JPH0441524A - Polyester carbonate, its production, and optical material comprising the same - Google Patents

Abstract

PURPOSE:To obtain a polyester carbonate having excellent mechanical properties, heat resistance and transparency and a low photoelastic constant by polycondensing specified monomers and a specified oligomer as starting materials. CONSTITUTION:A reaction system comprising a bisphenol [I] of formula I and a phthalic acid dihalide is mixed with a polycarbonate oligomer comprising repeating units [II] of formula II, and the mixture is polycondensed. In this way, the aimed polyester carbonate comprising repeating units of formulas III and II, a rate of the repeating units [III] to the total of the repeating units [III] and [II] in the range of 50-95mol% and a reduced viscosity as measured in a 0.5g/dl concentration methylene chloride solution of 0.2dl/g or above is obtained.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a polyester carbonate having a novel structure, a method for producing the same, and an optical material using the polyester carbonate as a material. It has excellent mechanical properties, heat resistance, transparency, low moisture absorption, etc., and has a low photoelastic coefficient that reduces birefringence, making it suitable for various optical materials such as optical discs, optical fibers, and optical lenses. Polyester carbonate, which can be suitably used in the field of manufacturing various polymeric materials, including materials for polyester carbonate, and its advantageous manufacturing method; The present invention relates to various optical material molded products such as optical discs and optical lenses, which have advantages such as small hardness, and optical materials used as molding materials thereof.

[Conventional technology]

Polycarbonate, which is obtained through a polycondensation reaction between bisphenols and carbonate-forming compounds such as phosgene, is widely used as a variety of engineering resins because it has mechanical properties such as high mechanical strength and heat resistance. In addition, those with excellent transparency are also used as raw materials for optical materials.

On the other hand, aromatic polyester resins and polyester carbonates having aromatic ester units and aromatic carbonate units that are similarly useful as engineering resins are also known.

For example, aromatic polyester resins obtained by polycondensing dicarboxylic acids such as terephthalic acid and isophthalic acid with bisphenols are well known, such as in Japanese Patent Publication No. 38-3598. In addition, Japanese Patent Application Laid-Open No. 47-27295 has 4
．． Aromatic polyester resin obtained using 4'-biphenols, and furthermore, aromatic polyester resin obtained by fivM combination of biphenyl-4,4'-carboxylic acid and bisphenols is disclosed in JP-A-54-110853. A resin is disclosed.

Aromatic polyester resins such as these polyester resins generally have relatively high heat resistance and mechanical strength,
In many cases, they have excellent transparency and low moisture absorption.

Conventionally known polyester carbonates include those having the following two types of repeating units obtained by reacting a mixture of bisphenol-A, terephthalic acid dichloride, and isophthalic acid dichloride with phosgene.

CH.

Furthermore, relatively recently, a polyester carbonate having a special structure obtained by reacting a 3,3'-diphenylbisphenol compound with isophthalic acid cybaride and/or terephthalic acid cybalide and phosgene has also been proposed.

Polyester carbonate has -C, excellent mechanical properties such as transparency and rigidity, and heat resistance can be set over a wide range by changing the content of ester units, making it an excellent polymer for practical use. It is used in many fields as a variety of industrial materials.

Thus, polycarbonate, polyester resin, and polyester carbonate are practically important resins each having the above-mentioned excellent properties.

However, as the uses of plastic products have diversified in recent years, there has been a demand for resins with even more excellent properties in addition to the above-mentioned excellent properties of these conventional resins.

For example, optical materials used for optical devices such as lenses, prisms, audio disks, and optical memory disks are required to have various properties in addition to transparency, heat resistance, and mechanical strength. In addition, a small photoelastic coefficient is required as an optical property. If the photoelastic coefficient is large, birefringence becomes large due to this, and there are disadvantages in that the sensitivity for reading recorded information on the disk decreases and errors occur. Furthermore, when used as a material for plastic containers, it is particularly required to have low water absorption.

However, when the above conventional aromatic polyester resin is used as an optical material, it has the drawback of high birefringence, which makes recording, reproduction, transmission, etc. particularly difficult for optical recording materials such as optical disks. Therefore, there is a problem that it is difficult to apply. Furthermore, the above-mentioned aromatic polyester resin disclosed in JP-A-47-27295 is unsuitable as an optical material because it crystallizes and becomes opaque.

Further, these conventional aromatic polyester resins have insufficient properties such as mechanical strength depending on the use, and improvement thereof is desired.

Furthermore, it is desired to further improve the properties of conventional polycarbonate and polyester carbonate as optical materials. There is a need to further reduce the birefringence of molded products.

By the way, in the case of polyester carbonate, more diverse resins can be considered depending on the types and combinations of repeating units than polycarbonate or polyester. Despite this, there are relatively few types of polyester carbonate known so far, and it is expected that by selecting the repeating unit and adjusting the content, it will be possible to obtain one that fully satisfies the above properties as an optical material. big.

The purpose is to provide

A second object of the present invention is to provide a suitable method for producing the novel polyester carbonate of the present invention.

A third object of the present invention is to provide an optical material which is made of the above-mentioned novel polyester carbonate of the present invention and is fully equipped with the above-mentioned excellent properties as an optical material. It is.

[Problem to be solved by the invention]

The present invention has been made in view of the above circumstances.

First, the present invention has excellent transparency, mechanical strength, heat resistance, and low moisture absorption (moisture resistance and low water absorption), and has a small photoelastic coefficient, which makes it possible to sufficiently reduce birefringence of molded products. [Means for solving problems] ] The present inventors have realized a molded article of an optical material that has various properties as an optical material, in particular has a small photoelastic coefficient and low birefringence, and is capable of producing a molded article of an optical material including high-performance optical materials. In order to develop a new polyester carbonate that can be advantageously used as a material for various polymeric materials, the ester unit was derived from phthalic acid instead of the conventional terephthalic acid or isophthalic acid. and a repeating unit having a structure derived from a more common specific bisphenol than the conventional 3,3-diphenyl type, and these It has been found that a polycarbonate polymer having a novel structure containing repeating units in a specific proportion range is an excellent polymer that satisfies the first objective.

In addition, the present inventors have conducted various studies regarding the production method of this new polyester carbonate, and have found that a method of using specific monomers and oligomers as raw materials and subjecting them to a polycondensation reaction is practical. We have found this to be a particularly advantageous method.

Furthermore, the present inventors have found that optical materials obtained using the novel polyester carbonate of the present invention as a main component fully satisfy the properties as various optical materials, and in particular have a small photoelastic coefficient. discovered that it is an excellent optical material that can sufficiently reduce the birefringence of optical material molded products.

The present inventors have completed the present invention based on these findings.

That is, the present invention provides the following general formula [Formula (I), R1, R2, R3 and R4 in (I[]
are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, XI and X2 are each independently a single bond, (here, R5 and R6 are each independently a hydrogen atom, a
-6 alkyl group or an aryl group having 6 to 12 carbon atoms. ) or ). ] having a repeating unit represented by the above repeating unit N)
and the content of the repeating unit (rlI) in a proportion of 50 to 95 mol% of the repeating unit (1).
and the concentration is within the range of 0.0.
Reduced viscosity at 20°C of 5 g/a solution [ηs, /C
] is 0.2 dl/g or more, and as a preferred method for producing the polyester carbonate of the present invention,
At least the following general formula [However, in formula (1), (DR', R'' and x' represent the same meaning as in the above general 2N).

] A reaction system consisting of bisphenols [■] represented by [■] and phthalic acid civalide and a polycarbonate oligomer consisting of a repeating unit (n) represented by the general formula (H) are mixed and a polycondensation reaction is performed. The present invention also provides a method for producing a polyester carbonate characterized by the following, and an optical material characterized by using the polyester carbonate of the present invention as a particularly effective use of the polyester carbonate of the present invention.

The polyester carbonate of the present invention has the above general formula (1
), that is, the repeating unit (1)
It is a polymer consisting of a repeating unit represented by the above general formula (II), that is, a repeating unit (IN).

Repeating unit (I) and repeating unit [R1 in I[)
, R2, R3 and R4 each independently represent an alkyl group having 1 to 6 carbon atoms, and specific examples of the alkyl group include:
Methyl group, ethyl group, propyl group, isopropyl group, butyl group, 5ec-butyl group, isobutyl group, tert-
Butyl group, pentyl group, isopentyl group, 5ec-pentyl group, tert-pentyl group, neopentyl group, cyclopentyl group, hexyl group, isohexyl group, 5ec-
hexyl group, tert-hexyl group, neohexyl group,
Examples include cyclohexyl group, methylcyclopentyl group, cyclohexyl group, methylcyclopentyl group, and cyclopentylmethyl group. Among these, methyl group is particularly preferred.

In the repeating unit [I], the repeating unit [■], and the polyester carbonate of the present invention, R1, RZ, R
3 and R4 may be the same or different in relation to each other and to each other.

R1 in repeating unit (1) and repeating unit (I[)
, R2, R3 and R4 are l? ' and R3 are methyl groups, I
Preferably, 12 and R4 are hydrogen.

XI and X2 in the repeating unit (1) and the repeating unit [■] represent a single bond or each of the above divalent groups.

When x1 and x2 are -CR5R6-, R5 and R6 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

Any one or more of R5 and R6 has 1 carbon number
-6 alkyl groups, specific examples of the alkyl groups include the aforementioned various alkyl groups exemplified as R1, R2, R3, or R4. Among these alkyl groups, a methyl group is particularly preferred.

Any one or more of R5 and R6 has 6 or more carbon atoms
In the case of aryl group 12, specific examples of the aryl group include phenyl group, 0-1m- or p-methylphenyl group, xylyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, isopropylphenyl group. , various alkylphenyl groups such as butylphenyl group, 5ec-7'tylphenyl group, tertbutylphenyl group, isobutylphenyl group, pentylphenyl group, hexylphenyl group, methylethylphenyl group, methylisopropylphenyl group, cyclohexylphenyl group, etc. , biphenylyl group, naphthyl group, methylnaphthyl group, etc. Among these aryl groups, phenyl groups are particularly preferred.

There are various specific examples of CR5R6- depending on the types of R5 and R6, but among them, preferred ones include -C(CI+3)2- -CH(C
H3) CPh(CHz) -2-C(Ph) z- (wherein, ph represents a phenyl group. The same applies hereinafter), etc., and particularly preferred ones include -C(CH3)
2- etc. can be mentioned.

preferably 4.5 or 7, particularly preferably 5. ), specific examples of this 1,1 cyclohexylidene group include 1,1-cyclopentylidene group, 1
, 1-cyclohexylidene group, (1), 1-cyclohebutylidene group and 1°1-cyclooctylidene group.

Among these, 11-cyclohexylidene group is particularly preferred.

x1 and x2 can be a single bond, -o--s--5o2-1, the above-mentioned various -CR3R'-, and the above-mentioned various 1,1-cycloalkylidene groups, but among these, particularly preferred ones are Examples thereof include -C(CHi)2, ie, 1,1-cyclohexylidene group.

In addition, repeating unit [xl in 1E and repeating unit (1
x2 in 1) may be the same or different.

The structural units in the repeating unit [1] and the structural units in the repeating unit [II] may be the same or different.

The polyester carbonate of the present invention can be a polymer having various configurations as long as it is composed of one or more types of repeating units (CI) and one or more types of repeating units [■].

That is, repeating unit [I] and repeating unit (ff
) may be a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, or a combination thereof. However, when producing a polymer having a branched structure such as a graft copolymer, an appropriate branching agent is used during its production.

Among these various types of polyester carbonates, random type copolymers and block type copolymers are usually preferred from the viewpoint of ease of production and ease of controlling properties as a material for optical materials. Particularly preferred are block copolymers produced by the production method of the present invention described later.

One of the important points in the polyester carbonate of the present invention is that the repeating units (
The ratio of the repeating unit [I] to the total of the content of I) and the content of the repeating unit [I[) is in the range of 50 to 95 mol%.

Here, if the proportion of this repeating unit (1) is less than 50 mol%, disadvantages may occur, such as the effect of reducing the photoelastic coefficient and the birefringence of the optical material molded product being insufficient. . On the other hand, the ratio of repeating unit CI) is 95
If the amount exceeds mol%, there may be problems such as difficulty in achieving a sufficiently high molecular weight when manufacturing using the manufacturing method of the present invention described below.

Further, the polyester carbonate of the present invention can be prepared at 20°C in a solution having a concentration of 0.5 g/a using methylene chloride as a solvent.
The reduced viscosity [η1/C] is 0.2 di/g or more, preferably in the range of 0.3 to 0.8 a/g.

If this reduced viscosity [η, p/C) is less than 0.2 a/g, the molecular weight will be too low to ensure sufficient mechanical strength and heat resistance of the molded product, while if it is too large, Molding may be difficult.

The polyester carbonate of the present invention has repeating units [1
) and a repeating unit (n), which is also known as a repeating unit of a relatively common bisphenol-based polycarbonate polymer, in the above-mentioned specific ratio. It has excellent properties such as excellent heat resistance, mechanical strength, etc., low hygroscopicity, and a sufficiently low photoelastic coefficient, so that the birefringence of molded products can be sufficiently reduced. Furthermore, it has excellent moldability, so it can be advantageously used in the field of manufacturing various polymer materials, including materials for various optical materials such as optical disks, optical fibers, and optical lenses. .

The polyester carbonate of the present invention may contain repeating units other than the repeating unit (1) and the repeating unit (It) within a range that does not impede the purpose of the present invention.

Further, the structure of the polymer terminal of the polyester carbonate of the present invention is not particularly limited, and it can be configured to have various terminal groups such as those commonly used as terminal groups of known polycarbonates and polyesters.

When using the polyester carbonate of the present invention, each of them may be used as is, or two or more types of structures,
Those with different compositions and reduced viscosities [η, , /C) may be appropriately mixed and used, and if necessary, various additives such as stabilizers such as antioxidants or other additives may be used. It can be used by adding and blending polymer components and the like.

The polyester carbonate of the present invention is not particularly limited in its general manufacturing method, and can be manufactured using various methods such as known methods.

For example, bisphenols represented by the general formula [I[[], that is, bisphenols [nl], phthalate diester-forming compounds such as phthalic acid civalide, and carbonate ester-forming compounds such as phosgene, haloformates, and low-molecular carbonate esters. A polymerization method in which a compound is mixed simultaneously or stepwise in a predetermined ratio, and if necessary, in the presence of an acid acceptor, a catalyst, a molecular weight regulator, and a solvent, one-stage polymerization or two or more consecutive steps are performed. It can be obtained by a reaction method.

Among these various manufacturing methods, the method for manufacturing polyester carbonate of the present invention described above (hereinafter sometimes referred to as the method of the present invention) is particularly preferably employed.

The method of the present invention will be explained in detail below.

As described above, the method of the present invention consists of a reaction system consisting of at least bisphenols (1) represented by the following general formula and phthalic acid civalide, and a repeating unit (It) represented by the general formula (IN). It is characterized in that the polyester carbonate of the present invention is obtained by mixing polycarbonate oligomers and performing a polycondensation reaction.

Since the bisphenols (I[I] correspond to at least the structural unit in the repeating unit (1), specific examples of R1, R2, and xl of the -S formula (Ill),
Preferred examples are as described above.

Specific examples of this bisphenol [l11) include R
1, R2, and χ1, and any of them can be used, but representative examples include, for example:
Bis(4-hydroxyphenyl)methane, 1-bis(4-hydroxyphenyl)ethane, 2.2-bis(4
-hydroxyphenyl)propane, 2,2-bis(4-
hydroxyphenyl)butane, 3.3-bis(4-hydroxyphenyl)pentane, 2.2-bis(4-hydroxyphenyl)octane, 4.4-bis(4-hydroxyphenyl)butane, 1. I-bis(4-hydroxyphenyl)-1,1-diphenylmethane, 1゜1-bis(4-hydroxyphenyl)-1-phenylethane, 1
．． 1-bis(4-hydroxyphenyl)-1-phenylmethane, bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) sulfide, bis(4-
hydroxyphenyl) sulfone, 1,1-bis(4-hydroquinphenyl)noclobencune, 11-bis(4-
hydroxyphenyl)cyclohexane, 1.1bis(3
-Methyl-4-hydroxyphenyl)methane, 1.1-
bis(3-methyl-4-hydroquinphenyl)ethane,
2.2-bis(3-methyl-4-hydroxyphenyl)
Propane, 2,2-bis(3-methyl-4-hydroxyphenyl)butane, 2-(3-methyl-4-hydroxyphenyl)-2-(4-hydroxyphenyl)propane, 2-(3-methyl-4 -hydroxyphenyl)-2-
(4-hydroxyphenyl)-1-phenylethane, bis(3-methyl-4-hydroxyphenyl) sulfide, bis(3-methyl-4-hydroxyphenyl) sulfone, 1,1-bis(3-methyl-4- hydroxyphenyl)cyclohexane, ■-(3-methyl-4-hydroxyphenyl)-1-(4-hydroxyphenyl)cyclohexane, 44'-dihydroxybiphenyl, 3.3'
-dimethyl-4,4'-dihydroxybiphenyl, 22
-bis(2-methyl-4-hydroxyphenyl)propane, 1,1-bis(2-butyl-4-hydroxy-5-methylphenyl)butane, 1,1-bis(2-tert-
butyl 4-hydroxy-3-methylphenyl)ethane,
1.1-bis(2-tert-butyl-4-human)
y-5-methylphenyl)propane, 11bis(2-L
ert-butyl-4-hydroquine 5-methylphenyl)
Butane, 1,1-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)isobutane, 1,1-bis(2tert-butyl-4-hydroxy-5-methylphenyl)hebutane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl)-1-phenylmethane, 1,1-bis(2-tert-amyl-
4-hydroxy-5-methylphenyl)butane, 1.1
-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane and the like.

Among these, particularly preferred are, for example, 2.
2-bis(4-hydroxyphenyl)propane, 2,2
-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane, etc. Among them, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(
Mention may be made of 3-methyl-4-hydroxyphenyl)cyclohexane.

Note that these may be used alone or in combination of two or more as a mixture.

Examples of the halogen atom in the phthalic acid sybaride (i.e., 1.2-bis(herocarbonyl)benzene) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a chlorine atom is preferred. Note that the two halogen atoms in the phthalic acid sybaride molecule may be the same or different.

Specific examples of the phthalic acid civalide include phthalic acid difluoride, phthalic acid dichloride, phthalic acid dibromide, phthalic acid diaiodide, phthalic acid chloride fluoride F, and the like. Among these, phthalic acid dichloride is particularly preferred.

Incidentally, these phthalic acid sybarides may be used alone or in combination of two or more as a mixture.

In the method of the present invention, the polycarbonate oligomer is a relatively low molecular weight polycarbonate compound composed of the repeating unit (II) or a polycarbonate precursor (polymerization intermediate product) containing this as a main component; ) and the phthalic acid sybaride to the reaction system consisting of the reduced viscosity [η, , /
As long as it can be polycondensed into the polyester carbonate of the present invention in the CI range, there are no particular restrictions on its molecular weight and molecular weight distribution, even if it contains monomers such as bisphenols (TV) described below. good.

There are no particular limitations on the method for producing such polycarbonate oligomers, and they can be produced by various methods, including known methods. For example, they can be suitably produced by the following method.

That is, the polycarbonate oligomer has at least the following general formula (IV) [However, R3, R4 and X2 in formula [IV] each represent the same meaning as in the above formula (U).

] Bisphenol [(mV) represented by the following can be synthesized advantageously in practice by reacting a carbonate ester-forming compound under appropriate conditions and atmosphere.

The bisphenols represented by the general formula [IV], that is, the bisphenols [■], correspond to at least the structural units in the repeating unit [■], so R3, R4, and Specific examples and preferred examples of ×2 are the same as R1, R2, and XI, respectively.

Specific examples, preferred examples, and particularly preferred examples of the bisphenols [■] include the bisphenols (II).
Each of the examples exemplified as I) can be mentioned. These may be used alone or in combination of two or more as a mixture.

As the carbonate ester-forming compound, various compounds used in the field of ordinary polycarbonate production can be used. Typical examples include various carbonyl dihalides including phosgene, haloformates such as chloroformate compounds, and carbonate ester compounds. Among these, phosgene is particularly preferably used.

The polycarbonate oligomer can be produced by reacting one or more of the bisphenols [IV] with at least one of the carbonate-forming compounds.

There are no particular limitations on the method of this reaction (reaction atmosphere, conditions, reaction system, operating method, etc.), and generally any known method used in the production of polycarbonate oligomers may be used as appropriate.

For example, when using a carbonyl dihalide such as phosgene or a haloformate such as chloroformate as a carbonate forming compound, this reaction is carried out in an appropriate solvent with an acid acceptor (such as an alkali metal hydroxide or alkali metal hydroxide). This can be carried out in the presence of a basic alkali metal compound such as a metal carbonate or an organic base).

Various types of alkali metal hydroxides and alkali metal carbonates can be used, but from an economical point of view, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. are usually preferably used. Ru. These can usually be suitably used as an aqueous solution. The proportion of the carbonate-forming compound to be used may be appropriately adjusted in consideration of the stoichiometric ratio of the oligomer production reaction.

When using a gaseous carbonate-forming compound such as phosgene, a method of injecting it into a reaction system containing bisphenols [■] as a starting material can be suitably employed.

The proportion of the acid acceptor to be used may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the oligomer production reaction. Specifically, it is preferable to use about 2 equivalents of the acid acceptor relative to the total number of moles of bisphenols (IV) used (usually 1 mole corresponds to 2 equivalents).

As the solvent, various solvents such as those used in the production of known polycarbonate oligomers or polycarbonates may be used alone or as a mixed solvent. As a typical example, halogenated hydrocarbon solvents such as methylene chloride can be suitably used.

In addition, when carrying out this reaction, a molecular weight regulator or a reaction accelerator (for example, an alkylamine, etc.) may be used as desired.
may be added to adjust the reaction rate and molecular weight.

However, when adjusting the molecular weight, the obtained polycarbon 7
Care should be taken so that the oligomer 〇-end 'fM& has sufficient reactivity with the reaction system consisting of bisphenol i [1III:] and phthalic acid civalide described below.

The reaction temperature during the synthesis reaction of polycarbonate oligomers is usually 0 to 50°C, preferably 10 to 30°C.
It is appropriate to set it within the range of .

The reaction pressure can be any of reduced pressure, normal pressure, and increased pressure, but usually normal pressure or about the autopressure of the reaction system can be suitably used. The reaction time is usually about 10 to 60 minutes, preferably about 15 to 30 minutes.

As the reaction method, any of a continuous method, a semi-continuous method, a batch method, etc. can be adopted.

In the manner described above, a polycarbonate oligomer suitably used in the method of the present invention can be obtained.

The polycarbonate oligomer thus produced may be used after being separated and purified as necessary, but it is usually used as a mixture with the solvent used (preferably methylene chloride), etc., as described below. It is used as a raw material for the synthesis reaction of Ne-1.

In the method of the present invention, the polycarbonate oligomer, preferably the polycarbon 2-oligomer produced as described above, at least one of the bisphenols [111] and at least one of the phthalic civalides (preferably phthalate) are combined. The polyester carbonate of the present invention is produced by mixing with a reaction system consisting of acid dichloride) and carrying out a polycondensation reaction under appropriate conditions and atmosphere.

The type and composition of the bisphenols [I) used may be the same as the bisphenols (TV) used in the production of the polycarbonate oligomer, or may be different.

The ratio of bisphenols Cn1) and phthalic acid cybalide to be used may be appropriately selected in consideration of the stoichiometric ratio of the polycondensation reaction (although there is no particular restriction, for -a, the ratio of phthalic acid cybalide Bisphenols [■] 1
It is appropriate that the amount is about 1 mol per mol. however,
When an excess amount of bisphenols (TV) is used in the production process of the polycarbonate oligomer and it remains as a monomer component in the raw polycarbonate oligomer, the remaining bisphenols [■] or its alkali metal salts are converted into bisphenol lit ( I
It is preferable to consider it as the I[) component and adjust its proportion.

The ratio of the bisphenols (I [ 1) and repeating unit [■]
There is no particular restriction as long as the ratio is set appropriately so that it falls within the predetermined ratio range.

Here, in the same manner as above, an excessive amount of bisphenols (IV) is used in the manufacturing process of the polycarbonate oligomer.
If this is used as a monomer component and remains in the raw polycarbonate oligomer, it is better to consider the remaining bisphenols (IV) or its alkali metal salts as bisphenols [I [[] component and adjust the proportion thereof. .

The reaction system consisting of bisphenols [■] and phthalic acid sybaride to be subjected to the polycondensation reaction can be constructed by various methods, but it is usually prepared using an aqueous solution of the alkali metal hydroxide or alkali metal carbonate. A method of dissolving bisphenols [1 [ It can be suitably prepared by, etc.

In this reaction system, a condensation reaction between bisphenols [(1) acid component (mainly alkali metal salt)] and phthalic acid cybaride proceeds to produce a polyester oligomer consisting of the repeating unit (1).

In the method of the present invention, at least bisphenol i
(I[I) and a reaction system prepared from phthalic acid cybalide (hereinafter sometimes referred to as system-1) and a system containing the polycarbonate oligomer (hereinafter sometimes referred to as system-2). are mixed and subjected to a polycondensation reaction to synthesize a desired polycarbonate oligomer.

There are no particular restrictions on the method of mixing System-1 and System-2, but usually a method of adding and mixing System-2, a system containing a polycarbonate oligomer, to a reaction system, System-1, is used. Suitably adopted.

As System-1 and System-2 to be mixed, it is preferable to use those prepared by the respective methods exemplified above.

That is, usually, a polycarbonate oligomer produced by the above-mentioned method (preferably a solution of the polycarbonate oligomer such as a methylene chloride solution) is mixed with the reaction system prepared by the above-mentioned method, and the mixture is subjected to a polycondensation reaction. is preferably adopted.

The reaction temperature when performing the polycondensation reaction (reaction of system-1 and system-2) is usually about 0 to 50°C, preferably about 5 to 50°C.
A range of about 20°C is appropriate. The reaction time is usually about 5 minutes to 3 hours, preferably 10 minutes to 1 hour.
, approximately 5 hours is sufficient. Note that this polycondensation reaction is desirably carried out under sufficient stirring.

The reaction pressure is not particularly limited, but the reaction can normally be carried out suitably from normal pressure to slightly increased pressure.

When carrying out this polycondensation reaction, if necessary, a suitable molecular weight regulator and polymerization promoter (catalyst) are added to the reaction system.
It is possible to add additional components such as or a solvent.

Various types of molecular weight regulators can be used, but those commonly used in the production of conventional bisphenol polycarbonates, such as p-terL, are usually used.
- Monovalent phenols such as butylphenol (PTBP), nonylphenol, 0-phenylphenol, monovalent acid halides or polyvalent acid monohalide esters, monohaloformates such as phenyl chloroformate, phthalic acid Terminal capping agents such as phthalic acid monohalide monoesters such as monochloride esters are preferably used. Further, if necessary, a branching structure or a graft structure can be appropriately introduced into the polymer by adding a small amount of a branching agent such as trivalent or higher phenols or acid halides.

It is usually preferable to add such a molecular weight regulator as a terminal capper when the polycondensation reaction has sufficiently progressed to some extent.

For example, after the polycondensation reaction has progressed to a certain extent, PTBP
For example, a monohydric phenol such as the following is added as a solution dissolved in a dilute solution of a polycarbonate oligomer (preferably a diluted methylene chloride solution), and then, after continuing the reaction for a while, a terminal capping agent such as phenyl chloroformate is added. methods etc. are suitably adopted.

Similarly, as the polymerization accelerator (catalyst), those used in the production of known polycarbonates [for example, organic amines such as triethylamine (TEA), etc. are suitably used.

This polymerization promoter (catalyst) is preferably added before or after the start of the polycondensation reaction, preferably before the start of the polycondensation reaction.

The solvent is appropriately added when the solvents from system-1 and system-2 are insufficient.

Various types of solvents can be used as this solvent, but normally, those commonly used in polymerization reactions in the production of known bisphenol polycarbonates or polyester carbonates may be used as appropriate, such as methylene chloride, etc. Neutral polar solvents and mixed solvents mainly containing these solvents, particularly methylene chloride, are preferably used.

The polyester carbonate of the present invention can be advantageously synthesized as described above. In addition, in order to adjust the reduced viscosity (ηs, /C) of the obtained polyester carbonate to the above-mentioned predetermined range, adjustment of the amount of the molecular weight regulator added, the composition of the reaction system, and reaction conditions such as reaction temperature and time are necessary. This can be done by selecting, etc.

The polyester carbonate synthesized in this manner is subjected to post-treatment such as an appropriate separation/purification method, separated and recovered from the reaction product mixture, and obtained as a product with a desired purity (purification degree).

There are no particular restrictions on the method of separation, recovery and purification.
This can be carried out using various methods such as known methods.

For example, the polymerization solution obtained in the above polycondensation reaction may be mixed with a suitable solvent such as methylene chloride that is incompatible with water and an appropriate amount of water (
The organic phase containing the polyester carbonate is washed with an aqueous acid solution such as hydrochloric acid and then with water, and the organic phase obtained by phase separation is mixed with a polyester carbonate, which is a poor solvent for the polyester carbonate. A method of adding a suitable solvent to precipitate polyester carbonate as a resin and recovering the resin is preferably employed. Further, if necessary, the obtained resin can be dissolved again in a suitable solvent such as methylene chloride and reprecipitated in the same manner to purify the resin to a desired purity.

The polyester carbonate thus obtained is
It has excellent transparency, mechanical strength, and heat resistance, and has a small photoelastic coefficient and low anisotropy, making it useful as a material for optical equipment, such as audio discs, optical memory discs, still cameras, video cameras, telescopes, Useful for eyeglasses, contact lenses, prisms, optical fibers, etc. It also has low water absorption, making it useful as a material for various molded products, such as a material for containers.

The novel polyester carbonate of the present invention can be molded by methods normally used for molding polyester carbonate, such as injection molding, extrusion molding, blow molding, etc., and can be molded using commonly used molding equipment. can.

In the above molding method, the polyester carbofoot of the present invention may be molded as is, but if necessary, antioxidants, flame retardants, ultraviolet absorbers, antistatic agents, lubricants, coloring agents, etc., are usually added to the polyester carbonate. - Additives added to the bonate can be blended.

The antioxidants used include, for example, 2゜6-di-t-butyl-P-cresol, butylated hydroxyanisole, 2,6-dibutyl-4-ethylphenol, stearyl-β-(3゜5 -di-t-butyl-4-
hydroxyphenyl) propionate, 2,2'-methylenebis(4-methyl-6-t-butylphenol),
2.2'-methylene-bis(4-ethyl-6-butylphenol), 4.4'-thiobis(3-methyl-6
-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), tetrakis[methylene-3-(3'5-di-t-butyl-4
-Hydroxyphenyl)propionate comethane, 1,
1.3-) Lis(2-methyl-4-hydroxy-5-t
phenolic compounds such as -butylphenyl)butane, amine compounds such as phenyl-β-naphthylamine, N,N'-diphenyl-p-phenylenediamine, tris(nonylphenyl)phosphite, triphenylphosphite, triotadecylphosphite Examples include phosphorus-based compounds such as phite, diphenylisodecyl phosphite, and sulfur compounds such as dilaurylthiodipropionate, simiristylthiodipropionate, and distearylthiodipropionate.

Examples of flame retardants used include halogen flame retardants such as polybromobutylene, decabromodiphenyl ether, and tetrabromobisphenol A; phosphorus retardants such as ammonium phosphate, tricresyl phosphate, triethyl phosphate, and acidic phosphate esters; refueling agent, tin oxide,
Examples include inorganic flame retardants such as antimony trioxide.

Examples of the UV absorbers used include salicylic acid UV absorbers such as phenyl salicylate and pt-butylphenyl salicylate, and benzophenone UV absorbers such as 2°4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone. agent, 2- (2'
-Hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-mo-butylphenyl)benzotriazole, and other benzotriazole-based ultraviolet absorbers.

Examples of the antistatic agent used include nonionic antistatic agents such as polyoxyethylene alkylamine and polyoxyethylene alkylamide, anionic antistatic agents such as alkyl sulfonate and alkylbenzene sulfonate, quaternary ammonium chloride, Examples include cationic antistatic agents such as quaternary ammonium sulfate, and amphoteric antistatic agents such as alkyl betaine type and alkylimidapurine type.

Examples of the lubricant used include aliphatic hydrocarbon, higher aliphatic alcohol, fatty acid amide, metal soap, and fatty acid ester lubricants.

As the colorant used, common colorants used for coloring plastics can be used.

Furthermore, other parts, such as phosphite esters to prevent coloring and deterioration of transparency, and plasticizers to increase the melt index value, are added to the polyester carbonate of the present invention during molding. can do.

The phosphite esters and 1- used in this case include, for example, tributyl phosphite, tris (2-ethylhexyl) phosphite, tributyl phosphite, tris-stearyl phosphite, triphenyl phosphite, tricresyl phosphite, tris- (nonylphenyl)phosphite, 2-ethylhexyldiphenylphosphite, decyldiphenylphosphite, phenyl-di-2
-Ethylhexyl phosphite, phenyldidecyl phosphite, tricyclohexyl phosphite, distearyl pentaerythrityl diphosphite, diphenylpentaerythrityl diphosphite, and the like.

Examples of plasticizers include alkyl phthalates such as 2-ethylhexyl phthalate, n-butyl phthalate, isodecyl phthalate, tridecyl phthalate, heptyl phthalate, and nonyl phthalate, 2-ethylhexyl adipate, and 2-ethyl phthalate. Alkyl esters of dibasic acids such as xyl sebacate, phosphoric acid alkyl esters such as tributyl phosphate, trioctyl phosphate, tricresyl phosphate, and triphenyl phosphate, epoxy esters such as epoxidized octyl oleate, and epoxidized butyl oleate. Examples include chlorinated fatty acid esters, polyester plasticizers, and chlorinated fatty acid esters.

Further, other resins may be blended and molded as long as the properties of the polyester carbonate of the present invention are not impaired.

The optical material of the present invention can be used for the purpose of producing the above-mentioned various optical material molded products obtained by using at least one of the polyester carbonates of the present invention, preferably the polyester carbonate produced by the method of the present invention, as a raw material. Various molding materials are prepared. Therefore, the optical material of the present invention can have various compositions suitable for manufacturing optical material molded products depending on the purpose. For example, the polyester carbonate of the present invention may be used as is, or conventional optical materials may be added to it. It is also possible to appropriately contain various additive components commonly used as components of the material. Optical materials (molding materials) containing, preferably as a main component, the polyester carbonate of the present invention and having compositions suitable for these purposes may be molded into optical material moldings in various shapes suitable for desired uses. As long as the polyester carbonate of the present invention is used in the molded article, it is considered to be an optical material of the present invention.

The optical material of the present invention can be used, for example, in various optical disks such as audio disks, optical memory disks, still camera disks, and video camera disks, various lenses such as telescopes, glasses, and contact lenses, prisms, and optical fibers. It can be realized as various optical material molded products such as and various molding materials used for manufacturing the same.

Since the optical material of the present invention uses the polyester carbonate of the present invention having the above-mentioned excellent properties, the molded product has good mechanical properties such as transparency and mechanical strength.
It has various advantages such as excellent heat resistance, low moisture absorption, and sufficiently low birefringence.
Therefore, it can be advantageously used in various fields of application and production of molded optical materials.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these Examples, and various modifications and applications can be made without departing from the spirit of the present invention. is possible.

In addition, evaluation of each resin as an optical material in the following Examples and Comparative Examples was performed as follows.

Birefringence: Each resin was molded into a flat plate using a minimat molding machine manufactured by Sumitomo Heavy Industries Co., Ltd., and the birefringence of this molded product was measured.

Photoelastic coefficient (C,): Each resin is melt-spun using a cavilograph manufactured by Toyo Seiki Co., Ltd., the thread is pulled with a winder, and the stress applied to the thread and the slope of birefringence are calculated as the photoelastic coefficient (C,) of the molten state. C,).

These evaluation results were mainly used as an index of optical properties.

The reduced viscosity [η sp/C) of each resin is 2
It is shown as the value at 0'C.

Further, the viscosity average molecular weight Mv was determined in terms of polycarbonate.

Example 1 1.1-bis(3-methyl-4-hydroxyphenyl)
170 g (0.57 mol) of cyclohexane was added to 2N-Na
Dissolved in OH1500at, methylene chloride 650yj
! Add 1200% of phosgene gas while stirring vigorously.
It was blown at a flow rate of d/sin. At the time of PHIO, the supply of phosgene gas was stopped and the reactor was left standing to obtain a methylene chloride solution of an oligomer having a chloroformate end and a degree of polymerization of 2 to 10.

Separately, 49.3 g (0,17
mol) was dissolved in 2N-NaOH aqueous solution 400 mol to form a bisphenol aqueous solution, while phthalic acid dichloride 3
4.0 g (0.17 mol) was dissolved in 270 m of methylene chloride to obtain a phthalic acid dichloride solution.

This bisphenol aqueous solution and phthalic acid chloride solution were mixed and stirred, and 25 d of the methylene chloride solution of the oligomer obtained above and TEA (7% aqueous solution) 1 were added thereto and reacted with stirring, and after 5 minutes, 25 d of a methylene chloride solution of the oligomer and 0.2 g of P T B P were added. After a further 40 minutes, phenyl chloroformate Log was added, and the reaction was stopped after a total of 1 hour.

After the reaction, the polymerization solution was diluted 3 times with methylene chloride and water,
Water washing, 0.2N HC1aq washing, 0.05NHCl
It was washed in the following order: aq and water twice. The obtained methylene chloride solution was added dropwise to a mixed solvent of acetone/methanol (2:1) to recover the polymer.

The obtained polymer was dissolved in methylene chloride and reprecipitated by adding acetone/methanol (2:3) to purify and recover the polymer. It was then dried at 100°C under reduced pressure, and
g of polymer was obtained. This polymer was found to have 80% phthalate parts and 20% polycarbonate parts by H-NMR. Reduced viscosity [η,, /C)
is 0.377d1/g (corresponds to Mv-14,900)
Met. Also, the photoelastic coefficient (C) of this polymer in a molten state.

) is 860 (B), and the birefringence of the molded product is normal incidence 15 nm, 30″ oblique incidence 45 nm, and 30°
The difference in birefringence between incident and normal incidence was 30 nm. Furthermore, the glass transition temperature (Tg), thermal decomposition temperature (Td 5% weight loss), and water absorption rate of this polymer were as follows.

Tg: 157°C Td: 435°C Water absorption: 0.07% (23°C 24hr) Example 2 11-bis(3-methyl-4-hydroxyphenyl)cyclohexane 29.6g (0.1 mol) 2N- NaO
Dissolve in 300d of H aqueous solution.

20.3 g (0.1 mol) of phthalic acid chloride
017! of methylene chloride. The above two melts were mixed and stirred, and 75 ai! and 1 d of TEA (7% aqueous solution) were added and reacted with stirring. After 5 minutes, add 75 d of diluted oligomer solution and 2 g of P T B P O, and then add 4 g of diluted oligomer solution.
After 0 minutes, 7 g of phenyl chloroformate was added to stop the reaction in a total of 1 hour.

The obtained polymer was recovered in the same manner as in Example 1,
67 g of polymer was obtained. This polymer was found to have the following structure and properties.

According to H-NMR, 50% of phthalate parts and 50% of polycarbonate parts were found. Reduced viscosity [η□/C) is 0.453d1/g (equivalent to Mv, = 18.400)
and the photoelastic coefficient in the molten state (C.

) was 1200 (B). The birefringence of the molded product is normal incidence 20 nm, 30' oblique incidence 60 nm, and 30°
The difference in birefringence between incident and normal incidence was 40 nm. Also, Tg=152°C, Td=430°C2 water absorption rate -0
,07% (23°C, 24hr).

Example 3 2.2-bis(3-methyl-4-hydroxyphenyl)
A methylene chloride solution of the oligomer was obtained in the same manner as in Example 1 using 153 g (0.60 mol) of propane.

2. 61.7 g (0°24 mol) of 2-bis(3-methyl4-hydroxyphenyl)propane was dissolved in 2N-NaOH3
0d to t8, while phthalic acid chloride 45g (0
, 22 mol) was dissolved in 200 m methylene chloride.

These two solutions were mixed and stirred, and then 70 d of the above oligomer methylene chloride solution was diluted with methylene chloride to 100 d.
50ml of the solution diluted in d and TEA1d were added, and the reaction was carried out under stirring.

After 5 minutes, add 50 g of diluted oligomer solution and 12 g of PTBPO.
After 40 minutes, 10 g of phenyl chloroformate was added and the reaction was continued for a total of 1 hour.

The obtained polymer was recovered in the same manner as in Example 1, and 62 g of polymer was obtained. The structure and properties of this polymer were as follows.

Phthalate ester part 75% Polycarbonate part 25% Reduced viscosity [η, p/C] =0.404 dl/g (M
(Equivalent to v=16,100) Photoelastic coefficient in molten state (C,): l800 (B) Birefringence of molded product: Normal incidence -10% m, 30° oblique incidence 45 nm, 30° incidence and normal incidence The difference in birefringence is 55
%m.

Comparative Example 1 11-bis(4-hydroxyphenyl)cyclohexane and phosgene were reacted to obtain a homopolycarbonate. The properties of this polycarbonate were as follows.

Reduced viscosity [ηs, /C) = 0.560 dl/g (Mv
=23,300) Photoelastic coefficient in molten state (C,''): 3.io.

Comparative Example 2 The optical properties of a commercially available molded plate of polycarbonate made from bisphenol A were measured, and the following results were obtained.

Photoelastic coefficient (C,) in molten state: 4.400 Birefringence of molded product: Normal incidence -30% m, 30" oblique incidence 110 nm
The difference in birefringence with normal incidence at 30° was 140 nm.

〔Effect of the invention〕

According to the present invention, a novel polymer containing a specific proportion of an aromatic ester repeating unit having a specific structure called bisphenol-phthalic acid diester system and an aromatic carboxylic yarn repeating unit commonly used in bisphenol polycarbonate is developed. It has excellent transparency, mechanical strength, heat resistance, low moisture absorption (moisture resistance and low water absorption), and has a small photoelastic coefficient and can sufficiently reduce birefringence of molded products. It is possible to provide a polyester carbide having a novel structure that can be advantageously used in various fields of polymeric materials, particularly optical materials.

Further, according to the present invention, a reaction system consisting of bisphenols and phthalic acid civalide as a raw material component corresponding to the aromatic ester repeating unit and a polycarbonate oligomer as a raw material component corresponding to the bisphenol yarn repeating unit are mixed, By using the specific method of subjecting to the condensation reaction, it is possible to provide a method for advantageously producing the polyester carbon of the present invention having the above-mentioned convenient properties.

Furthermore, according to the present invention, by using the polycarbonate futon of the present invention having the above-mentioned excellent properties, it has excellent mechanical properties such as transparency and mechanical strength, heat resistance, etc. INDUSTRIAL APPLICABILITY It is possible to provide various high-performance optical material molded products having low hygroscopicity and sufficiently reduced birefringence, or an optical material that can be advantageously used in the production thereof.

Claims (1)

[Claims] 1. The following general formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [Formula [ I ], [II] , R^1, R^2, R^3 and R^4 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X^1 and X^2 are each independently a single bond. , -O-, -S-, -SO_2-, ▲Mathematical formulas, chemical formulas, tables, etc.▼ (Here, R^5 and R^6 each independently represent a hydrogen atom, an alkyl having 1 to 6 carbon atoms, group or aryl group having 6 to 12 carbon atoms) or ▲Mathematical formula, chemical formula, table, etc.▼(Here, n is 4 to 12)
It is an integer of 7. ) is shown. ] has a repeating unit represented by [
The repeating unit [I] relative to the sum of the content of the repeating unit [I] and the content of the repeating unit [II]
The ratio of Features polyester carbonate. 2. At least the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [III] [However, R^1, R^2 and X^1 in formula [III] are each as defined in claim 1 Represents the same meaning as in general formula [I]. ] A reaction system consisting of bisphenols [III] represented by [III] and phthalic acid dihalide and a polycarbonate oligomer consisting of a repeating unit [II] represented by the general formula [II] according to claim 1 are mixed,
The method for producing polyester carbonate according to claim 1, characterized in that a polycondensation reaction is carried out. 3. An optical material comprising the polyester carbonate according to claim 1.