injection machine (including an injection molding machine) equipped with a matrix characterized by a degree of surface roughness and the presence of recesses and grooves that satisfy the technical conditions required for optical disks. In this case, the thickness of the substrate of the disk is in the range from 0.3 to 1.2 mm.

An injection molding machine may be a machine that is generally used. However, from the point of view of suppressing the formation of carbides and increasing the reliability of the substrate of the disk, it is preferable to use a machine in which the cylinder and screw exhibit low adhesion to the polymer and which is made of a material having corrosion and abrasion resistance. For the purpose of the present invention, the environment in the molding step is preferably as clean as possible. In addition, it is important to completely dry the molded material in order to remove water, and you need to be careful not to save moisture, which can cause decomposition of the molten polymer.

After that, in order to obtain an optical disk, at least one reflective film is formed on one surface of the substrate of the optical disk. As a material for it, metal elements can be used individually or as a combination of two or more. Among them, it is preferable to use one Al, one Au, Al alloy containing from 0.5 to 10 wt.%, Particularly preferably from 3.0 to 10 wt.% Ti, or Al alloy containing from 0.5 to 10 wt. .% Cr. In addition, a reflective film can be formed using methods such as ion beam sputtering, direct current sputtering, or high frequency sputtering.

In general, in order to obtain an optical disc of the present invention, in addition to this thin metal film (reflective layer), a recording layer 4 (phase transition film or dye in the case of DVD-RAM (random access memory device on a digital video disc) is usually formed ) and DVD-R (recordable digital video disc) and a film for magneto-optical recording in the case of a magneto-optical disc) and a transparent protective layer 5.

As a phase transition film, for example, a chalcogen or a chalcogen compound is used. More specifically, Te, Se and chalcogenite-based materials are used, such as Ge-Sb-Te, Ge-Te, In-Sb-Te, In-Se-Te-Ag, In-Se, In-Se-Tl-Co , In-Sb-Se, Bi ₂ Te ₃ , BiSe, Sb ₂ Se ₃ and Sb ₂ Te ₃ .

In addition, a film with a perpendicular magnetic texture having magneto-optical properties such as the Kerr effect and the Faraday effect, for example a thin film of an amorphous alloy such as Tb-Fe-Co, is used as a film for magneto-optical recording.

After that, a transparent protective film 5 was formed on the recording layer 4. A transparent protective film 5 was obtained from a material through which the laser beam was able to pass. Illustrative examples of the material include thermoplastic polymers such as polycarbonate and an amorphous polyolefin polymer, and thermosetting polymers. In particular, a polycarbonate polymer containing biscresolfluorene in an amount of at least 20 mol%, based on the total amount of aromatic dihydroxy components, is suitably used.

Illustrative examples of methods for forming a transparent protective film include a method comprising applying a sheet made of a thermoplastic polymer, such as polycarbonate or an amorphous polymer based on a polyolefin, or a transparent plate, such as a glass plate, onto a recording layer 4, and a method comprising applying ultraviolet curable polymer coatings according to a technique such as centrifugal coating, and then polymer coated coating with ultraviolet rays to obtain a transparent protective film. In addition, the thickness of the transparent protective film is limited to 3 to 200 μm in order to maintain the degree of coma at the lowest possible level.

Although the basic structure of the optical disk of the present invention has already been described in the presentation, dielectric layers can be introduced into the structure to control the optical properties and thermophysical properties. In this case, a reflective layer 3, a first dielectric layer, a recording layer 4, a second dielectric layer and a transparent protective layer 5 are sequentially formed on the substrate 2.

The optical disc of the present invention is suitable for use as a recording medium, characterized by excellent stiffness, damping, heat resistance and water absorption, and having a recording capacity with high density.

Fourth Aspect: Plastic Mirror

A fourth aspect of the present invention relates to a plastic mirror. More specifically, it relates to a plastic mirror formed from a polycarbonate copolymer, which is characterized by excellent bending modulus, fluidity, resistance to water absorption and heat resistance, and which is able to very accurately print on the surface of the mold.

Polycarbonate polymers are widely used in various fields because they are characterized by excellent transparency, heat resistance, mechanical properties and the ability to maintain dimensions. In recent years, they have been actively used for the manufacture of plastic mirrors in connection with such an advantage as transparency.

Meanwhile, in order to correspond to recent reductions in mass, thickness, length and size and high-speed rotations occurring for a rotating mirror, it is desirable that the polymers exhibit improved melt flowability, the ability to print in the form, the ability to maintain dimensions and rigidity.

In addition, for plastic mirrors, the need for a higher dimensional stability due to water absorption is becoming ever more urgent.

An object of the fourth aspect of the present invention is to provide a plastic mirror that is satisfactory in terms of stiffness, resistance to water absorption, modulus of elasticity in bending, and ability to accurately print in a mold, and has excellent melt flow and heat resistance.

The plastic mirror of the fourth aspect of the present invention includes a polycarbonate substrate and a metal reflective film, the polycarbonate substrate includes a polycarbonate copolymer, the polycarbonate copolymer containing from 20 to 70 mol.%, Preferably from 30 to 60 mol.%, Repeating units (component a), described by the general formula (I), and from 80 to 30 mol%, preferably from 70 to 40 mol%, repeating units (component b), described by the general formula (II-1) and / or the general formula (II-2) wherein the polycarbonate substrate is character rizuetsya

(A) glass transition temperature from 120 to 230 ° C,

(B) water absorption equal to 0.2 wt.% Or less after immersion in water at 23 ° C for 24 hours, and

(C) the modulus of elasticity in bending from 2500 to 4000 MPa.

The plastic mirror is preferably such that the polycarbonate copolymer preferably contains from 20 to 70 mol.%, Preferably from 30 to 60 mol.%, Repeating units (component a) described by the general formula (I), and from 80 to 30 mol.%, preferably from 70 to 40 mol.%, repeating units (component b) described by the general formula (II-1), and that the polycarbonate substrate is characterized by the following properties, namely

(A) a glass transition temperature of from 160 to 230 ° C,

(B) water absorption equal to 0.2 wt.% Or less after immersion in water at 23 ° C for 24 hours, and

(C) the modulus of elasticity in bending from 2500 to 3500 MPa.

The plastic mirror is also preferably such that the polycarbonate copolymer preferably contains from 20 to 70 mol.%, Preferably from 30 to 60 mol.%, Repeating units (component a) described by the general formula (I), and from 80 to 30 mol.% , preferably from 70 to 40 mol.%, repeating units (component b) described by the general formula (II-2), and that the polycarbonate substrate is characterized by the following properties, namely

(A) a glass transition temperature of from 120 to 180 ° C,

(B) water absorption equal to 0.1 wt.% Or less after immersion in water at 23 ° C for 24 hours, and

(C) the modulus of elasticity in bending from 2800 to 4000 MPa.

Glass transition temperature

The polycarbonate copolymer is characterized by a glass transition temperature from 120 to 230 ° C.

Water absorption

The polycarbonate copolymer is characterized by water absorption, measured in accordance with ISO 62 after immersion in water at 23 ° C for 24 hours, equal to 0.2 wt.% Or less, preferably 0.1 wt.% Or less. If the water absorption will exceed 0.2 wt.%, Then a plastic mirror with a reflective film formed on a substrate for a plastic mirror will tend to warpage due to water absorption, which is disadvantageous. Particularly preferably, water absorption equal to 0.085 wt.% Or less.

Flexural modulus

A polycarbonate copolymer is characterized by a bending modulus measured in accordance with ISO 178, equal to from 2500 to 4000 MPa, more preferably from 2800 to 4000 MPa, much more preferably from 2500 to 3500 MPa. If the bending elastic modulus is less than 2500 MPa, then due to insufficient stiffness it will be difficult to reduce the thickness of the molded product. Meanwhile, if the bending elastic modulus exceeds 4000 MPa, then a brittle substrate for a plastic mirror will be formed, and it may turn out to be difficult to form.

Specific viscosity

The polycarbonate copolymer preferably exhibits a specific viscosity of from 0.1 to 0.5, more preferably from 0.15 to 0.4, when measured at 20 ° C. after dissolving 0.7 g of the copolymer in 100 ml of methylene chloride. In the case where the specific viscosity falls into the above range, the polycarbonate copolymer will have good melt flow and excellent formability; in the best case, a molded article having satisfactory optical power is obtained.

Fluidity

The polycarbonate copolymer preferably shows a flowability expressed as the MVR value obtained in the measurement conditions of 300 ° C and 1.2 kg of 5 cm ^3/10 minutes or more, more preferably 20 ^cm3 / 10 minutes or more, much more preferably 30 cm ^3/10 minutes or more.

Other copolymerizable components

In a polycarbonate copolymer, components a and b are desirably at least 80 mol%, preferably at least 90 mol%, based on the total amount of aromatic dihydroxy components. However, the polycarbonate copolymer may also contain other dihydroxy components in an amount not exceeding 20 mol%, preferably not exceeding 10 mol%, based on the total amount of aromatic dihydroxy components.

Other copolymerizable components may be any components other than component a and component b, which are commonly used as dihydroxy components of aromatic polycarbonate. Illustrative examples of such copolymerizable components include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl ) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4 '- (p- phenylenediisopropylindene) diphenol, 9,9-bis (4-hydroxyphenyl) fluorene and 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane.

Metal reflective film

As the metal reflective film, a thin film obtained from aluminum or the like is used.

The material for molding a plastic mirror of the present invention is generally obtained by injection molding of a polycarbonate polymer at a polymer temperature of from 260 to 340 ° C and a mold temperature of from 60 to 130 ° C, or is obtained by laminating onto each other products obtained by injection molding molding.

The form

The plastic mirror of the present invention is a spherical, non-spherical, concave, flat or multifaceted mirror, which is primarily used in equipment for office automation. The plastic mirror of the present invention, in particular, is a polyhedral mirror, a mirror for the projector or a film mirror, but it is not limited to these mirrors.

The plastic mirror of the present invention is obtained using a polycarbonate copolymer characterized by low water absorption and a specific bending modulus at a specific glass transition temperature. Therefore, it has high rigidity and excellent ability to maintain dimensions and the ability to be imprinted in the mold during molding.

Fifth aspect: conductive polymer composition, transportation tray

A fifth aspect of the present invention relates to a conductive polymer composition. More specifically, it relates to a conductive polymer composition characterized by good heat resistance, excellent conductivity and low water absorption and does not cause skin irritation. In addition, a fifth aspect of the present invention relates to a transport tray made of a polymer composition and used for electronic components such as semiconductor devices, optical recording media and hard drives.

Polycarbonate polymer is widely used in various fields, individually or in the form of a polymer composition, which also contains other thermoplastic polymers, fiberglass, carbon fibers and the like, it is used in a wide range of areas as a structural plastic, because it is characterized by excellent transparency, heat resistance, mechanical properties and the ability to maintain dimensions. However, in recent years, materials having excellent heat resistance and conductivity have become desirable.

As a material having improved heat resistance, a polymer composition is known comprising a polycarbonate copolymer containing 9.9 bis (4-hydroxyphenyl) fluorene and an inorganic filler (JP-A 7-268197).

However, this composition has a problem in that 9,9-bis (4-hydroxyphenyl) fluorene is characterized by low reactivity during polymerization, so it is difficult to obtain a polycarbonate copolymer.

In addition, the problem is taken into account that the vapors generated from 9,9-bis (4-hydroxyphenyl) fluorene, which arise as a result of decomposition during extrusion or molding from the melt, have an extremely strong irritating effect on the skin.

In addition, a polycarbonate copolymer containing 9.9-bis (4-hydroxyphenyl) fluorene has a problem associated with high water absorption and poor mechanical properties.

An object of the fifth aspect of the present invention is to provide a conductive polymer composition characterized by heat resistance and conductivity that does not cause skin irritation and is characterized by low water absorption, and a tray for transporting electronic parts that contains the polymer composition.

The conductive polymer composition comprises a polycarbonate copolymer and a carbon-based filler. The polycarbonate copolymer contains from 5 to 95 mol.%, Preferably from 7 to 90 mol.%, More preferably from 10 to 85 mol.%, Repeating units (component a) described by the general formula (I), and from 95 to 5 mol. %, preferably from 93 to 10 mol.%, more preferably from 90 to 15 mol.% of repeating units (component b) described by the general formula (II).

If the content of the repeating units described by the general formula (I) is less than 5 mol%, it will be difficult to sufficiently improve the heat resistance. Meanwhile, if the content of the repeating units described by the general formula (I) is greater than 95 mol.%, The melt flow of the polymer composition will be low and accordingly molding will be difficult.

As the polycarbonate copolymer, a copolymer containing from 5 to 95 mol%, preferably from 7 to 90 mol%, more preferably from 10 to 85 mol%, repeating units described by the general formula (I), and from 95 to 5 is preferred mol%, preferably from 93 to 10 mol%, more preferably from 90 to 15 mol%, of the repeating units described by the general formula (II-1).

Specific viscosity

The polycarbonate copolymer preferably exhibits a specific viscosity in the range of 0.17 to 0.55, more preferably 0.21 to 0.45, when measured at 20 ° C. after dissolving 0.7 g of the copolymer in 100 ml of methylene chloride.

Glass transition temperature

The polycarbonate copolymer is preferably characterized by a glass transition temperature (Tg) of not less than 150 ° C. as measured at a temperature increase rate of 20 ° C./min. A more preferred Tg is 155 ° C.

Carbon based filler

Meanwhile, illustrative examples of a carbon-based filler included in the conductive polymer composition of the present invention include carbon fibers, carbon blacks, graphites, carbon nanotubes, and fullerenes. Given the effect of improving conductivity and cost, carbon fibers and carbon blacks are particularly preferred.

There are no particular restrictions on carbon fibers, and they can be various known carbon fibers, for example carbon fibers and graphite fibers obtained using polyacrylonitrile, cellulose, tar, rayon, lignin, gaseous hydrocarbon and the like, and carbon fibers on polyacrylonitrile based, characterized by excellent fiber strength. In addition, the surfaces of carbon fibers can be oxidized by the currently known method, representative of which are methods using ozone, plasma, nitric acid or electrolysis. The oxidation treatment is preferably carried out in order to increase adhesion to the polymer component. Carbon fibers are generally in the form of chopped filaments, a tow of fibers, chopped fibers, and the like.

To impart conductivity to the carbon fibers and the like, a metal coating can be applied to the surface of the fibers. In particular, the diameter of the carbon fiber coated with a metal is preferably in the range of 6 to 20 microns. A carbon-coated carbon fiber is a carbon fiber that is coated by a known cladding method, spraying method, and the like from a metal such as nickel, copper, cobalt, silver, aluminum, iron, or an alloy thereof. The metal is preferably one or more metals selected from nickel, copper and cobalt in terms of conductivity, corrosion resistance, performance and economic efficiency. In particular, the metal-coated carbon fiber is preferably nickel-coated carbon fiber.

In addition, as these carbon fibers, it is appropriate to use fibers that adhere under the action of a bonding agent such as epoxy resin, urethane resin or acrylic resin. The use of epoxy resin and / or urethane resin is preferred.

Illustrative examples of carbon black grades include the well-known ketjenblack, acetylene black, furnace black, lamp black, thermal black, duct gas black, roll black and disc gas black. Among these carbon black grades, ketjenblack, acetylene black and furnace black are particularly preferred.

The conductive polymer composition of the present invention contains the aforementioned polycarbonate copolymer and a carbon-based filler, and the contents of the components vary depending on the situation. However, the polycarbonate copolymer content is generally in the range of 40 to 99% by weight, preferably 50 to 90% by weight, and the carbon-based filler content is generally in the range of 60 to 1% by weight, preferably 50 up to 10 wt.%. If the content of the carbon-based filler is less than 1 wt.%, The effect of improving the conductivity is likely to be negligible, while if the content of the carbon-based filler is more than 60 wt.%, The fluidity will deteriorate, which may make it more difficult mixing and molding the polymer, which is disadvantageous.

Inorganic filler

In the present invention, in order to improve the rigidity or conductivity of the polymer, inorganic fillers can be added in addition to the carbon-based filler mentioned above. As inorganic fillers, mention may be made of glass materials, metal-based fillers and various mineral fillers.

As glass materials used as inorganic fillers, for example, glass fiber, finely chopped glass fiber, glass beads, glass flakes and powder glass can be used.

The glass materials used are not limited to specific glass compositions, such as glass A, glass C and glass E, and in some cases they may contain components such as TiO ₂ , Zr ₂ O, BeO, CeO ₂ , SO ₃ and P ₂ O ₅ . However, glass E (alkali-free glass) is more preferred, which is preferred because it does not adversely affect the polycarbonate copolymer.

Glass fiber is obtained by tempering molten glass by stretching the glass to obtain a given fiber shape, using various methods. In this case, special restrictions are not imposed also on hardening and stretching. As for the cross-sectional shape, in addition to the usual flawlessly round glass fiber, it is possible to use fiberglass with different cross-sections of irregular shape, a typical representative of which are flawlessly round fiberglass threads grouped together parallel to each other. In addition, it is also possible to use mixtures of fiberglass with a flawlessly round cross-section and cross-sections of irregular shape.

Glass fiber has an average fiber diameter in the range of 1 to 25 microns, preferably 5 to 17 microns. If you use fiberglass with an average fiber diameter of less than 1 micron, formability will deteriorate, while if you use fiberglass with an average fiber diameter of more than 25 microns, the appearance will deteriorate, and the hardening effect will be insufficient.

To impart conductivity to the glass fiber and the like, a metal coating can be applied to the surface of the fibers. In particular, the diameter of the metal coated glass fiber is preferably in the range of 6 to 20 microns. Metal coated glass fiber is a glass fiber that is coated by a known cladding method, spraying method, and the like from a metal such as nickel, copper, cobalt, silver, aluminum, iron, or an alloy thereof. The metal is preferably one or more metals selected from nickel, copper and cobalt in terms of conductivity, corrosion resistance, performance and economic efficiency.

The metal-based fillers used in the present invention are not particularly imposed, and they denote metal fibers, metal coated fibers and metal flakes. Illustrative examples of materials for them include metals such as stainless steel, aluminum, copper and brass. They can be used as a combination of two or more. The diameter of the metal fiber is preferably in the range from 4 to 80 microns, particularly preferably from 6 to 60 microns.

As glass flakes and metal flakes used in the present invention, those in which the average particle diameter is in the range of 10 to 1000 microns are preferred. In addition, if the average particle diameter is denoted by (a) and the thickness by (c), then those in which the ratio (a) / (c) is in the range from 5 to 500 will be preferable, those in which the ratio (a) / (c) is in the range of 6 to 450, and those in which the ratio (a) / (c) is in the range of 7 to 400 are much more preferred. If the average particle diameter is less than 10 microns or the ratio (a) / (c) is less than 5, then the rigidity will be unsatisfactory. Meanwhile, if the average particle diameter is more than 1000 microns or the ratio (a) / (s) is more than 500, then a molded product will be obtained that will have an unsatisfactory appearance and will be characterized by low welding strength, which is disadvantageous. The average particle diameter for glass flakes and metal flakes is calculated as the median diameter of the mass distribution of particle sizes determined by the standard sieve analysis method.

In addition, as various mineral fillers, it is possible to use, for example, whiskers, such as whiskers of potassium titanate, whiskers of aluminum borate, whiskers of silicon carbide and whiskers of silicon carbide, calcium carbonate, magnesium carbonate, dolomite, silicon dioxide diatomaceous earth, aluminum oxide, iron oxide, zinc oxide, magnesium oxide, calcium sulfate, magnesium sulfate, calcium sulfite, talc, clay, mica, kaolin, asbestos, calcium silicate, mo ntmorillonite, bentonite, wollastonite, graphite, iron powder, lead powder and aluminum powder.

The surface of the inorganic fillers is preferably treated with a silane coupling agent, a titanate coupling agent, an aluminum coupling agent and the like. A silane coupling agent is particularly preferred. As a result of this surface treatment, the decomposition of the polycarbonate copolymer is suppressed and the adhesion is further improved, so that it becomes possible to improve the mechanical properties, which is an object of the present invention.

A silane coupling agent is a silane compound described by the following formula:

where Y represents a group having reactivity or affinity for a polymer matrix, such as an amino group, an epoxy group, a carboxylic acid group, a vinyl group, a mercapto group, or a halogen atom, each of Z ¹ , Z ² , Z ³ and Z ⁴ represents a single bond or an alkylene group having from 1 to 7 carbon atoms, the alkylene chain may contain molecular amide bond, ester bond, ether bond or imine bond, and each of X ^1, X ² and X ³ represents an alkoxy group, prefer no alkoxy group having from 1 to 4 carbon atoms or a halogen atom.

Specific examples of the silane compound include vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-aminophenyl-aminopropyltrimethoxylpropyltrimethoxylpropyltrimethoxylpropyltrimethoxylpropyltrimethoxysilane γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and γ-chloropropyltrimethoxysilane.

In addition, these metal-based fillers can be concentrated using olefin resin, styrene resin, ester-based polyester resin, epoxy resin, urethane resin and the like. These fibrous fillers can be used individually or as a combination of two or more.

Flame retardant

The conductive polymer composition of the present invention may contain a flame retardant in such an amount that will not impede the solution of the problem of the present invention.

Illustrative examples of a flame retardant include a polycarbonate type flame retardant based on halogenated bisphenol A, an organic salt based flame retardant, an aromatic phosphoric acid ester flame retardant, a fluoride based flame retardant, and a siloxane based flame retardant. The composition may contain one or more of these flame retardants.

Specific examples of a halogenated bisphenol A-based polycarbonate type flame retardant include a tetrachlorobisphenol A-based polycarbonate type flame retardant, a tetrachlorobisphenol A-type flame retardant flame retardant, a tetrachlorobisphenol A-based flame retardant, and a polycarbonate-based flame retardant-based flame retardant type based on tetrabromobisphenol A and bisphenol A.

Specific examples of an organic salt-based flame retardant include dipotassium diphenylsulfon-3,3'-disulfonate, potassium diphenylsulfon-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, potassium 2,4,5-trichlorobenzenesulfonate, bis (2,6-dibromo- 4-cumylphenyl) potassium phosphate, sodium bis (4-cumylphenyl) phosphate, potassium bis (p-toluenesulfone) imide, potassium bis (diphenylphosphoric acid) imide, bis (2,4,6-tribromophenyl) potassium phosphate, bis (2,4- dibromophenyl) potassium phosphate, bis (4-bromophenyl) potassium phosphate, potassium diphenyl phosphate, sodium diphenyl phosphate, potassium perfluorobutanesulfonate, sodium lauryl sulfate, potassium lauryl sulfate, sodium hexadecyl sulfate and potassium hexadecyl sulfate.

Specific examples of a halogenated aromatic phosphoric acid ester flame retardant include tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate and tris (4-bromophenyl) phosphate.

Specific examples of an aromatic phosphoric acid ester flame retardant include triphenyl phosphate, tris (2,6-xylyl) phosphate, tetrakis (2,6-xylyl) resorcin diphosphate, tetrakis (2,6-xylyl) hydroquinone diphosphate, tetrakis (2,6-xyl) ) -4,4'-biphenol diphosphate, tetraphenylresorcinol diphosphate, tetraphenylhydroquinone diphosphate, tetraphenyl-4,4'-biphenol diphosphate, aromatic polyphosphate, the aromatic ring precursors of which are resorcinol and phenol, and which does not contain a phenolic OH group, aromatic polyphosphate precursor the natural ring of which is resorcinol and phenol, and which contains a phenolic OH group, an aromatic polyphosphate, the precursors of the aromatic ring of which are hydroquinone and phenol, and which does not contain a phenolic OH group, an aromatic polyphosphate, the precursors of the aromatic ring of which are hydroquinone and phenol, and which contains a phenolic OH group (hereinafter, "aromatic polyphosphate" means both an aromatic polyphosphate containing a phenolic OH group and an aromatic polyphosphate sphat, which does not contain a phenolic OH group), aromatic polyphosphate, the precursors of the aromatic ring of which are bisphenol A and phenol, aromatic polyphosphate, the precursors of the aromatic ring of which are tetrabromobisphenol A and phenol, aromatic polyphosphate, the precursors of the aromatic ring of which are resorcinol and 2,6- xylene, aromatic polyphosphate, the precursors of the aromatic ring of which are hydroquinone and 2,6-xylenol, aromatic polyphosphate, the aromatic precursors on rings which are bisphenol A and 2,6-xylenol, and aromatic polyphosphate whose aromatic ring precursors are tetrabromobisphenol A and 2,6-xylenol.

Among these flame retardants, a polycarbonate type flame retardant based on halogenated bisphenol A is preferred, a polycarbonate type flame retardant based on tetrabromobisphenol A and a copolymerized polycarbonate based on tetrabromobisphenol A and bisphenol A, and a polycarbonate type A flame retardant based on flame retardant A are preferred.

As the salt-based flame retardant, dipotassium diphenyl sulfon-3,3'-disulfonate, potassium diphenyl sulfon-3-sulfonate and sodium 2,4,5-trichlorobenzenesulfonate are preferred.

As a flame retardant based on aromatic phosphoric acid ester, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, resorcinbis (dixylene phenophosphate), bis (2,3-dibromopropyl) phosphate and tris (2,3-dibromopropyl) phosphate are preferred. Among them, triphenyl phosphate, tricresyl phosphate and resorcinbis (dixylene phenophosphate), which are flame retardants based on aromatic phosphoric acid ester that do not cause ozone depletion, are most preferred. As a fluoride-based flame retardant, fluorinated polyolefins, such as a fluoride resin, for example PTFE, in particular those that form fibrils, are preferred. As a siloxane-based flame retardant, a polysiloxane containing an aromatic ring is preferred.

Other polymers

The conductive polymer composition of the present invention may also contain other resins in an amount that does not complicate the solution of the problem of the present invention.

Illustrative examples of other resins include ester-based polyester resin, such as polyethylene terephthalate, polybutylene terephthalate or polyethylene naphthalate, polyamide resin, polyimide resin, ether-based polyether resin, polyurethane resin, polyolefin resin, resin-based polyolefin resin resin, such as polyethylene or polypropylene, polystyrene resin, acrylonitrile / styrene copolymer (AS-resin), acrylonitrile / butadiene / styrene minutes copolymer (ABS-resin), polymethacrylate resin, phenol resin and epoxy resin.

In addition, illustrative examples of the elastomer include isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, silicone rubber, polyester based elastomer, polyamide based elastomer, methyl methacrylate butadiene styrene (MBS methacrylate butadiene styrene (MBS) acrylated methacrylate butadiene styrene (MBS) .

Obtaining a conductive polymer composition

Any method is used to produce a conductive polymer composition of the present invention. For example, where appropriate, a mixing method is used using a drum mixer, a V-shaped mixer, a super mixer, a NAUTA mixer, a Banbury mixer, a plasticizing roll, an extruder or the like. The aromatic polycarbonate polymer composition thus obtained can be molded to form a molded article directly or after granulation in a melting extruder by a well-known method such as an injection molding method, an extrusion method or a direct compression method. In addition, to improve the miscibility of the composition based on aromatic polycarbonate polymer and obtain stable ability to be removed from the form and physical properties, it is preferable to use a twin-screw extruder during extrusion from the melt. In addition, if inorganic filler is added, then any representative selected from the method comprising adding filler directly from the opening of the hopper of the extruder or from the middle of the extruder, a method comprising pre-mixing the filler with a polycarbonate copolymer, a method including pre-mixing, can be used. filler with a portion of a polycarbonate copolymer in order to obtain a masterbatch, and then adding the masterbatch, and the method, This turns the addition of the masterbatch of the middle part of the extruder.

The conductive polymer composition of the present invention is preferably characterized by a specific surface resistivity value measured in accordance with ASTM D257 of 1 × 10 ¹² or less, more preferably 1 × 10 ¹⁰ or less, most preferably 1 × 10 ⁸ or less. If the value of the specific surface resistance is greater than 1 × 10 ¹² , then the conductivity will go beyond the required range, and when the polymer composition is used as a tray for transporting electronic equipment, a short circuit may occur for electronic equipment, which is undesirable.

It is safe to work with the conductive polymer composition of the present invention since the fumes from the polycarbonate copolymer which are formed during extrusion or melt molding are not irritating and therefore do not cause skin irritation.

Thus obtained conductive polymer composition of the present invention is suitable for the manufacture of cases and blocks of equipment for office automation, such as a personal computer, word processor, fax machine, copy machine and printer, a transport tray used to transport a semiconductor device, storage device or hard disk during the manufacture of these components, internal parts of equipment for office automation, such as a tray, unit, turntable, sensor unit, and devices for optical discs and magneto-optical discs, such as CD, CD-ROM, CD-R (recordable CD), CD-RW (recordable CD), MO ( magneto-optics), DVD, DVD-ROM and DVD-R, housings and parts for household electrical devices, such as a TV, VCR, DVD player, video game device, electric washing machine, electric dryer and vacuum cleaner, electric tools such as an electric saw powered and electric drill, det Lei optical equipment, such as a tube of the telescope, the microscope tube, the body of the camera, the camera box and tube camera, and instrument panels for cars.

The conductive polymer composition of the present invention has the advantage that it is characterized by good heat resistance, excellent conductivity and low water absorption and does not cause skin irritation. Therefore, it is suitable for use as a tray for transporting electronic components such as a semiconductor device, an optical recording medium and a hard disk.

A method of obtaining a polycarbonate copolymer

The polycarbonate copolymers used in the present invention (including in the first to fifth aspects) are prepared by conventional per se known reaction methods to produce a polycarbonate copolymer, for example, by a process comprising reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or carboxylic acid diester. Next, briefly describes the main provisions of the method of obtaining.

As the carbonate precursor, a carbonyl halide, a carbonic ester or a haloformate are used. Specific examples thereof include phosgene, diphenyl carbonate and the dihalo formate of an aromatic dihydroxy component.

If, in order to obtain a polycarbonate polymer, the aromatic dihydroxy component and the carbonate precursor are reacted with each other by the interfacial polymerization mechanism or by the fusion method, it is possible to use a catalyst, an end-blocking agent, and an antioxidant such as dihydric phenol.

The reaction according to the method of interfacial polymerization in the General case is a reaction between diatomic phenol and phosgene, and it is carried out in the presence of an acid binding agent and an organic solvent. As the acid binding agent, an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, or an amine compound, such as pyridine, is used. A halogenated hydrocarbon such as methylene chloride or chlorobenzene is used as an organic solvent. In addition, a catalyst such as a tertiary amine, a quaternary ammonium compound or a quaternary phosphonium compound, for example triethylamine, tetra-n-butylammonium bromide and tetra-n-butylphosphonium bromide can also be used to accelerate the reaction. In this case, the reaction temperature is generally in the range of 0 to 40 ° C., the reaction time is in the range of about 10 minutes to 5 hours, and the pH during the reaction is preferably kept at a level of 9 or more.

The fusion method reaction is generally a transesterification reaction between a dihydric phenol and a carbonic ester, and it is carried out by a method comprising mixing, while heating, a dihydric phenol and a carbonic ester in the presence of an inert gas and distilling the resulting alcohol or phenol. The reaction temperature varies in accordance with the boiling point of the resulting alcohol or phenol, but in the General case, it is in the range from 120 to 350 ° C. At the last stage of the reaction, the pressure in the system is reduced to a value of from about 1.3 × 10 ³ to 1.3 × 10 Pa in order to facilitate the distillation of the resulting alcohol or phenol. The reaction time is generally in the range of about 1 to 4 hours.

Illustrative examples of a carbonic ester include esters with an aryl group having from 6 to 10 carbon atoms, an aralkyl group and an alkyl group having from 1 to 4 carbon atoms that may be substituted. Specific examples thereof include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate and dibutyl carbonate. Among them, diphenyl carbonate is preferred.

Polymerization catalyst

In addition, in order to increase the polymerization rate in the fusion method, a polymerization catalyst can be used. As a polymerization catalyst, it is possible to use catalysts that are generally used in the esterification reaction and transesterification reaction, for example, alkali metal compounds such as sodium hydroxide, potassium hydroxide, dihydric phenol sodium and potassium dihydric phenol, alkaline earth metal compounds such as hydroxide calcium, barium hydroxide and magnesium hydroxide, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine, alkoxides of alkali metals and alkaline earth metals, organic salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds, manganese compounds, titanium compounds and zirconium compounds. These catalysts can be used individually or as a combination of two or more. The amount of the polymerization catalyst is selected from a range of from 1 × 10 ^-8 to 1 × 10 ^-3 equivalents, preferably from 1 × 10 ^-7 to 1 × 10 ^-3 equivalents, more preferably from 1 × 10 ^-6 to 5 × 10 ^-4 equivalents per mole of dihydric phenol, which is the feedstock.

End Blocking Agent

In the polymerization reaction to obtain a polycarbonate copolymer, it is possible to use monofunctional phenol, which is generally used as an end blocking agent. In particular, monofunctional phenol is generally used as an end blocking agent to control molecular weight in the case of a reaction using phosgene as a precursor, and since the resulting polymer will have end groups blocked by monofunctional phenol groups, the polymer will differ in better thermal stability in comparison with those in which the end groups will not be blocked by groups based on monofunctional phenol.

A monofunctional phenol can be any monofunctional phenol that is used as an end-blocking agent for a polycarbonate polymer, and in general, an example of it is a monofunctional phenol, which is phenol or phenol substituted by lower alkyl, described by the following general formula:

where A represents a hydrogen atom, a linear or branched alkyl group having from 1 to 9 carbon atoms, or an arylalkyl group, and r represents an integer from 1 to 5, preferably from 1 to 3.

Specific examples of monofunctional phenol include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

In addition, other monofunctional phenols, such as phenols, and benzoic acid chloride having as a substituent a long chain alkyl group or an aliphatic ester group, and long chain alkyl carboxylic acid chlorides, can also be used. If the end groups of the polycarbonate copolymer are blocked using these monofunctional phenols, the latter will be used not only as an end blocking agent or molecular weight regulator, but will also improve the melt flow of the polymer, thereby facilitating molding and also improving physical properties substrate. In particular, these monofunctional phenols have an effect on reducing polymer water absorption, and accordingly, their use is preferred. They are described by the following general formulas from (III-1) to (III-8):

where X is —RO—, —R — CO — O— or —RO — CO—, where R is a single bond or a divalent aliphatic hydrocarbon group having from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, T represents a single bond or the same bonds as the above X, and n represents an integer from 10 to 50;

Q represents a halogen atom or a monovalent aliphatic hydrocarbon group having from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, p represents an integer from 0 to 4, Y represents a divalent aliphatic hydrocarbon group having from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, and W ¹ represents a hydrogen atom, —CO — R ¹³ , —CO — OR ¹⁴ or R ¹⁵ , where R ¹³ , R ¹⁴ and R ¹⁵ each represents a monovalent aliphatic hydrocarbon group having from 1 to 10 carbon atoms, pre preferably 1 to 5 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 8 carbon atoms, preferably 5 or 6 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, preferably 6 to 12 carbon atoms;

l represents an integer from 4 to 20, preferably from 5 to 10, m represents an integer from 1 to 100, preferably from 3 to 60, particularly preferably from 4 to 50, Z represents a single bond or a divalent aliphatic hydrocarbon group having from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, and W ² represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, a monovalent alicyclic Carbs portly group having from 4 to 8 carbon atoms, preferably 5 or 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, preferably from 6 to 12 carbon atoms.

Among them, substituted phenols described by formulas (III-1) and (III-2) are preferred. As substituted phenol (III-1), a compound in which n is in the range from 10 to 30, in particular from 10 to 26 is preferred. Specific examples thereof include decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol, octadecyl phenol, eicosyl phenol, docosyl phenol and tricon.

Meanwhile, as a substituted phenol of formula (III-2), a compound in which X is —R — CO — O— and R is a single bond is suitable, and a compound in which n is in the range from 10 to 30, in particular from 10 to 26. Specific examples thereof include decylhydroxybenzoate, dodecylhydroxybenzoate, tetradecylhydroxybenzoate, hexadecylhydroxybenzoate, eicosylhydroxybenzoate and triaconti.

The position of the substituent in substituted phenols or substituted benzoic acid chlorides described by the above general formulas (III-1) to (III-7) preferably corresponds to the para or ortho position, and a mixture of both is preferred.

The above-mentioned monofunctional phenols are desirably administered in an amount of at least 5 mol%, preferably at least 10 mol%, of the total number of end groups in the obtained polycarbonate copolymer. In addition, monofunctional phenols can be used individually or as a mixture of two or more.

In addition, if 9,9-bis (4-hydroxy-3-methylphenyl) fluorene will comprise at least 80 mol% of the total amount of diatomic phenolic components in the polycarbonate copolymer of the present invention, the fluidity of the polymer may be impaired. For this reason, it is preferable to use substituted phenols or substituted benzoic acid chlorides as the terminal blocking agent described by the above general formulas (III-1) to (III-7).

Thermal stabilizers

In the present invention, the aforementioned polycarbonate copolymer may contain at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid and their esters, in an amount of from 0.0001 to 0.05 wt.% based on the amount of copolymer. By adding a phosphorus compound, the thermal stability of the polycarbonate copolymer is improved, and a decrease in molecular weight and color deterioration during molding can be prevented.

The phosphorus compound is at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid and their esters, and preferably it is at least one phosphorus compound selected from the group consisting of compounds described by the following general formulas from (IV-1) to (IV-4):

where R ¹ -R ¹² each independently represents a hydrogen atom, an alkyl group having from 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, a nonyl, decyl, dodecyl, hexadecyl or octadecyl, aryl group having from 6 to 15 carbon atoms, such as phenyl, tolyl or naphthyl, or an aralkyl group having from 7 to 18 carbon atoms, such as benzyl or phenethyl. In addition, if two alkyl groups are present in one compound, then two alkyl groups can be joined together to form a ring.

Illustrative examples of the phosphorus compound described by the above formula (IV-1) include triphenylphosphite, trisnonylphenylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphenylphosphyl diphylphosphyl diphylphosphyl diphosphite, didecylmonophenylphosphyl diphosphyl diphylphosphyl diphylphosphyl diphylphosphyl diphylphosphyl diphylphosphyl diphylphosphyl diphylphosphyl diphylphosphyl diphylphosphyl diphylphosphyl diphylphosphyl diphylphosphyl diphylphosphyl diphylphosphyl monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4- di-tert-butylphenyl ) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and distearylpentaerythritol diphosphite.

Illustrative examples of the phosphorus compound described by the above formula (IV-2) include tributyl phosphate, trimethyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl mono-ortho-xenyl phosphate, dibutyl phosphate, dioctyl phosphate and diisopropyl phosphate.

Illustrative examples of the phosphorus compound described by the above formula (IV-3) include tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylene phosphonite.

Illustrative examples of the phosphorus compound described by the above formula (IV-4) include dimethylbenzene phosphonate, diethylbenzene phosphonate and dipropylbenzene phosphonate.

Among them, preferably used are distearyl pentaerythritol diphosphite, triethyl phosphate, dimethylbenzene phosphonate and bis (2,4-dicumylphenyl) pentaerythritol diphosphite.

The amount of phosphorus compound is in the range from 0.0001 to 0.05 wt.%, Preferably from 0.0005 to 0.2 wt.%, Particularly preferably from 0.001 to 0.01 wt.%, Based on the amount of polycarbonate copolymer . If the amount is less than 0.0001 wt.%, The effect described above will be difficult to achieve, while if the amount is more than 0.05 wt.%, The phosphorus compound will adversely affect the thermal stability of the polycarbonate copolymer, as well as the durability to hydrolysis, which is disadvantageous.

Antioxidant

A well-known antioxidant can be added to the polycarbonate copolymer of the present invention in order to prevent oxidation of the copolymer. Illustrative examples of an antioxidant include phenol based antioxidant and lactone based antioxidant. Specific examples of phenol-based antioxidant include triethylene glycolbis (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate), 1,6-hexanediolbis (3- (3,5-di-tert-butyl-4- hydroxyphenyl) propionate), pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamide) 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocia urate and 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5 5) undecane.

In addition, specific examples of a lactone-based antioxidant include 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one and 5,7-di-tert-butyl-3- (2,3-dimethylphenyl) -3H-benzofuran-2-one. The antioxidant is preferably added in an amount of from 0.0001 to 0.05 wt.% Based on the amount of polycarbonate copolymer.

Mold grease

In addition, an ester derived from a higher fatty acid and a monohydric or polyhydric alcohol can also be added to the polycarbonate copolymer of the present invention. As a result of the addition of an ester derived from a higher fatty acid and a monohydric or polyhydric alcohol, the polycarbonate copolymer mentioned above improves the ability to be removed from the mold during molding, and when forming an optical product, the load on the molded product will be low and deformation of the molded product can be prevented. as a result of inappropriate extraction from the mold. In addition, the addition of a higher fatty acid ester also provides an advantage in improving the melt flow of the polycarbonate copolymer.

The higher fatty acid ester is preferably a partial ester or full ester of a monohydric or polyhydric alcohol having from 1 to 20 carbon atoms and a saturated fatty acid having from 10 to 30 carbon atoms.

In addition, specific examples of a partial ester or full ester of a monohydroxy or polyhydric alcohol and a saturated fatty acid include monoglyceride stearate, monosorbitate stearate, monoglyceride behenate, pentaerythritol monostearate, pentaerythritol tetrate sterate, methyl propylene glycol, stearyl stearate, Among them, the use of monoglyceride stearate and pentaerythritetetrastearate is preferred.

The amount of ester derived from alcohol and a higher fatty acid is in the range from 0.01 to 2 wt.%, Preferably from 0.015 to 0.5 wt.%, More preferably from 0.02 to 0.2 wt.%, based on the amount of polycarbonate copolymer. If the amount is less than 0.01 wt.%, The above effect will not be obtained, while if the amount is more than 2 wt.%, The ester will cause stains on the surface of the mold.

Other additives

Additives such as a light stabilizer, a dye, an antistatic agent and a lubricant may also be added to the polycarbonate copolymer of the present invention in an amount that will not adversely affect the thermal stability and transparency. The above additives can be mixed with the polycarbonate copolymer of the present invention using a predetermined method. For example, where appropriate, a mixing method is used using a drum mixer, a V-shaped mixer, a NAUTA mixer, a Banbury mixer, a plasticizing roll, an extruder, and the like.

Examples

Hereinafter, the present invention will be further described with reference to examples. However, the present invention is not limited to these examples. In the examples, "parts" mean "mass parts".

Examples 1-3 and comparative example 1

Solder Reflow Detail

Physical properties were evaluated using the following methods.

(1) Specific viscosity

It was measured at a temperature of 20 ° C after dissolving 0.7 g of the polymer in 100 ml of methylene chloride.

(2) Glass transition temperature (Tg)

It was measured at a temperature increase rate of 20 ° C / min using a type 2910 DSC instrument from TA INSTRUMENTS JAPAN CO., LTD.

(3) Volumetric melt flow rate (MVR).

It is measured as the amount of polymer (cm ³ ) that flowed out for 10 minutes at 320 ° C under a load of 1.2 kg using an MFR (melt flow rate) device of type L251-11 from TECHNOL SEVEN CO., LTD. according to JIS K-7210.

(4) Transmission

Passage for a test sample obtained by injection molding and having a thickness of 1.0 mm, a width of 10 mm and a length of 20 mm, in the wavelength regions of 400 nm, 500 nm, 600 nm, 700 nm, 1300 nm, 1400 nm, 1500 nm and 1600 nm were measured using a U-4001 type spectrophotometer from HITACHI, LTD.

(5) Thermal stability during reflow soldering

but. Test sample

A test sample obtained by injection molding and having a thickness of 1.0 mm, a width of 10 mm and a length of 20 mm was dried under reduced pressure at 120 ° C. for 10 hours. This test sample was processed in a solder reflow oven (manufactured by Asahi Engineering Co., Ltd., TPF-20L) using both infrared light and hot air. The temperature profile during heating was set so that the action of the peak temperature of 250 ° C continued for 5 seconds after heating at 150 ° C for 60 seconds. If the molded element after processing during reflow soldering did not deform, then it was rated as "○", and if it was deformed, then it was rated as "x".

b. Lens

A flat-convex lens obtained by injection molding and having an outer diameter of 2.0 mm, a thickness at the center of 0.80 mm and a focal length of 2.0 mm was dried under reduced pressure at 120 ° C for 10 hours. This test sample was processed in a solder reflow oven (manufactured by Asahi Engineering Co., Ltd., TPF-20L) using both infrared light and hot air. The temperature profile during heating was set so that the action of the peak temperature of 250 ° C continued for 5 seconds after heating at 150 ° C for 60 seconds. If the magnitude of the change in focal length of a plano-convex lens after processing during reflow soldering was less than 0.10 mm, then the lens was evaluated as "○", and if the magnitude of the change was 0.10 mm or more or the lens was deformed, then it was evaluated as "x "

Example 1

Polymerization

In a reactor equipped with a thermometer, a stirrer and a reflux condenser, 2270 parts of water were placed after ion exchange and 444 parts of an aqueous solution of sodium hydroxide with a concentration of 48%, and then 76.8 parts of bisphenol A, 509.1 parts of 9.9 were dissolved bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as "bis-cresolfluorene") and 1.2 parts of hydrosulfite. Then, after adding 1430 parts of methylene chloride at 18-23 ° C, 225 parts of phosgene were purged with stirring for 60 minutes. After purging the phosgene, 11.4 parts of p-tert-butylphenol and 6.9 parts of an aqueous sodium hydroxide solution with a concentration of 48% were added, and the resulting mixture was stirred at 25-30 ° C. for 40 minutes, thereby completing the reaction.

After completion of the reaction, the resulting product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and then washed with water. When the electrical conductivity of the aqueous phase became almost the same as that of water after treatment by the ion exchange method, methylene chloride was evaporated using a plasticizer. Thus, 600 parts of a whitish-yellow polymer were obtained with a bisphenol A / biscresolfluorene molar ratio of 20:80, a specific viscosity of 0.244 and a Tg of 223 ° C (95% yield).

Molding

To this powdered polycarbonate polymer was added 0.050% tris (2,4-di-tert-butylphenyl) phosphite, 0.010% octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and 0.030% pentaerythritetetrastearate and a mixture granulated using a ⌀30 mm twin screw extruder with gas suction, and thereafter, an injection molded article having a thickness of 1.0 mm, a width of 10 mm and a length of 20 mm was obtained from it using an injection molding machine from Japan using an N-20C injection machine Steel Works, LTD. at a cylinder temperature of 340 ° C and a mold temperature of 150 ° C. For a molded product, transmission was measured and a test was carried out to determine its heat resistance during reflow soldering. The results are shown in table 1.

Lens

In addition, when using an N-20C injection molding machine from Japan Steel Works, LTD. at a cylinder temperature of 340 ° C and a mold temperature of 150 ° C, a plano-convex lens having an outer diameter of 2.0 mm, a center thickness of 0.80 mm, and a focal length of 2.0 mm were obtained from the above-mentioned granules by injection molding. The transmission of the lens was measured and a test was carried out to determine its heat resistance during reflow soldering. The results are shown in table 1.

Example 2

Polymerization

In a reactor equipped with a thermometer, stirrer and reflux condenser, 2060 parts of water were placed after treatment by the ion exchange method and 404 parts of an aqueous solution of sodium hydroxide with a concentration of 48% and then 111.6 parts of bisphenol A, 431.7 parts of 9.9 were dissolved bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as "bis-cresolfluorene") and 1.1 parts of hydrosulfite. Then, after adding 1390 parts of methylene chloride at 18-23 ° C. with stirring for 60 minutes, 210 parts of phosgene were purged through the mixture. After purging the phosgene, 11.0 parts of p-tert-butylphenol and 6.7 parts of an aqueous solution of sodium hydroxide with a concentration of 48% were added, and the resulting mixture was stirred at 25-30 ° C. for 40 minutes, thereby completing the reaction.

After completion of the reaction, the resulting product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and then washed with water. When the electrical conductivity of the aqueous phase became almost the same as that of water after treatment by the ion exchange method, methylene chloride was evaporated using a plasticizer. Thus, 560 parts of a whitish yellow polymer with a molar ratio of bisphenol A / biscresolfluorene of 30:70, specific viscosity 0.258 and Tg 216 ° C (yield 94%) were obtained.

Molding

To this powdered polycarbonate polymer was added 0.050% tris (2,4-di-tert-butylphenyl) phosphite, 0.010% octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and 0.030% pentaerythritetetrastearate and a mixture granulated using a ⌀30 mm twin screw extruder with gas suction, and thereafter, an injection molded article having a thickness of 1.0 mm, a width of 10 mm and a length of 20 mm was obtained from it using an injection molding machine from Japan using an N-20C injection machine Steel Works, LTD. at a cylinder temperature of 330 ° C and a mold temperature of 140 ° C. For a molded product, transmission was measured and a test was carried out to determine its heat resistance during reflow soldering. The results are shown in table 1.

Lens

In addition, when using an N-20C injection molding machine from Japan Steel Works, LTD. at a cylinder temperature of 330 ° C and a mold temperature of 140 ° C, a plano-convex lens having an outer diameter of 2.0 mm, a center thickness of 0.80 mm, and a focal length of 2.0 mm was obtained from the above-mentioned granules by injection molding. The transmission of the lens was measured and a test was carried out to determine its heat resistance during reflow soldering. The results are shown in table 1.

Example 3

Polymerization

621 parts of a whitish-yellow polymer with a bisphenol A / biscresolfluorene molar ratio of 15:85, specific viscosity 0.240 and Tg 232 ° C were obtained (yield 94%) in the same manner as in example 1, except that the amount of bisphenol And, used in example 1, changed, making it equal to 57.6 parts, and the fact that the amount of biscresolfluorene used in example 1, changed, making it equal to 540.9 parts.

Molding

To this powdered polycarbonate polymer was added 0.050% tris (2,4-di-tert-butylphenyl) phosphite, 0.010% octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and 0.030% pentaerythritetetrastearate and a mixture granulated using a ⌀30 mm twin screw extruder with gas suction, and thereafter, an injection molded article having a thickness of 1.0 mm, a width of 10 mm and a length of 20 mm was obtained from it using an injection molding machine from Japan using an N-20C injection machine Steel Works, LTD. at a cylinder temperature of 350 ° C and a mold temperature of 165 ° C. For a molded product, transmission was measured and a test was carried out to determine its heat resistance during reflow soldering. The results are shown in table 1.

Lens

In addition, when using an N-20C injection molding machine from Japan Steel Works, LTD. at a cylinder temperature of 350 ° C. and a mold temperature of 165 ° C., a plano-convex lens having an outer diameter of 2.0 mm, a center thickness of 0.80 mm, and a focal length of 2.0 mm were obtained from the above-mentioned granules by injection molding. The transmission of the lens was measured and a test was carried out to determine its heat resistance during reflow soldering. The results are shown in table 1.

Comparative Example 1

Polymerization

In a reactor equipped with a thermometer, stirrer and reflux condenser, 2270 parts of water were placed after ion exchange and 444 parts of an aqueous solution of sodium hydroxide with a concentration of 48%, and then 7.68 parts of bisphenol A, 623.6 parts of biscresolfluorene and 1 were dissolved , 2 parts of hydrosulfite. Then, after adding 2000 parts of chloroform at 18-23 ° C, 225 parts of phosgene were purged with stirring for 60 minutes. After the phosgene purge was completed, 10.1 parts of p-tert-butylphenol and 6.9 parts of an aqueous sodium hydroxide solution with a concentration of 48% were added, and the resulting mixture was stirred at 25-30 ° C. for 40 minutes, thereby completing the reaction.

After completion of the reaction, the resulting product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and then washed with water. When the electrical conductivity of the aqueous phase became almost the same as that of water after treatment by the ion exchange method, methylene chloride was evaporated using a plasticizer. Thus, 637 parts of a whitish yellow polymer were obtained with a bisphenol A / biscresolfluorene molar ratio of 2:98, specific viscosity 0.245 and Tg 238 ° C (93% yield).

Molding

To this powdered polycarbonate polymer was added 0.050% tris (2,4-di-tert-butylphenyl) phosphite, 0.010% octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and 0.030% pentaerythritetetrastearate and a mixture granulated using a ⌀30 mm twin screw extruder with gas suction, and thereafter, an injection molded article having a thickness of 1.0 mm, a width of 10 mm and a length of 20 mm was obtained from it using an injection molding machine from Japan using an N-20C injection machine Steel Works, LTD. at a cylinder temperature of 360 ° C and a mold temperature of 170 ° C. For a molded product, transmission was measured and a test was carried out to determine its heat resistance during reflow soldering. The results are shown in table 1.

Lens

In addition, when using an N-20C injection molding machine from Japan Steel Works, LTD. at a cylinder temperature of 360 ° C and a mold temperature of 170 ° C, a plano-convex lens having an outer diameter of 2.0 mm, a center thickness of 0.80 mm, and a focal length of 2.0 mm were obtained from the above-mentioned granules by injection molding. The transmission of the lens was measured and a test was carried out to determine its heat resistance during reflow soldering. The results are shown in table 1.

Table 1 unit of measurement Example 1 Example 2 Example 3 Comparative Example 1 The ratio of components in the composition (mol.%) Biscresolfluoren 80 70 85 98 Bisphenol A twenty thirty fifteen 2 Evaluation Results MVR cm ^3/10 min 1,5 2,5 0.6 0.1 Skipping 400 nm % 68.9 68.5 66.6 58.9 500 nm % 80.2 80.5 80.2 78.0 600 nm % 82.3 82.5 81.8 81.2 700 nm % 84.0 84.6 84.0 83.3 1300 nm % 88.5 88.7 87.9 87.6 1400 nm % 81.7 81.5 81.8 81.4 1500 nm % 86.5 86.7 86.3 85.0 1600 nm % 84.3 84.3 84.5 83.9 Heat resistance during reflow soldering Test sample ○ ○ ○ ○ Lens ○ ○ ○ ○

Examples 4-18 and comparative examples 2-7

Detail for transforming the path of a ray of light

Physical properties were evaluated using the following methods.

(1) Specific viscosity

It was measured at a temperature of 20 ° C after dissolving 0.7 g of the polymer in 100 ml of methylene chloride.

(2) Glass transition temperature (Tg)

It was measured at a temperature increase rate of 20 ° C / min using a type 2910 DSC instrument from TA INSTRUMENTS JAPAN CO., LTD.

(3) Temperature reduction in mass by 5% (Td)

It was measured at a temperature increase rate of 20 ° C / min using a type 2950 TGA apparatus from TA INSTRUMENTS JAPAN CO., LTD.

(4) Photoelasticity coefficient

It was measured using a PA-150 photoelasticity measuring device from Riken Keiki Co., Ltd.

(5) Transmission (T ₅₅₀ )

The transmittance at 550 nm for the manufactured molded plate was measured using a U-4001 type spectrophotometer from Hitachi, Ltd.

(6) Delay (Re ₅₅₀ )

The delay at 550 nm for the manufactured molded plate was measured using an M-220 type ellipsometer from JASCO Corporation.

Polymerization

EX-RS1

In a reactor equipped with a thermometer, stirrer and reflux condenser, 2050 parts of water were placed after ion exchange and 434 parts of an aqueous solution of sodium hydroxide with a concentration of 48% and 111.6 parts of bisphenol A were dissolved (hereinafter abbreviated hereinafter referred to as "BPA" ), 431.7 parts of 9.9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as “BCF”) and 1.1 parts of hydrosulfite. Then, after adding 1360 parts of methylene chloride at 18-23 ° C. with stirring for 60 minutes, 215 parts of phosgene were purged through the mixture. After purging the phosgene, 11.0 parts of p-tert-butylphenol and 67 parts of an aqueous solution of sodium hydroxide with a concentration of 48% were added, and the resulting mixture was stirred at 25-30 ° C. for 45 minutes, thereby completing the reaction.

After completion of the reaction, the resulting product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and then washed with water. When the electrical conductivity of the aqueous phase became almost the same as that of water after treatment by the ion exchange method, methylene chloride was evaporated using a plasticizer. Thus, 550 parts of a whitish-yellow polymer with a molar ratio of BPA / BCF of 30:70, specific viscosity of 0.260 and Tg of 215 ° C were obtained (yield 92%).

EX-RS2

In a reactor equipped with a thermometer, stirrer and reflux condenser, 3608 parts of water were placed after ion exchange and 482 parts of an aqueous solution of sodium hydroxide with a concentration of 48%, and then 156.1 parts of 1,3-bis {2- (4 β-hydroxyphenyl) propyl} benzene (hereinafter abbreviated as “BPM”), 461.0 parts of BCF and 1.3 parts of hydrosulfite. Then, after adding 1704 parts of methylene chloride at 18-23 ° C. with stirring for 60 minutes, 215 parts of phosgene were purged through the mixture. After purging the phosgene, 12.5 parts of p-tert-butylphenol and 69 parts of an aqueous solution of sodium hydroxide with a concentration of 48% were added, and the resulting mixture was stirred at 25-30 ° C. for 45 minutes, thereby completing the reaction.

After completion of the reaction, the resulting product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and then washed with water. When the electrical conductivity of the aqueous phase became almost the same as that of water after treatment by the ion exchange method, methylene chloride was evaporated using a plasticizer. Thus, 619 parts of a whitish-yellow polymer were obtained with a BPM / BCF molar ratio of 27:73, specific viscosity 0.260 and Tg 212 ° C (92% yield).

EX-RS3

560 parts of a whitish yellow polymer with a molar ratio of BPA / BCF of 33:67, specific viscosity of 0.262 and Tg of 212 ° C were obtained (yield 94%) in the same manner as in the preparation of EX-PC1, except that the quantity The BPA used to obtain EX-PC1 was changed to 124.4 parts, and the amount of BCF used to receive EX-PC1 was changed to 418.9 parts.

EX-RS4

630 parts of a whitish yellow polymer with a BPM / BCF molar ratio of 45:55, specific viscosity 0.280 and Tg 190 ° C were obtained (95% yield) in the same manner as in the preparation of EX-PC2, except that the amount The BPM used to obtain EX-PC2 was changed to 260.1 parts, and the amount of BCF used to receive EX-PC2 was changed to 347.3 parts.

EX-RS5

595 parts of a whitish-yellow polymer with a molar ratio of BPA / BCF of 20:80, specific viscosity of 0.250 and Tg of 220 ° C were obtained (yield 94%) in the same manner as in the preparation of EX-PC1, except that the quantity The BPA used in obtaining EX-PC1 was changed to 79.3 parts, and the amount of BCF used in receiving EX-PC1 was changed to 504.6 parts.

SEX-RS1

584 parts of a whitish-yellow BPA homopolymer with a specific viscosity of 0.280 and Tg 144 ° C were obtained (95% yield) in the same manner as in the preparation of EX-PC1, except that the amount of BPA used in the preparation of EX-PC1 were changed by making it equal to 605.3 parts, BCF was not added, and the amount of p-tert-butylphenol was changed by making it equal to 13.0 parts.

CEX-PC2

From 40 parts of a polycarbonate polymer containing bis (4-hydroxy-3,5-dimethylphenyl) propane with a specific viscosity of 0.550 and 60 parts of an acrylonitrile styrene copolymer having a weight average molecular weight of 100,000 and copolymerized with 10% acrylonitrile component, a dry powder was prepared mixture using a drum mixer.

Examples 4-8 and comparative examples 2 and 3

Molded product

To the obtained polymers, 0.050% bis (2,4-dicumylphenyl) pentaerythritol diphosphite and 0.10% pentaerythritetetrastearate were added, and the resulting mixtures were granulated using a ⌀30 mm single screw extruder with gas suction, and then from them by injection molding under molding conditions shown in Table 2, molded plates were obtained, each having a thickness of 1.0 mm, a width of 1.0 mm and a length of 2.0 mm, using an N-20C injection molding machine from Japan Steel Works, LTD. For molded plates, transmission and retention were measured. The results are shown in table 2.

table 2 Position Poly measures PC The ratio of components in the composition Evaluation Results Molding conditions Evaluation Results BCF BPA BPM Tg Td Photoelasticity coefficient Cylinder temperature Mold temperature T ₅₅₀ Re ₅₅₀ unit of measurement - mol% mol% mol% ° C ° C × 10 ¹³ cm ² / din ° C ° C % nm Example 4 EX-RS1 70 thirty 215 495 38 350 140 89 1,5 Example 5 EX-RS2 73 27 212 482 thirty 350 140 88 1,2 Example 6 EX-RS3 67 33 212 497 39 350 140 89 1.3 Example 7 EX-RS4 55 45 165 490 40 320 125 88 7.3 Example 8 EX-RS5 80 twenty 220 485 35 350 140 89 5,4 Reference Example 2 SEX-RS1 one hundred 144 497 80 300 115 90 72 Reference Example 3 SEX-RS2 129 403 eighteen 270 90 88 9.6

Examples 9-13 and comparative examples 4 and 5

Lens

To the obtained polymers were added 0.050% bis (2,4-dicumylphenyl) pentaerythritol diphosphite and 0.10% pentaerythritol tetrastearate and the mixture was granulated using a ⌀30 mm single screw extruder with gas suction, and then from them by injection molding under molding conditions shown in table 3, received a convex lens, each of which had an outer diameter of 2.0 mm, a thickness in the center of 0.80 mm and a focal length of 2.0 mm, when using an injection molding machine N-20C from Japan Steel Works, LTD.

Polarizing plates with a phase difference of 90 ° were located front and rear of the molded plano-convex lens. One of the polarizing plates was illuminated with white light and visual observations were made of the appearance of an interference color on a plano-convex lens in order to evaluate the degree of birefringence based on the following criteria.

⓪: no interference fringes.

: одна интерференционная полоса.

: one interference band.

x: two or more interference fringes.

The results of molding and evaluation are shown in table 3.

Table 3 Position PC Polymers The ratio of components in the composition Molding conditions Evaluation Results BCF BPA BPM Cylinder temperature Mold temperature Formability Two-beam refraction unit of measurement - mol% mol% mol% ° C ° C %

Example 9 EX-RS1 70 thirty 350 140 No problems ⓪ Example 10 EX-RS2 73 27 350 140 No problems ⓪ Example 11 EX-RS3 67 33 350 140 No problems ⓪ Example 12 EX-RS4 55 45 320 125 No problems

Example 13 EX-RS5 80 twenty 350 140 No problems

Reference Example 4 SEX-RS1 one hundred 320 115 No problems x Reference Example 5 SEX-RS2 300 one hundred A large number of gaseous cracking products, difficult to mold x

Examples 14-18 and comparative examples 6 and 7

Prism

To the obtained polymers, 0.030% bis (2,4-dicumylphenyl) pentaerythritol diphosphite and 0.15% pentaerythritetetrastearate were added and the mixture was granulated using a ⌀30 mm single screw extruder with gas suction, and then from them by injection molding under molding conditions shown in table 4, received rectangular prisms, each of which had a size of 20.0 mm × 28.3 mm × 20.0 mm, using an injection molding machine N-20C from the company Japan Steel Works, LTD.

Polarizing plates with a phase difference of 90 ° were located front and rear of the molded prism. One of the polarizing plates was illuminated with white light and visual observations were made of the appearance of an interference color on the prism in order to evaluate the degree of birefringence based on the following criteria.

⓪: no interference fringes.

: одна интерференционная полоса.

: one interference band.

x: two or more interference fringes.

Table 4 Position PC Polymers The ratio of components in the composition Molding conditions Evaluation Results BCF BPA BPM Cylinder temperature Mold temperature Formability Two-beam refraction unit of measurement - mol% Mol% mol% ° C ° C %

Example 14 EX-RS1 70 thirty 360 150 No problems ⓪ Example 15 EX-RS2 73 27 360 150 No problems ⓪ Example 16 EX-RS3 67 33 360 150 No problems ⓪ Example 17 EX-RS4 55 45 360 130 No problems

Example 18 EX-RS5 80 twenty 365 155 No problems

Reference Example 6 SEX-RS1 one hundred 350 125 No problems x Reference Example 7 SEX-RS2 300 110 A large number of gaseous cracking products, difficult to mold x

Examples 19-23 and comparative examples 8 and 9

Optical disc

Physical properties were evaluated using the following methods.

(1) Deformation resistance

It was measured under a load of 1.81 MPa in accordance with ISO 75-1, -2.

(2) Water absorption upon reaching saturation

The polymer was immersed in pure water at 23 ° C and water absorption when saturation was achieved was measured in accordance with ISO 62 when the rate of change per day reached 0.01% or less.

(3) Bending modulus

Upon completion of the drying of the granules at 120 ° C. for 5 hours by injection molding, a test sample was obtained from them using an injection molding machine (SG-150 from Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 290 ° C. The bending modulus of the test specimen was measured in accordance with ISO 178.

(4) Initial mechanical properties

A disk substrate having a diameter of 120 mm and a thickness of 1.2 mm was obtained by injection molding from each type of granule using an M35B-D-DM machine from MEIKI CO., LTD. Table 5 shows the molding conditions for each substrate. After that, a reflective film, a dielectric layer 1, a recording film with a phase transition, and a dielectric layer 2 were deposited onto the disk substrate obtained by injection molding and deposited onto the substrate, and the coating layer was laminated on top of a thin polycarbonate film, thereby obtaining the substrate of interest optical disk.

After that, distance stops were inserted between the disks to prevent contact between the disks, and the resulting disks were left at a temperature of 23 ° C and a humidity corresponding to 50% relative humidity for at least two days. The angular deviation (initial substrate shape) was evaluated using DLD-3000U three-dimensional shape measuring equipment from Japan EM Co., Ltd., when the change in angular deviation caused by thermal contraction and changes in the environment reached a stationary value and was taken as initial mechanical properties.

(5) ΔTilt

After the substrate of the disk, for which an assessment of its initial mechanical properties was obtained, was exposed to the environment (environment A), where the temperature was 30 ° C and the humidity corresponded to 90% relative humidity until saturation by water absorption was reached, the disk substrate transferred to the environment (environment B), where the temperature was 23 ° C and the humidity corresponded to 50% relative humidity. After transferring the substrate of the disk over time, we measured the change in angular deviation at a distance of 58 mm from the center, which occurred as a result of environmental changes, using the DLD-3000U three-dimensional shape measuring equipment from Japan EM Co., Ltd. The difference between the maximum value of the change in angular deviation and the value at which the change in angular deviation reaches a stationary value was taken as ΔTilt.

(6) Damping (tanδ)

It was measured at 40 ° C and 18 Hz using an RDAII instrument from REOMETRICS CO., LTD. in accordance with ISO 6721-4.

Example 19

Polymerization

In a reactor equipped with a thermometer, stirrer, reflux condenser and phosgene injection tube, 31,500 parts of water were placed after ion exchange and 1730 parts of sodium hydroxide, and 2040 parts of 9.9-bis (3-methyl-4-hydroxyphenyl) fluorene were dissolved (hereinafter abbreviated as "BCF"), 2802 parts of 4,4 '- (m-phenylenediisopropylidene) diphenol (hereinafter abbreviated as "BPM") and 10 parts of hydrosulfite. Then, after adding 13770 parts of methylene chloride at 16-18 ° C. with stirring for 60 minutes, 1670 parts of phosgene were purged through the mixture. After the phosgene purge was completed, 81 parts of p-tert-butylphenol and 178 parts of sodium hydroxide were added, 4 parts of triethylamine were additionally added, and the resulting mixture was stirred at 30 ° C for 1 hour, thereby completing the reaction. After completion of the reaction, the resulting product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and then washed with water. When the electrical conductivity of the aqueous phase became almost the same as that of water after treatment by the ion exchange method, methylene chloride was evaporated using a plasticizer. Thus, a white powder was obtained with a molar ratio of BCF / BPM of 40:60. This powder had a specific viscosity of 0.283.

To this powder was added 0.003 parts of tris (2,4-di-tert-butylphenyl) phosphite, 0.005 parts of trimethyl phosphate and 0.045 parts of monoglyceride stearate per 100 parts of powder. After that, the powder was mixed in the melt using a twin-screw extruder with a gas suction (KTX-46 from Kobe Steel, Ltd.) at a cylinder temperature of 260 ° C with degassing, granulation, and then injection molding to obtain a disk substrate having a diameter of 120 mm and a thickness of 1.2 mm when using the M35-D-DM from MEIKI CO., LTD.

Optical disc

In turn, a reflective film, a first dielectric layer, a phase-transition recording film and a second dielectric layer were applied to the substrate of the disk by spraying, and the cover layer was laminated on top of it in the form of a thin film of polycarbonate, thereby obtaining an optical disk of interest. Initial mechanical properties, ΔTilt and damping were evaluated for the disk substrate. The evaluation results are shown in table 5.

Example 20

Polymerization

By the same method as in Example 19, a white powder was obtained with a BCF / BPM molar ratio of 35:65, except that phosgene purging was carried out using 1814 parts of BCF used in Example 19 and 3084 parts of BPM used in Example 19, and after purging with phosgene 86 parts of p-tert-butylphenol were added. This powder had a specific viscosity of 0.283.

The same additives were added to this powder as those used in Example 19, and in the same quantities as those used in Example 19, and the resulting mixture was melt-blended and granulated in the same manner as in Example 19. Thereafter, the granules were injection molded in the same manner as in Example 19, so as to obtain an optical disk.

Optical disc

In turn, a reflective film, a first dielectric layer, a phase-transition recording film and a second dielectric layer were applied to the substrate of the disk by spraying, and the cover layer was laminated on top of it in the form of a thin film of polycarbonate, thereby obtaining an optical disk of interest. Initial mechanical properties, ΔTilt and damping were evaluated for the disk substrate. The evaluation results are shown in table 5.

Example 21

Polymerization

By the same method as in Example 19, a white powder was obtained with a BCF / BPM molar ratio of 50:50, except that phosgene purging was carried out using 2277 parts of BCF used in Example 19 and 2084 parts of BPM used in Example 19, and after purging with phosgene, 74 parts of p-tert-butylphenol were added. This powder was characterized by a specific viscosity of 0.263.

The same additives were added to this powder as those used in Example 19, and in the same quantities as those used in Example 19, and the resulting mixture was melt-blended and granulated in the same manner as in Example 19. Thereafter, the granules were injection molded in the same manner as in Example 19, so as to obtain an optical disk.

Optical disc

In turn, a reflective film, a first dielectric layer, a phase-transition recording film and a second dielectric layer were applied to the substrate of the disk by spraying, and the cover layer was laminated on top of it in the form of a thin film of polycarbonate, thereby obtaining an optical disk of interest. Initial mechanical properties, ΔTilt and damping were evaluated for the disk substrate. The evaluation results are shown in table 5.

Example 22

Polymerization

By the same method as in Example 19, a white powder was obtained with a BCF / BPM / THPE molar ratio of 40: 60: 0.5, except that after purging with phosgene in Example 19, 23 parts of THPE and 81 parts of p- were added. tert-butylphenol. This powder had a specific viscosity of 0.283.

The same additives were added to this powder as those used in Example 19, and in the same quantities as those used in Example 19, and the resulting mixture was melt-blended and granulated in the same manner as in Example 19. Thereafter, the granules were injection molded in the same manner as in Example 19, so as to obtain a disk substrate.

Optical disc

In turn, a reflective film, a first dielectric layer, a phase-transition recording film and a second dielectric layer were applied to the substrate of the disk by spraying, and the coating layer was laminated on top of it in the form of a thin film of polycarbonate, thereby obtaining an optical disk of interest. Initial mechanical properties, ΔTilt and damping were evaluated for the disk substrate. The evaluation results are shown in table 5.

Example 23

Polymerization

By the same method as in Example 19, a white powder was obtained with a BCF / BPC molar ratio of 40:60, except that phosgene purging was carried out using 2277 parts of BCF used in Example 19 and 2313 parts of 2.2- bis (3-methyl-4-hydroxyphenyl) propane (hereinafter abbreviated as “BPC”) instead of the BPM used in Example 19, and after purging with phosgene, 72 parts of p-tert-butylphenol were added. This powder was characterized by a specific viscosity of 0.279.

The same additives were added to this powder as those used in Example 19, and in the same quantities as those used in Example 19, and the resulting mixture was melt-blended and granulated in the same manner as in Example 19. Thereafter, the granules were injection molded in the same manner as in Example 19, so as to obtain a disk substrate.

Optical disc

In turn, a reflective film, a first dielectric layer, a phase-transition recording film and a second dielectric layer were applied to the substrate of the disk by spraying, and the cover layer was laminated on top of it in the form of a thin film of polycarbonate, thereby obtaining an optical disk of interest. Initial mechanical properties, ΔTilt and damping were evaluated for the disk substrate. The evaluation results are shown in table 5.

Reference Example 8

Polymerization

By the same method as in Example 19, 4750 parts of a colorless polymer were obtained, except that only 4320 parts of bisphenol A (BPA) were used as the dihydroxy component. This powder had a specific viscosity of 0.289.

The same additives were added to this powder as those used in Example 19, and in the same quantities as those used in Example 19, and the resulting mixture was melt-blended and granulated in the same manner as in Example 19. Thereafter, the granules were injection molded in the same manner as in Example 19, so as to obtain a disk substrate.

Optical disc

In turn, a reflective film, a first dielectric layer, a phase-transition recording film and a second dielectric layer were applied to the substrate of the disk by spraying, and the cover layer was laminated on top of it in the form of a thin film of polycarbonate, thereby obtaining an optical disk of interest. Initial mechanical properties, ΔTilt and damping were evaluated for the disk substrate. The evaluation results are shown in table 5.

Reference Example 9

A disk substrate having a diameter of 120 mm and a thickness of 1.2 mm was obtained by the injection method of polymethyl methacrylate (VLD-100) from Rohm & Haas Japan Co., Ltd. when using the M35B-D-DM machine from MEIKI CO., LTD. In turn, a reflective film, a first dielectric layer, a phase-transition recording film and a second dielectric layer were applied to the substrate of the disk by spraying, and the coating layer was laminated on top of it in the form of a thin film of polycarbonate, thereby obtaining an optical disk of interest.

Initial mechanical properties, ΔTilt and damping were evaluated for the disk substrate. The evaluation results are shown in table 5.

As shown in table 5, the polymers shown in examples 19-23 can provide a reduction in water absorption when saturation is reached to 0.3% or less, and ΔTilt values to 0.5 or less. In addition to this, they are also characterized by rather high values of the bending elastic modulus and tanδ, the oscillating surface vibration that occurs when the molded optical disks rotate at a high speed can be kept at a low level.

PC-A from comparative example 8 is characterized by low stiffness and tanδ. Thus, the oscillatory surface vibration that occurs when the optical disk rotates at high speed has a significant amplitude. In addition, it is also characterized by higher water absorption when saturation is achieved in comparison with the examples; the ΔTilt value for it is large.

PMMA from comparative example 9 is characterized by high water absorption upon reaching saturation of 2.0% or more. Thus, the value of ΔTilt is very large, reaching 5.0 or more, and therefore it was recognized that it is not suitable for practical use.

Table 5 Example 19 Example 20 Example 21 Example 22 Example 23 Reference Example 8 Reference Example 9 The ratio of components in the composition (mol.%) BCF Component a 40 35 fifty 40 40 - - Bisphenol
fluoren - - - - - - - BPM Component b 60 65 fifty 60 - - - HRV Component b - - - - 60 - - TNRE - - - 0.5 - - - VRA one hundred PMMA - - - - - - one hundred Grade Results for Polymers Specific viscosity - 0.283 0.284 0.274 0.283 0.279 0.289 - Deformation resistance (° C) 134 129 149 134 145 126 89 tanδ - 0,039 0,037 0,042 0,039 0,032 0.007 0,078 Flexural modulus (MPa) 3100 3040 3170 3170 2910 2400 3630 Water absorption upon reaching saturation wt.% 0.26 0.26 0.23 0.25 0.22 0.37 2.00 Evaluation Results for Discs Cylinder temperature (° C) 320 Form Clamping Force Ton 32 Mold temperature (° C) 127 122 140 126 136 119 81 The initial form of the substrate (degree) 0.20 0.20 0.20 0.20 0.20 0.20 0.36 ΔTilt (degree) 0.46 0.46 0.42 0.46 0.43 0.78 5.00 or more

Examples 24-31 and comparative examples 10-13

Plastic mirror

Physical properties were measured using the following methods.

(1) Specific viscosity: it was measured at a temperature of 20 ° C after dissolving 0.7 g of the polymer in 100 ml of methylene chloride.

(2) Glass transition temperature (Tg): it was measured at a temperature increase rate of 10 ° C / min using a type 2910 DSC instrument from TA INSTRUMENTS JAPAN CO., LTD.

(3) Water absorption: Water absorption was measured after immersion in water at 23 ° C for 24 hours in accordance with ISO 62.

(4) Bending modulus: the bending modulus of a test specimen obtained by drying the granules at 120 ° C for 5 hours, and then performing the injection molding pellets using an injection machine (SG-150 from Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 300 ° C, measured in accordance with ISO 178.

(5) Degree of warpage: a disk substrate having a diameter of 120 mm and a thickness of 1.2 mm was obtained by injection molding using an M35B-D-DM machine from MEIKI CO., LTD. After that, an aluminum film was applied to one surface of the substrate. After the disk substrate was exposed to the environment (environment A), where the temperature was 30 ° C and the humidity corresponded to 90% relative humidity, until saturation by water absorption was reached, the disk substrate was transferred to the environment (environment B), where the temperature was 23 ° C, and the humidity corresponded to 50% relative humidity. After transferring the substrate of the disk over time, we measured the change in angular deviation at a distance of 58 mm from the center, which occurred as a result of environmental changes, using a DLD-3000U three-dimensional shape measuring instrument from Japan EM Co., Ltd. The difference between the maximum value of the change in angular deviation and the value at which the change in angular deviation reaches a stationary value was taken as ΔTilt.

(6) The ability to imprint in the form: the degree of surface roughness of the molded substrate was measured using a SURFCORDER SE1100 instrument from Kosaka laboratory Ltd.

Example 24

Polymerization

19580 parts of water after ion exchange treatment and 3850 parts of an aqueous solution of sodium hydroxide with a concentration of 48.5% were placed in a reactor equipped with a thermometer and a stirrer, and then 1175 parts of BCF, 2835 parts of 2,2-bis (4-hydroxyphenyl) were dissolved ) propane (hereinafter abbreviated as "BPA") and 9 parts of hydrosulfite. Then, after adding 13210 parts of methylene chloride at 15 ° C. with vigorous stirring for approximately 40 minutes, 2000 parts of phosgene were purged through the mixture in order to initiate a reaction. After purging the phosgene, the temperature increased to 28 ° C, and in order to stimulate the passage of emulsification, 94 parts of p-tert-butylphenol and 640 parts of sodium hydroxide were added. After that, 6 parts of triethylamine were added, and the resulting mixture was continuously stirred for 1 hour, thereby completing the reaction.

After completion of the reaction, the organic phase was separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and then washed with water. When the electrical conductivity of the aqueous phase became almost the same as that of water after treatment by the ion exchange method, methylene chloride was evaporated using a plasticizer. Thus, 4080 parts of a colorless powder with a 20: 80 BCF / PCA molar ratio were obtained. This powder was characterized by a specific viscosity of 0.285 and Tg of 172 ° C.

Molding

To this powder was added 0.003 parts of tris (2,4-di-tert-butylphenyl) phosphite, 0.005 parts of trimethyl phosphate and 0.045 parts of monoglyceride stearate per 100 parts of powder. After that, the powder was mixed in the melt using a twin-screw extruder with a gas suction (KTX-46 from Kobe Steel, Ltd.) at a cylinder temperature of 280 ° C with degassing, granulation, and then injection molding to obtain a disk substrate having a diameter of 120 mm and a thickness of 1.2 mm when using the M35 B-D-DM machine from MEIKI CO., LTD. The substrate had a sufficiently smooth surface to be used as a plastic mirror.

In addition, aluminum was deposited onto a substrate to a thickness of 50 nm using an EKC-1 Ion Plating apparatus from Sumitomo Heavy Industries, Ltd. The maximum degree of warpage as a result of water absorption in the substrate with precipitated aluminum was 0.9 degrees. In addition, the substrate was also characterized by the values of water absorption of 0.170 wt.% And the modulus of elasticity in bending 2700 MPa.

Example 25

Polymerization

By the same method as in Example 24, 4830 parts of a colorless powder with a 50:50 BCF / BPA molar ratio were obtained, except that 2937 parts of BCF, 1772 parts of BPA and 84 parts of p-tert-butylphenol were used. This powder was characterized by a specific viscosity of 0.278 and Tg of 195 ° C.

Molding

The same additives were added to this powder as those used in Example 24, and in the same quantities as those used in Example 24, and the resulting mixture was melt blended and granulated in the same manner as in Example 24, except that the cylinder temperature was 300 ° C. After that, these granules were injection molded in the same way as in example 24, so as to obtain a substrate. The substrate had a sufficiently smooth surface to be used as a plastic mirror.

Aluminum was precipitated onto the substrate. The maximum degree of warpage as a result of water absorption in the substrate with precipitated aluminum was 0.9 degrees. In addition, the substrate was also characterized by the values of water absorption of 0.160 wt.% And the modulus of elasticity in bending 2950 MPa.

Example 26

Polymerization

By the same method as in Example 24, 4050 parts of a colorless powder with a molar ratio of BCF / BPA / THPE of 20: 80: 0.5 were obtained, except that after purging the phosgene, 24 parts of 1,1,1- were added. tris (4-hydroxyphenyl) ethane (hereinafter abbreviated as “THPE”), and the amount of p-tert-butylphenol was changed to 104 parts. This powder was characterized by a specific viscosity of 0.285 and Tg of 173 ° C.

Molding

The same additives were added to this powder as those used in Example 24, and in the same quantities as those used in Example 24, and the resulting mixture was melt blended and granulated in the same manner as in Example 24. Thereafter, these granules were injection molded in the same manner as in Example 24, so as to obtain a substrate. The substrate had a sufficiently smooth surface to be used as a plastic mirror.

Aluminum was precipitated onto the substrate. The maximum degree of warpage as a result of water absorption in the substrate with precipitated aluminum was 0.9 degrees. In addition, the substrate was also characterized by the values of water absorption of 0.160 wt.% And the modulus of elasticity in bending 2720 MPa.

Example 27

Polymerization

In the same method as in Example 24, 5,300 parts of a colorless powder with a 70: 30 BCF / BPA molar ratio were obtained, except that 4,112 parts of BCF, 1,063 parts of BPA and 84 parts of p-tert-butylphenol were used. This powder was characterized by a specific viscosity of 0.261 and Tg of 210 ° C.

Molding

The same additives were added to this powder as those used in Example 24, and in the same quantities as those used in Example 24, and the resulting mixture was melt-blended and granulated in the same manner as in Example 24, except that the cylinder temperature was 320 ° C. After that, these granules were injection molded in the same way as in example 24, so as to obtain a substrate. The substrate had a sufficiently smooth surface to be used as a plastic mirror.

Aluminum was precipitated onto the substrate. The maximum degree of warpage as a result of water absorption in the substrate with precipitated aluminum was 0.9 degrees. In addition, the substrate was also characterized by the values of water absorption of 0.150 wt.% And the modulus of elasticity in bending 3200 MPa.

Reference Example 10

Polymerization

In the same method as in Example 24, 3670 parts of a colorless polymer were obtained, except that only 3543 parts of BPA were used as the dihydroxy component and 140 parts of p-tert-butylphenol were used. This powder was characterized by a specific viscosity of 0.290 and Tg of 142 ° C.

Molding

The same additives were added to this powder as those used in Example 24, and in the same quantities as those used in Example 24, and the resulting mixture was melt blended and granulated in the same manner as in Example 24. Thereafter, these granules were injection molded in the same manner as in Example 24, so as to obtain a substrate. The substrate had a sufficiently smooth surface to be used as a plastic mirror. After that, aluminum was precipitated onto the substrate. The maximum degree of warpage as a result of water absorption in the substrate with precipitated aluminum was 1.4 degrees. In addition, the substrate was also characterized by a high value of water absorption of 0.21 wt.% And a low value of the modulus of elasticity in bending 2350 MPa.

Reference Example 11

Polymerization

By the same method as in Example 24, 3650 parts of a colorless polymer were obtained, except that only 3542 parts of BPA were used as the dihydroxy component and 140 parts of p-tert-butylphenol were used. This powder was characterized by a specific viscosity of 0.289 and Tg of 142 ° C.

Molding

The same additives were added to this powder as those used in Example 24, and in the same quantities as those used in Example 24, and the resulting mixture was melt-blended and granulated in the same manner as in Example 24. In addition, 1188 parts of 13 micron fiber glass from Nippon Electric Glass Co., Ltd. were added to this polymer. After they were mixed in a drum mixer until a homogeneous mixture was obtained, the mixture was melt-mixed at 240 ° C using a twin-screw extruder with gas exhaust (KTX-46 from Kobe Steel, Ltd.) with degassing, resulting in granules. Thereafter, a disc substrate having a diameter of 120 mm and a thickness of 1.2 mm was obtained from the granules by the injection molding method using an M35 B-D-DM machine from MEIKI CO., LTD. In addition, aluminum was deposited onto the substrate to a film thickness of 50 nm using an EKC-1 Ion Plating apparatus from Sumitomo Heavy Industries, Ltd. Despite the fact that the substrate with precipitated aluminum showed a significantly improved stiffness of 6330 MPa, some fiberglass strands protruded onto the surface of the substrate, thereby making it impossible to use the substrate as a mirror. In addition, the substrate with precipitated aluminum was characterized by water absorption values of 0.13 wt.% And a maximum degree of warpage as a result of water absorption of 0.1 degrees.

The results for these examples and comparative examples are shown in table 6.

Multifaceted mirror

In addition, the granules obtained in the above examples 24-27 and comparative examples 10 and 11 were dried at 120 ° C for 5 hours. After that, an injection molding machine (SG150U from Sumitomo Heavy Industries, Ltd.) was used at a cylinder temperature of 340 ° C and a mold temperature of 115 ° C. Polyhedral mirrors were formed, which were similar in type to hexagonal mirrors, each of which had a distance between the center and each a mirror surface of 25 mm, a minimum plate thickness in each mirror section of 5 mm and a mirror height of 15 mm. The results of evaluations of the ability to print in the form for polyhedral mirrors are shown in table 6.

After that, a film of Al was deposited onto these substrates to a thickness of 80 nm, obtaining polyhedral mirrors. Comparative example 11 could not be used to obtain a mirror, because it obtained unsatisfactory surface properties. In comparative example 10, an unsatisfactory flexural modulus was obtained, and the distortion of the mirror portions during rotation turned out to be significant. In examples 24-27, good surface properties were obtained, in this case, the distortion of the mirror sections was small due to the high values of the bending elastic modulus, and therefore these materials were sufficiently acceptable for practical use.

Table 6 Position Example 24 Example 25 Example 26 Example 27 Reference Example 10 Reference Example 11 BCF Component a twenty fifty twenty 70 - - VRA Component b 80 fifty 80 thirty one hundred one hundred TNRE - - 0.5 - - - Fiberglass - - - - - 25 Specific viscosity - 0.285 0.278 0.285 0.261 0.290 0.289 Glass transition temperature (° C) 172 195 173 210 142 142 Flexural modulus (MPa) 2700 2950 2720 3200 2350 6330 Water absorption wt.% 0.170 0.160 0.160 0.150 0.210 0.130 Cylinder temperature (° C) 320 340 320 350 280 280 Form Clamping Force (ton) 65 65 65 65 65 65 Mold temperature (° C) one hundred 130 one hundred 130 one hundred one hundred Maximum degree of warping as a result of water absorption (degree) 0.9 0.9 0.9 0.9 1.4 0.1 Surface roughness Disk nm 40 fifty 45 51 thirty 600 Multifaceted Mirror Substrate nm 38 fifty 48 45 32 570

Example 28

Polymerization

32,165 parts of water after ion exchange treatment and 1757 parts of sodium hydroxide were placed in a reactor equipped with a thermometer, stirrer, reflux condenser and phosgene injection tube, and 2213 parts of 9.9-bis (3-methyl-4-hydroxyphenyl) fluorene were dissolved (hereinafter abbreviated as "BCF"), 3039 parts of 4,4 '- (m-phenylenediisopropylidene) diphenol (hereinafter abbreviated as "BPM") and 11 parts of hydrosulfite. Then, after adding 10950 parts of methylene chloride at 16-18 ° C., 1667 parts of phosgene were purged with stirring for 60 minutes. After the phosgene purge was completed, 92 parts of p-tert-butylphenol and 293 parts of sodium hydroxide were added, 4 parts of triethylamine were additionally added, and the resulting mixture was stirred at 30 ° C for 1 hour, thereby completing the reaction.

After completion of the reaction, the resulting product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and then washed with water. When the electrical conductivity of the aqueous phase became almost the same as that of water after treatment by the ion exchange method, methylene chloride was evaporated using a plasticizer. Thus, 5554 parts of a colorless powder were obtained with a 40:60 BCF / BPM molar ratio. This powder was characterized by a specific viscosity of 0.285 and Tg of 144 ° C.

Molding

To this powder was added 0.003 parts of tris (2,4-di-tert-butylphenyl) phosphite, 0.005 parts of trimethyl phosphate and 0.045 parts of monoglyceride stearate per 100 parts of powder.

After that, the powder was mixed in the melt using a twin-screw extruder with a gas suction (KTX-46 from Kobe Steel, Ltd.) at a cylinder temperature of 240 ° C with degassing, granulation, and then injection molding to obtain a disk substrate having a diameter of 120 mm and a thickness of 1.2 mm when using the M35 B-D-DM machine from MEIKI CO., LTD. The substrate had a sufficiently smooth surface to be used as a plastic mirror.

In addition, aluminum was deposited onto a substrate to a thickness of 50 nm using an EKC-1 Ion Plating apparatus from Sumitomo Heavy Industries, Ltd. The maximum degree of warpage as a result of water absorption in the substrate with precipitated aluminum was 0.4 degrees. In addition, the substrate was characterized by MVR values of 34 g / 10 min, water absorption of 0.083 wt.% And a flexural modulus of 3260 MPa.

Example 29

Polymerization

By the same method as in Example 28, 5224 parts of a colorless powder with a 50:50 BCF / BPM molar ratio were obtained, except that 2596 parts of BCF and 2377 parts of BPM were used. This powder was characterized by a specific viscosity of 0.269 and Tg of 155 ° C.

Molding

The same additives were added to this powder as those used in Example 28, and in the same quantities as those used in Example 28, and the resulting mixture was mixed in the melt and granulated in the same manner as in Example 28. After that, these granules were injection molded in the same manner as in Example 28, so as to obtain a substrate. The substrate had a sufficiently smooth surface to be used as a plastic mirror. After that, aluminum was precipitated onto the substrate. The maximum degree of warpage as a result of water absorption in the substrate with precipitated aluminum was 0.4 degrees. In addition, the substrate was characterized by MVR values of 26 g / 10 min, water absorption of 0.080 wt.% And a flexural modulus of 3330 MPa.

Example 30

Polymerization

By the same method as in Example 28, 5,245 parts of a colorless powder were obtained with a BCF / BPM / THPE molar ratio of 40: 60: 0.5, except that after purging the phosgene, 21 parts of 1,1,1 were additionally added. tris (4-hydroxyphenyl) ethane (hereinafter abbreviated as “THPE”), and the amount of p-tert-butylphenol was changed to 113 parts. This powder was characterized by a specific viscosity of 0.288 and Tg of 143 ° C.

Molding

The same additives were added to this powder as those used in Example 28, and in the same quantities as those used in Example 28, and the resulting mixture was melt-mixed and granulated in the same way as in Example 28. After that, these granules were injection molded in the same manner as in Example 28, so as to obtain a substrate. The substrate had a sufficiently smooth surface to be used as a plastic mirror. After that, aluminum was precipitated onto the substrate. The maximum degree of warpage as a result of water absorption in the substrate with precipitated aluminum was 0.4 degrees. In addition, the substrate was characterized by MVR values of 36 g / 10 min, water absorption of 0.083 wt.% And a flexural modulus of 3280 MPa.

Example 31

Polymerization

By the same method as in Example 28, 5460 parts of a colorless powder were obtained with a BCF / BPM molar ratio of 65:35, except that 3598 parts of BCF and 1773 parts of BPM were used. This powder was characterized by a specific viscosity of 0.264 and Tg of 175 ° C.

Molding

The same additives were added to this powder as those used in Example 28, and in the same quantities as those used in Example 28, and the resulting mixture was mixed in the melt and granulated in the same manner as in Example 28, except that the cylinder temperature was 280 ° C. After that, these granules were injection molded in the same manner as in Example 28, so as to obtain a substrate. The substrate had a sufficiently smooth surface to be used as a plastic mirror. After that, aluminum was precipitated onto the substrate. The maximum degree of warpage as a result of water absorption in the substrate with precipitated aluminum was 0.5 degrees. In addition, the substrate was characterized by MVR values of 26 g / 10 min, water absorption of 0.080 wt.% And a flexural modulus of 3330 MPa.

Reference Example 12

Polymerization

By the same method as in Example 28, 4750 parts of a colorless polymer were obtained, except that only 4320 parts of bisphenol A were used as the dihydroxy component. This powder had a specific viscosity of 0.289 and Tg of 142 ° C.

Molding

The same additives were added to this powder as those used in Example 28, and in the same quantities as those used in Example 28, and the resulting mixture was mixed in the melt and granulated in the same manner as in Example 28. After that, these granules were injection molded in the same manner as in Example 28, so as to obtain a substrate. The substrate had a sufficiently smooth surface to be used as a plastic mirror. After that, aluminum was precipitated onto the substrate. The maximum degree of warpage as a result of water absorption in the substrate with precipitated aluminum was as much as 1.4 degrees. In addition, the substrate was characterized by a magnitude of MVR of 69 g / 10 min, a high value of water absorption of 0.21 wt.% And a low value of the elastic modulus in bending of 2350 MPa.

Reference Example 13

Polymerization

By the same method as in Example 28, 4750 parts of a colorless polymer were obtained, except that only 4320 parts of bisphenol A were used as the dihydroxy component. This powder had a specific viscosity of 0.286 and Tg of 142 ° C.

Molding

The same additives were added to this powder as those used in Example 28, and in the same quantities as those used in Example 28, and the resulting mixture was mixed in the melt and granulated in the same manner as in Example 28. In addition, 1188 parts of fiberglass with a fiber diameter of 13 microns from Nippon Electric Glass Co., Ltd. were added to this polymer. After they were mixed in a drum mixer until a homogeneous mixture was obtained, the mixture was melt-mixed at 240 ° C using a twin-screw extruder with gas exhaust (KTX-46 from Kobe Steel, Ltd.) with degassing, resulting in granules. Thereafter, a disc substrate having a diameter of 120 mm and a thickness of 1.2 mm was obtained from the granules by the injection molding method using an M35 B-D-DM machine from MEIKI CO., LTD. In addition, aluminum was deposited onto the substrate to a film thickness of 50 nm using an EKC-1 Ion Plating apparatus from Sumitomo Heavy Industries, Ltd. Despite the fact that the substrate with precipitated aluminum showed a significantly improved stiffness of 6330 MPa, some fiberglass strands protruded onto the surface of the substrate, thereby making it impossible to use the substrate as a mirror. In addition, the substrate with precipitated aluminum was characterized by values of MVR 64 g / 10 min, water absorption of 0.13 wt.% And a maximum degree of warpage as a result of water absorption of 0.1 degrees.

The results for these examples and comparative examples are shown in table 7.

Multifaceted mirror

In addition, the granules obtained in the above examples 28-31 and comparative examples 12 and 13 were dried at 120 ° C for 5 hours. After that, an injection machine (SG150U from Sumitomo Heavy Industries, Ltd.) was used at a cylinder temperature of 300 ° C and a mold temperature of 100 ° C. Polyhedral mirrors were formed, which were similar in type to hexagonal mirrors, each of which had a distance between the center and each a mirror surface of 25 mm, a minimum plate thickness in each mirror section of 5 mm and a mirror height of 15 mm. The results of evaluations of the ability to print in the form for polyhedral mirrors are shown in table 7.

After that, a film of Al was deposited onto these substrates to a thickness of 80 nm, obtaining polyhedral mirrors. Comparative example 12 could not be used to obtain a mirror, because it obtained unsatisfactory surface properties. In comparative example 12, an unsatisfactory flexural modulus was obtained, and the distortion of the mirror portions during rotation turned out to be significant. In examples 28-31, good surface properties were obtained, in this case, the distortion of the mirror sections was small due to the high values of the bending elastic modulus, and therefore these materials were quite acceptable for practical use.

Table 7 Position Example 28 Example 29 Example 30 Example 31 Reference Example 12 Reference Example 13 BCF Component a 40 fifty 40 65 - - BPM Component b 60 fifty 60 35 - - VRA - - - - one hundred one hundred TNRE - - 0.5 - - - Fiberglass - - - - - 25 Specific viscosity - 0.285 0.269 0.288 0.264 0.289 0.286 Glass transition temperature (° C) 144 155 143 175 142 142 Flexural modulus (MPa) 3260 3330 3280 3520 2350 6330 Water absorption wt.% 0,083 0,080 0,083 0,079 0.210 0.130 MVR cm ³ 34 26 36 9 69 64 Cylinder temperature (° C) 280 280 280 320 280 280 Form Clamping Force (ton) 65 65 65 65 65 65 Mold temperature (° C) one hundred one hundred one hundred 120 one hundred one hundred Maximum degree of warping as a result of water absorption (degree) 0.4 0.4 0.4 0.5 1.4 0.1 Surface roughness Disk nm thirty 35 35 34 thirty 600 Multifaceted Mirror Substrate nm 32 34 36 35 32 570

Examples 32-36 and comparative examples 14 and 15

Conductive polymer composition

Physical properties were evaluated using the following methods.

(1) Specific viscosity

It was measured at a temperature of 20 ° C after dissolving 0.7 g of the polymer in 100 ml of methylene chloride.

(2) Glass transition temperature (Tg)

It was measured at a temperature increase rate of 20 ° C / min using a type 2910 DSC instrument from TA INSTRUMENTS JAPAN CO., LTD.

(3) Heat Resistance

Heat resistance under a load of 18.5 kg was measured in accordance with ASTM D648.

(4) Electrical conductivity

The surface resistance value was measured in accordance with ASTM D257.

(5) water absorption

Water absorption was measured after immersion in water at 23 ° C for 24 hours in accordance with ASTM D-0570.

(6) Irritation

The polymer that causes the appearance of irritation on the skin, when evaluated, received the designation "x", and the polymer, which does not cause the appearance of irritation on the skin, when evaluated, received the designation "○", the evaluation was carried out during the preparation of molded products for measurements by the following methods.

(7) Heat Cycle Test

The injection tray obtained by the injection molding method, having dimensions of 153 mm × 142 mm × 165 mm and a pitch between grooves of 4.76 mm and capable of accommodating 25 5-inch disks, was subjected to 10 cycles, each of which included 20 hours at 150 ° C and 4 hours at 23 ° C, and observed the appearance of deformation in the molded product.

Polymerization

RS1

21538 parts of water after ion exchange treatment and 4229 parts of an aqueous solution of sodium hydroxide with a concentration of 48% were placed in a reactor equipped with a thermometer, stirrer and reflux condenser, and 1949 parts of bisphenol A, 3231 parts of biscresolfluorene and 10.9 parts of hydrosulfite were dissolved. Then, after adding 14530 parts of methylene chloride at 16-20 ° C. with stirring for 60 minutes, 2200 parts of phosgene were purged through the mixture. After purging the phosgene, 115.4 parts of p-tert-butylphenol and 705 parts of an aqueous solution of sodium hydroxide with a concentration of 48% were added, 2.6 parts of triethylamine were additionally added, and the resulting mixture was stirred at 20-27 ° C for 40 minutes , thereby completing the reaction.

After completion of the reaction, the resulting product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and then washed with water. When the electrical conductivity of the aqueous phase became almost the same as that of water after treatment by the ion exchange method, methylene chloride was evaporated using a plasticizer. The result was 5520 parts of a whitish-yellow polymer with a molar ratio of bisphenol A / biscresolfluoren 50:50, specific viscosity 0.272 and Tg 197 ° C (96% yield).

To this polycarbonate copolymer, 0.050% tris (2,4-di-tert-butylphenyl) phosphite, 0.010% octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.030% pentaerythritol tetra-stearate and the resulting as a result, the mixture was extruded using an extruder at a cylinder temperature of 300 ° C to obtain polycarbonate copolymer (PC1) granules.

PC2

19580 parts of water after ion exchange and 3845 parts of an aqueous solution of sodium hydroxide with a concentration of 48% were placed in a reactor equipped with a thermometer, stirrer and reflux condenser, and 2835 parts of bisphenol A, 1175 parts of biscresolfluorene and 8.4 parts of hydrosulfite were dissolved. Then, after adding 13209 parts of methylene chloride at 18-20 ° C. with stirring for 60 minutes, 2000 parts of phosgene were purged through the mixture. After the phosgene purge was completed, 93.2 parts of p-tert-butylphenol and 641 parts of an aqueous sodium hydroxide solution with a concentration of 48% were added, 2.0 parts of triethylamine were additionally added, and the resulting mixture was stirred at 20-27 ° C for 40 minutes , thereby completing the reaction.

After completion of the reaction, the resulting product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and then washed with water. When the electrical conductivity of the aqueous phase became almost the same as that of water after treatment by the ion exchange method, methylene chloride was evaporated using a plasticizer. The result was 4230 parts of a whitish-yellow polymer with a molar ratio of bisphenol A / biscresolfluorene of 80:20, specific viscosity 0.374 and Tg 173 ° C (yield 94%).

To this polycarbonate copolymer, 0.050% tris (2,4-di-tert-butylphenyl) phosphite, 0.010% octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.030% pentaerythritol tetra-stearate and the resulting as a result, the mixture was extruded using an extruder at a cylinder temperature of 280 ° C. to obtain polycarbonate copolymer (PC2) granules.

S-PC1

20,980 parts of water after ion exchange and 1523 parts of potassium hydroxide were placed in a reactor equipped with a thermometer, stirrer and reflux condenser, and 886 parts of bisphenol A, 1360 parts of 9.9-bis (4-hydroxyphenyl) fluorene (hereinafter, in the present) were dissolved document called "bisphenolfluorene") and 4.7 parts of hydrosulfite. Then, after adding 13210 parts of methylene chloride at 18-20 ° C. with stirring for 60 minutes, 1000 parts of phosgene were purged through the mixture. After purging the phosgene, 52.4 parts of p-tert-butylphenol and 218 parts of potassium hydroxide were added, 2.7 parts of triethylamine were added, and the resulting mixture was stirred at 20-27 ° C for 40 minutes, thereby completing the reaction.

After completion of the reaction, the resulting product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and then washed with water. When the electrical conductivity of the aqueous phase became almost the same as that of water after treatment by the ion exchange method, methylene chloride was evaporated using a plasticizer. The result was 2250 parts of a whitish-yellow polymer with a molar ratio of bisphenol A / bisphenol-fluorene of 50:50, specific viscosity 0.272 and Tg 205 ° C (yield 90%).

To this polycarbonate copolymer, 0.050% tris (2,4-di-tert-butylphenyl) phosphite, 0.010% octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 0.030% pentaerythritol tetra-stearate and the resulting as a result, the mixture was extruded using an extruder at a cylinder temperature of 300 ° C to obtain polycarbonate copolymer granules (C-PC1).

C-RS2

By the same method as that used in the preparation of PC1, 3870 parts of a whitish-yellow polymer with a molar ratio of bisphenol A / biscresolfluorene 99: 1, specific viscosity 0.390 and Tg 148 ° C (95% yield) were obtained, except that they were used 3907 parts of bisphenol A and 59 parts of biscresolfluorene. By the same method as used in the preparation of PC1, granules of an aromatic polycarbonate polymer (C-PC2) were obtained from the polymer.

Carbon based filler

Carbon fiber: BESFIGHT HTA-C6-U from TOHO RAYON CO., LTD., Based on PAN (polyacrylonitrile), adhered by epoxy, fiber diameter 7 microns.

Carbon black: ketjenblack EC600JD from Lion Corporation (hereinafter referred to as "CB").

Examples 32-36 and comparative examples 14 and 15

Molding

The PC1 and PC2, C-PC1 or C-PC2 obtained above and the components shown in Tables 8 and 9 were mixed until homogeneous using a drum mixer, and then granulated using a ⌀30 mm twin screw extruder with gas exhaust (CTX-30 from KobeSteel, Ltd.) at a cylinder temperature of 300 ° C and a vacuum level of 10 mm Hg. when carrying out degassing. The obtained granules were dried at 120 ° C for 5 hours, and then using a molding machine (SG150U from Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 330 ° C and a mold temperature of 100 ° C, molded products were made for measurements. The evaluation results are shown in tables 8 and 9.

Transport tray

Then, after the granules obtained by the same method as described above were dried at 120 ° C for 5 hours, transport trays were made by injection molding at a cylinder temperature of 350 ° C and a mold temperature of 100 ° C. each of which had dimensions of 153 mm × 142 mm × 165 mm and a pitch between grooves of 4.76 mm and was able to accommodate 25 5-inch wheels. The results of the tests for the thermal cycle are shown in tables 8 and 9.

From the comparisons between the above examples and comparative examples, it clearly follows that compositions based on an aromatic polycarbonate polymer containing the polycarbonate copolymers of the present invention and carbon fibers have better heat resistance and conductivity compared to compositions of comparative examples using aromatic polycarbonate polymers and do not cause the appearance of irritation on the skin.

Table 8 unit of measurement Example 32 Example 33 Example 34 Example 35 Example 36 Songs Polycarbonate Polymers RS1 Mass parts one hundred one hundred one hundred one hundred PC2 Mass parts one hundred Carbon based fillers Carbon fiber Mass parts twenty twenty 12 10 NE Mass parts 10 one Grades Deformation resistance ° C 192 171 191 186 189 Conductivity Ohm 10 ⁴ 10 ⁴ 10 ⁵ 10 ³ 10 ³ Water absorption wt.% 0.16 0.18 0.17 0.18 0.17 Irritation - ○ ○ ○ ○ ○ Heat cycle test - Good Good Good Good Good

Table 9 unit of measurement Reference Example 14 Reference Example 15 Songs Polycarbonate Resins RS1 Mass parts PC2 Mass parts S-PC1 Mass parts one hundred C-RS2 Mass parts one hundred Carbon based fillers Carbon fiber Mass parts twenty twenty NE Mass parts Grades Deformation resistance ° C 195 147 Conductivity Ohm 10 ⁴ 10 ⁴ Water absorption wt.% 0.26 0.20 Irritation - x ○

In accordance with the present invention, there is provided a polycarbonate copolymer characterized by excellent heat resistance and the ability to maintain dimensions and low water absorption and not causing skin irritation. In addition, the present invention provides heat-resistant parts containing a copolymer and suitable for various applications.

The reflow solder part of the present invention is characterized by excellent transparency and heat resistance and does not undergo deformation even after processing in a reflow solder furnace, the peak temperature of which reaches 250 ° C. Thus, it can be used as a part for introduction into the substrate by the method of reflow soldering, for example, the camera lens on a mobile phone with an integrated camera.

The detail for converting the trajectory of the light beam of the present invention is characterized by good heat resistance and thermal stability, very low birefringence and excellent transparency. Thus, it is suitable for use as a sensor lens, a camera lens, a micro-raster lens, a projector lens or a prism.

The optical disc of the present invention is characterized by excellent rigidity, damping, heat resistance and water absorption, and it is suitable for use as a recording medium having a recording container with a high density.

The plastic mirror of the present invention is characterized by high rigidity and excellent ability to maintain dimensions and the ability to be imprinted in the form during molding. Thus, it is suitable for use as a multifaceted mirror, a projector mirror, and the like.

The conductive polymer composition of the present invention has the advantage that it has good heat resistance, excellent conductivity, low water absorption, and that it does not cause skin irritation. Thus, it is suitable for use as a tray for transporting electronic parts, such as a semiconductor device, an optical recording medium or a hard disk.

OPPORTUNITY FOR INDUSTRIAL USE

The polycarbonate copolymer of the present invention can be used to manufacture optical components that require the presence of heat resistance, transparency and the ability to preserve dimensions, for example, lenses, prisms, optical disks and plastic mirrors. In addition, it can be used in a method of manufacturing electronic parts, for example, as a tray for transporting electronic parts.

Claims (38)

1. A heat-resistant part, consisting of a polycarbonate copolymer, while the polycarbonate copolymer contains from 5 to 95 mol.% Repeating units (component a), described by the following General formula (I):

and from 95 to 5 mol.% of repeating units (component b) described by the following general formula (II):

where R ^a —R ^d each independently represents a hydrogen atom, a hydrocarbon group which may contain an aromatic group having from 1 to 9 carbon atoms or a halogen atom, and W represents an alkyl group which may contain an aromatic group having from 1 up to 20 carbon atoms. 2. Detail for reflow soldering, consisting of a polycarbonate copolymer, while the polycarbonate copolymer contains from 60 to 95 mol.% Repeating units (component a) described by the following general formula (I):

and from 40 to 5 mol.% repeating units (component b) described by the following general formula (II-1):

3. The item according to claim 2, where the polycarbonate copolymer contains from 70 to 85 mol.% Repeating units described by the general formula (I), and from 30 to 15 mol.% Repeating units described by the general formula (II-1). 4. The item according to claim 2, where the polycarbonate copolymer has a specific viscosity of from 0.17 to 0.55, which is measured at 20 ° C when dissolving 0.7 g of the copolymer in 100 ml of methylene chloride. 5. The component of claim 2, wherein the polycarbonate copolymer has a glass transition temperature (Tg) of 200 to 250 ° C., which is measured at a temperature increase rate of 20 ° C./min. 6. The item according to claim 2, which is a lens, a lens barrel or a prism. 7. A part for converting the trajectory of a light beam containing a polycarbonate copolymer, wherein the polycarbonate copolymer contains from 5 to 95 mol.% Of repeating units (component a) described by the following general formula (I):

and from 95 to 5 mol.% of repeating units (component b) described by the following general formula (II):

where R ^a —R ^d each independently represents a hydrogen atom, a hydrocarbon group which may contain an aromatic group having from 1 to 9 carbon atoms or a halogen atom, and W represents an alkyl group which may contain an aromatic group having from 1 up to 20 carbon atoms. 8. The item according to claim 7, where the polycarbonate copolymer contains from 5 to 95 mol.% Repeating units (component a), described by the following General formula (I):

and from 95 to 5 mol.% repeating units (component b) described by the general formula (II-1)

9. Detail for converting the trajectory of the light beam, consisting of a polycarbonate copolymer, while the polycarbonate copolymer contains from 50 to 95 mol.% Repeating units (component a) described by the following general formula (I):

and from 50 to 5 mol.% repeating units (component b) described by the following general formula (II):

where R ^a —R ^d each independently represents a hydrogen atom, a hydrocarbon group which may contain an aromatic group having from 1 to 9 carbon atoms or a halogen atom, and W represents an alkyl group which may contain an aromatic group having from 1 up to 20 carbon atoms. 10. The item according to claim 9, where the polycarbonate copolymer contains from 65 to 75 mol.% Repeating units described by the general formula (I), and from 35 to 25 mol.% Repeating units described by the general formula (II). 11. The item according to claim 9, where the polycarbonate copolymer contains from 50 to 95 mol.% Repeating units (component a), described by the following General formula (I):

and from 50 to 5 mol% of repeating units (component b) described by the following general formulas (II-1) or (II-2):

12. The item according to claim 9, where the polycarbonate copolymer in the form of a molded plate is characterized by a transmission at 550 nm of 80% or more, and its characteristics satisfy the following expression: Re ₅₅₀ / d≤10, if the delay at 550 nm is denoted by Re ₅₅₀ (nm), and the thickness of the section on which transmittance and delay are measured, indicate d (mm). 13. The component of claim 9, which is a sensor lens, a camera lens, a micro-raster lens, a projector lens, or a prism. 14. An optical disk that includes a substrate with a thickness of 0.3 to 1.2 mm, on which there are embossed recesses or guide grooves, a reflective layer made of a metal film formed on the substrate, and a transparent protective layer made of polycarbonate with a thickness from 3 to 200 μm, which is formed on a reflective layer, and which reproduces the recorded data on the mechanism for changing the light intensity of the reflected light obtained by illuminating the disk with a beam of light from the transparent side of the protective layer, the substrate is essentially It consists of a polycarbonate copolymer, the polycarbonate copolymer contains from 20 to 95 mol.% repeating units (component a) described by the following general formula (I):

and from 80 to 5 mol.% repeating units (component b), described by the following General formula (II):

where R ^a —R ^d each independently represents a hydrogen atom, a hydrocarbon group which may contain an aromatic group having from 1 to 9 carbon atoms or a halogen atom, and W represents an alkyl group which may contain an aromatic group having from 1 up to 20 carbon atoms, the substrate is characterized by: (A) a modulus of elasticity in bending from 2800 to 4000 MPa, (B) water absorption equal to 0.3 wt.% Or less upon reaching saturation, (C) a tanδ value measured at 40 ° C and 18 Hz in accordance with ISO 6721-4 of at least 0.020, and (D) deformation resistance, measured under a load of 1.81 MPa in accordance with ISO 75-1, -2, equal to 110 ° C or more. 15. The disk according to 14, where the polycarbonate copolymer contains from 25 to 70 mol.% Repeating units (component a) described by the general formula (I), and from 75 to 30 mol.% Repeating units (component b) described by the general formula (II). 16. The disk according to 14, where the polycarbonate copolymer contains from 20 to 95 mol.% Repeating units (component a), described by the following General formula (I):

and from 80 to 5 mol.% repeating units (component b) described by the following general formulas (II-2) or (II-3):

17. The disc of claim 14, which further has a recording layer between the reflective layer and the transparent protective layer. 18. The disc of claim 17, wherein the embossed recesses or guide grooves form on both surfaces of the substrate and a reflective layer, a recording layer and / or a transparent protective layer are also formed on both of its surfaces. 19. The disc of claim 14, which has a multilayer structure in which a recording layer or a reflective layer is laminated several times. 20. The disk according to 14, where the polycarbonate copolymer has a specific viscosity of from 0.1 to 0.5, measured at 20 ° C when dissolving 0.7 g of the copolymer in 100 ml of methylene chloride. 21. The disk of claim 14, wherein the polycarbonate copolymer forming the transparent protective layer is the same as the copolymer forming the substrate. 22. A plastic mirror comprising a polycarbonate substrate and a metal reflective film, a polycarbonate substrate consists of a polycarbonate copolymer, a polycarbonate copolymer contains from 20 to 70 mol% of repeating units (component a) described by the following general formula (I):

and from 80 to 30 mol.% of repeating units (component b) described by the following general formulas (II-1) or (II-2):

polycarbonate substrate is characterized by: (A) a glass transition temperature of from 120 to 230 ° C, (B) water absorption equal to 0.2 wt.% Or less after immersion in water at 23 ° C for 24 hours, and (C) a modulus of elasticity in bending from 2500 to 4000 MPa. 23. The mirror according to item 22, where the molar ratio of component a and component b is in the range from 30:70 to 60:40. 24. The mirror according to item 22, where the polycarbonate copolymer contains from 20 to 70 mol.% Repeating units (component a) described by the general formula (I), and from 80 to 30 mol.% Repeating units (component b) described by the general formula (II-1), and where the polycarbonate substrate is characterized by the following properties, namely, (A) a glass transition temperature of from 160 to 230 ° C, (B) water absorption equal to 0.2 wt.% Or less after immersion in water at 23 ° C for 24 hours, and (C) a modulus of elasticity in bending from 2500 to 3500 MPa. 25. The mirror according to item 22, where the polycarbonate copolymer contains from 20 to 70 mol.% Repeating units (component a) described by the general formula (I), and from 80 to 30 mol.% Repeating units (component b) described by the general formula (II-2), and where the polycarbonate substrate is characterized by the following properties, namely, (A) a glass transition temperature of from 120 to 180 ° C, (B) water absorption equal to 0.1 wt.% Or less after immersion in water at 23 ° C for 24 hours, and (C) a modulus of elasticity in bending from 2800 to 4000 MPa. 26. The mirror according to item 22, where the polycarbonate copolymer has a specific viscosity of from 0.1 to 0.5, measured at 20 ° C when dissolving 0.7 g of the copolymer in 100 ml of methylene chloride. 27. A mirror according to claim 22, wherein the polycarbonate copolymer has a flowability expressed as the MVR value obtained under the measurement condition of 300 ° C and 1.2 kgf, equal to 5 cm ^3/10 minutes or more. 28. The mirror according to item 22, which has a spherical, non-spherical, flat or multifaceted shape. 29. The mirror according to item 22, which is a multifaceted mirror or a mirror of the projector. 30. A conductive polymer composition containing a polycarbonate copolymer and a carbon-based filler, wherein the polycarbonate copolymer contains from 5 to 95 mol.% Of repeating units (component a) described by the following general formula (I):

and from 95 to 5 mol.% of repeating units (component b) described by the following general formula (II):

where R ^a —R ^d each independently represents a hydrogen atom, a hydrocarbon group which may contain an aromatic group having from 1 to 9 carbon atoms or a halogen atom, and W represents an alkyl group which may contain an aromatic group having from 1 to 20 carbon atoms. 31. The composition according to p. 30, which contains from 40 to 99 wt.% Polycarbonate copolymer and from 60 to 1 wt.% Filler based on carbon. 32. The composition according to p. 30, where the polycarbonate copolymer contains from 5 to 95 mol.% Repeating units (component a), described by the following General formula (I):

and from 95 to 5 mol.% of repeating units (component b) described by the following general formula (II-1):

33. A tray for transporting an electronic component, wherein the tray consists of a composition according to claim 30. 34. The tray according to clause 33, where the electronic part is a semiconductor device, an optical medium for recording data or a hard disk. Priority on points: 05/14/2002 - pp. 14-21; 03/28/2002 - claims 1-13; 07.26.2002 - pp.22-29; 08/26/2002 - pp.30-34.

Images