JPS6310654A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. having excellent mechanical characteristics and optical properties such as low optical distortion, by blending a specified polycarbonate copolymer with a styrene polymer. CONSTITUTION:A blend of a dihydric phenol (a) of formula I [wherein X is a single bond, (thio)ether bond,-SO2- or a group of formula III, IV or V; R<3> and R<4> are each H, a 1-5C alkyl or phenyl; n is a number of 0-2; and n' is a number of 4-8] (e.g., 2,2-bis(3-phenyl-4-hydroxyphenyl)propane] and 10-50mol% of a dihydric phenol (b) of formula II (wherein Y is X; R<1> and R<2> are each R<3> or halogen; l and m are each a number of 1-4) [e.g., 2,2-bis(4- hydroxyphenyl)propane] is reacted with a carbonic ester forming compd. (C) (e.g., phosgene) in the presence of an acid acceptor in a solvent at a pH of 10 or higher and at 0-150 deg.C for 0.5min to 10hr to obtain a polycarbonate copolymer (A) composed of repeating units of formulas VI and VII. 50-97pts.wt. component A is blended with styrene polymer (B) (e.g., PS).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a thermoplastic resin composition having excellent optical properties and comprising a polycarbonate copolymer and a styrene copolymer.

[Conventional technology]

Traditionally, typical polycarbonate resins are 2.2
A product obtained by reacting -bis-(4'-hydroxyphenyl)propane (bisphenol A) with phosgene or diphenyl carbonate is known, and this product has excellent transparency, heat resistance, and mechanical properties. Because it has excellent properties such as good molding accuracy, it is widely used as an engineering plastic in many fields.

By the way, plastic optical elements have been gaining popularity in recent years because they have advantages such as being lighter than glass ones, having excellent impact resistance, no polishing required, easy mass production, and the ability to mass produce aspherical lenses. The demand for it is increasing.

Polycarbonate polymers are known to be useful as materials for plastic optical elements because they have excellent optical properties such as transparency, heat resistance, mechanical strength, and high refractive index. The stress and strain generated during injection molding are large, and therefore it cannot be said to be a sufficient material as an optical material. There has been an attempt to improve the optical properties by blending polystyrene into this polycarbonate (Japanese Patent Application Laid-Open No. 19656/1982), but the two are incompatible, resulting in large light scattering and optical distortion. have.

[Problem that the invention seeks to solve]

Under these circumstances, an object of the present invention is to provide a thermoplastic resin composition comprising a polycarbonate copolymer with low optical distortion and useful as a material for optical devices.

[Means for solving problems]

As a result of intensive research into polycarbonate resin compositions, the present inventors discovered that a composition containing a polycarbonate copolymer and a styrene polymer having a specific structure has small optical distortion. Based on this knowledge, we have completed the present invention.

and [wherein X and Y are a single bond, an ether bond, or a thioni-
chill bond, or -3O□-1-C- (however, R3
and R4 are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group), ÷CHz-h (where n is an integer of 2 to 10) or \l (where n' is an integer of 4 to 10), respectively. is an integer of 8), and X=Y
However, X≠Y is also acceptable. R' and RZ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and! and m are integers of 1 to 4, respectively.
The object of the present invention is to provide a thermoplastic resin composition characterized in that it contains 50 parts by weight.

A dihydric phenol represented by polycarbonate (in the formula, X, Y, R', R", 1, and m have the same meanings as above) used in the resin composition of the present invention, and a carbonate ester-forming compound It can be produced by reacting with.

The general formula (III) used as a raw material for this copolymer
Specifically, the compound having the structure represented by is bis(3-phenyl-4-hydroxyphenyl)methane,
1,1-bis(3-phenyl-4-hydroxyphenyl)ethane, 1,2-bis(3-phenyl-4-hydroxyphenyl)ethane, 2.2-bis(3-phenyl-4
-hydroxyphenyl)propane, 1,3-bis(3-
Phenyl-4-hydroxyphenyl)propane, 2゜2
-bis(3-phenyl-4-hydroxyphenyl)butane, 1,4-bis(3-phenyl-4-hydroxyphenyl)butane, 2.2-bis(3-phenyl-4-hydroxyphenyl)octane, 1. 8-bis(3-phenyl-4-hydroxyphenyl)octane, 1-phenyl-1,1-bis(3-phenyl-4-hydroxyphenyl)ethane, diphenyl-bis(3-phenyl-4-hydroxyphenyl)methane , 1,1-bis(3-phenyl-4-hydroxyphenyl)cyclopentane, 1.1
-bis(3-phenyl-4-hydroxyphenyl)cyclohexane, 3.3'-diphenyl-4,4'-dihydroxybiphenyl, 3゜3'-diphenyl-4,4'-
Dihydroxydiphenyl ether, 3.3'-diphenyl-4,4'-dihydroxydiphenyl sulfide, 3
．． Examples include 31-diphenyl-4,4'-dihydroxydiphenylsulfone.

In addition, the compound represented by -J'IQ formula (IV) includes 2,2-bis(4-hydroxyphenyl)propane,
2,2-bis(3-methyl-4-hydroxyphenyl)
Propane, bis(4-hydroxyphenyl)methane, 2
．． 2-bis(4-hydroxyphenyl)butane, 2.2
-bis(4-hydroxyphenyl)octane, 4.4-
Bis(4-hydroxyphenyl)hebutane, 2.2-(
3,5,3',5'-tetrabromo-4,4'-dihydroxydiphenyl)propane, (3,3'-dichloro-
4,4'-dihydroxydiphenyl)methane, bis-(
3,5-dimethyl-4-hydroxyphenyl)ether, bis-(3,5-dimethyl-4-hydroxyphenyl)sulfone, bis-(3゜5-dimethyl-4-hydroxyphenyl)sulfide, bis-(3, 5-dimethyl-
Examples include 4-hydroxyphenyl)cyclohexane.

On the other hand, examples of carbonate-forming compounds include phosgene, diphenyl carbonate, g-p-)lyl carbonate, phenyl-p-tolyl carbonate, and di-p-tolyl carbonate.
- bisaryl carbonates such as chlorophenyl carbonate and dinaphthyl carbonate.

The method for producing the copolymer includes known methods used in producing polycarbonate from bisphenol A, such as direct reaction of dihydric phenol and phosgene.
Alternatively, a method such as a transesterification reaction between a dihydric phenol and a bisaryl carbonate can be employed.

In the former direct reaction method of dihydric phenol and phosgene, the dihydric phenol represented by the general formulas (III) and (IV) is reacted with phosgene, usually in the presence of an acid binder and a solvent.

As the acid binder, for example, pyridine, sodium hydroxide, a hydroxide of an alkali metal such as J-ram, etc. are used, and as the solvent, for example, methylene chloride, chlorobenzene, xylene, etc. are used. Furthermore, in order to accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt is used, and a molecular weight compound such as pt-butylphenol or phenylphenol is added to adjust the degree of polymerization. It is desirable to carry out the reaction with the addition of a regulator. Further, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added as desired.

The blending ratio of dihydric phenols (III) and (IV) is arbitrary; if you want to obtain a copolymer with a high refractive index, the ratio of compound (III) to be used can be increased; ) has a copolymerization composition of dihydric phenol of 10 to 5.
It is preferable to set it to 0 mol%.

The reaction is usually carried out at a temperature ranging from 0 to 150°C, preferably from 5 to 40°C. The reaction time depends on the reaction temperature, but is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours.
It's time. Further, during the reaction, it is desirable to maintain the pH of the reaction system at 10 or higher.

On the other hand, in the latter transesterification method, the general formula (D
The dihydric phenols represented by I) and (IV) and bisaryl carbonate are mixed and reacted under reduced pressure at high temperature. The reaction is usually carried out at a temperature in the range of 150 to 350°C, preferably 200 to 300°C, and the final degree of vacuum is preferably 1 dragon Hg or less to remove the bisaryl carbonate produced by the transesterification reaction. The zero reaction time for distilling phenols out of the system depends on the reaction temperature, degree of vacuum, etc., but is usually 1.
~4 hours. The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon, and if desired, the above-mentioned molecules can be reacted with a regulator, an antioxidant, etc.
A reaction may also be carried out.

The polycarbonate copolymer thus obtained has repeating units represented by the above general formula, and is prepared at a temperature of 20°C in a solution of 0°5 g/dCt@degrees in methylene chloride as a solvent. reduced viscosity C77sp/c)
is 0.2 dl! /g or more is preferably used. If the reduced viscosity is less than 0.2 dll/g, the mechanical strength will be insufficient.

In addition to polystyrene, the styrene resins to be blended with the above-mentioned polycarbonate copolymer include poly(alkyl-substituted poly(p-methylstyrene), poly(m-methylstyrene), poly(α-methylstyrene), styrene), poly(p-chlorostyrene), poly(m
- (halogen-substituted styrene) such as (chlorostyrene), and mixtures thereof, as well as copolymers of styrene compounds and unsaturated monocarboxylic acids or unsaturated dicarboxylic acids or derivatives thereof, such as styrene-maleic anhydride. Examples include copolymers and other unsaturated compounds copolymerizable with styrene compounds, such as acrylonitrile, methyl methacrylate, methyl acrylate, etc., copolymerized with styrene compounds in an amount of up to 10 mol %.

The blending ratio of the above polycarbonate copolymer and styrene polymer is 50 to 97 parts by weight of the former and 3 parts by weight of the latter.
It is necessary to mix up to 50 parts by weight. If the blending ratio of the styrene polymer is less than 3 parts by weight, the effect of improving optical properties will be small, and if it exceeds 50 parts by weight, optical properties, heat resistance, and mechanical strength will decrease.

The polycarbonate polymer and the styrene polymer can be uniformly mixed by a known melt-kneading method using an injection molding machine, an extruder, a Nigoo mixer, a Banbury mixer, etc., or by dissolving them in a common solvent such as methylene chloride. Examples include a method in which the solvent is mixed with a solvent and then dried.

Examples of molding methods for the resin composition of the present invention include methods normally used for molding polycarbonate resins, such as injection molding, compression molding, the low-links method that is a combination of injection molding and compression molding, and micromolding. Any method can be used.

In the above molding method, the composition may be molded as is, but if desired, the composition may be added with various components, such as phosphorous esters and melt index to prevent coloring and deterioration of transparency. It may be molded by adding a plasticizer to increase the value, or it may be molded by adding other resins to the extent that the properties of the composition of the present invention are not impaired.

Examples of the phosphite esters used in this case include tributyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trisstearyl phosphite, triphenyl phosphite, tricresyl phosphite, and tris(2-ethylhexyl) phosphite. Noni, ruphenyl) phosphite, 2-ethylhexyldiphenylphosphite, decyldiphenylphosphite, phenyl-di2
-Ethylhexyl phosphite, phenyldidecyl phosphite, tricyclohexyl phosphite, distearylpentaerythrityl diphosphite, diphenylpentanyl slityl diphosphite, and the like.

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

These additives can be blended into the resin by tri-blending, by melt-mixing when pelletizing with an extruder, or by creating a master pellet with a high concentration of additives and tri-blending with pellets without additives. Examples include methods.

The thermoplastic resin composition of the present invention obtained in this manner has excellent transparency, heat resistance, and mechanical strength, and has the characteristics of low optical distortion.

〔Example〕

EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way.

510 g (3 mol) of 0-phenylphenol and 58 g (1 mol) of acetone were mixed, heated to 60°C to dissolve, then 10 g of mercaptoacetic acid was added as a catalyst, and hydrochloric acid gas was blown in for 36 hours while stirring. . After washing the obtained reaction product three times with warm water, the organic phase was heated to 190 ml under reduced pressure.
heated to ℃.

Then, the residue was dissolved in 400+ nl of methylene chloride,
After adding 500 ml of a 2N aqueous sodium hydroxide solution and stirring, the crystals were precipitated by cooling on ice, and the crystals were washed twice with 400 ml of methylene chloride, then washed with 500 ml of a 2N aqueous sodium hydroxide solution, and then washed with 500 ml of a 2N aqueous sodium hydroxide solution. Hydrochloric acid 27! After stirring, the crystals were filtered, washed several times with water, and then dried under reduced pressure.

In this way, 154 g of crystals (yield: 40%) were obtained.

The melting point of this compound is 58-60°C, and the purity is 99.
It was 3%. According to analysis by proton NMR, this compound is 2゜2-bis(3-phenylene) having the following structure.
Lt-4-Hydroxyphenyl Example 1 (1) Production of polycarbonate copolymer Into a flask with an internal volume of 11, 70 g (0,307 mol) of 2,2-bis(4'-hydroxyphenyl)propane was added at a concentration of 6%. was dissolved in 480 ml of an aqueous sodium hydroxide solution and 250 ml of methylene chloride were added thereto, and phosgene gas was blown in at a rate of 900+sl/min for 14 minutes while stirring. Then, the product was separated by standing to obtain a methylene chloride solution of a polycarbonate oligomer having a polymerization degree of 2 to 3 and having a chloroformate group terminal.

Next, this solution 30 (1 ml was diluted with methylene chloride to make 450 ml, 1.2 g of p-tert-butylphenol as a molecular weight regulator, and 2
, 2-bis(3-phenyl-4-hydroxyphenyl)
Add 29.0 g of propane? 8, water 120m
7 of the catalyst triethylamine while stirring.
% aqueous solution was added thereto, and 20 ml of a 12.5 normal concentration sodium hydroxide aqueous solution was added dropwise over 30 minutes.

Subsequently, the reaction was continued for 1 hour at room temperature while stirring. After completion of the reaction, the reaction product was diluted with 11 parts of methylene chloride, water, 0
．． After sequentially washing with 01N hydrochloric acid and water, the copolymer was poured into 51 methanol to obtain 108 g of a copolymer.

The copolymer obtained here has a reduced viscosity (Cηs p/c) of 0.44 dl/gT:;J at 20"c in a solution with a concentration of 0.5 g/dlt using methylene chloride as a solvent.

It was. Also, from infrared absorption spectrum analysis, 1650c
Absorption due to carbonyl group at m-' position, 1240C!
Absorption due to an ether bond was observed at the l-' position, indicating that the sample had a carbonate bond.

Further, from NMR spectrum analysis, the molar fraction of the repeating unit represented by the formula (1) was 0.33.

For these reasons, this copolymer is a polycarbonate copolymer obtained in the following (2) Production of a thermoplastic resin composition and a styrene homopolymer [Idemitsu Co., Ltd.] as a styrene polymer. Idemitsu styrene @US-305 (manufactured by the petrochemical company) was mixed at a blending ratio of former:latter = 90:10 parts by weight, and fed to an injection molding machine (manufactured by Sumitomo Heavy Industries: Minimat) and injected at 300°C. Molded. The shape of the molded product has a wall thickness of 2.75 fins,
The width was 12.6 fl and the length was 610 mm. The optical properties of this molded article were measured for light transmittance and birefringence. Birefringence was measured by measuring the optical path difference at a wavelength of 633 nm. These results are summarized in the table.

Example 2 Same as Example 1 except that the ratio of polycarbonate copolymer and polyethylene was 80:20 parts by weight.
Same as (2). The results are shown in the table.

Example 3 Example 1 ((
Same as 2). The results are shown in the table.

Example 4 As a styrenic copolymer, a copolymer of styrene and maleic anhydride [manufactured by Idemitsu Petrochemical a@: Moremax@U
The same procedure as in Example 1 (2) was carried out, except that 20 parts by weight of G460) was blended with 80 parts by weight of the polycarbonate copolymer. The results are shown in the table.

Example 5 (1) Production of polycarbonate copolymer 2.2-bis(
Instead of 4'-hydroxyphenyl)propane, 3,3-
Bis(4'-hydroxyphenyl)pentane 78g (0
Copolymer 112 consisting of the following repeating units was prepared in the same manner as in (1) of Example 1, except that 307 mol) was used.
I got g.

The reduced viscosity [ηsp/c) of this copolymer is 0.43 d
A resin composition was obtained in the same manner as in (2) of Example 1, except that 20 parts by weight of polystyrene was blended with 80 parts by weight of the polycarbonate copolymer obtained in (1) above. The optical properties of this material are shown in the table.

Comparative Example 1 Optical properties of the polycarbonate copolymer obtained in Example 1 (1) were measured. The results are shown in the table.

Comparative Example 2 The optical properties of a commercially available polycarbonate (manufactured by Idemitsu Petrochemical Co., Ltd.: Idemitsu Polycarbonate N2200) made from 2.2-bis(4'-hydroxyphenyl)propane were measured. The results are shown in the table.

Comparative Example 3 Optical properties of the polystyrene used in Example 1 (2) were measured. The results are shown in the table.

Comparative Example 4 Optical properties of the copolymer of styrene and maleic anhydride used in Example 4 were measured. The results are shown in the table.

Comparative Example 5 20 parts by weight of the commercially available polystyrene used in Example 1 (2) was added to 80 parts by weight of the commercially available polycarbonate used in Comparative Example 2.
Optical properties of the composition obtained by blending parts by weight were measured. The results are shown in the table.

Margin below *l: l: Effect of homopolymer light] The thermoplastic resin composition of the present invention has excellent mechanical properties and optical properties, and is particularly characterized by low optical distortion. It is used as a material for various optical equipment, such as still cameras, video cameras, telescopes,
It can be used for eyeglasses, contact lenses, prisms, optical fibers, video discs, audio discs, etc.

It is also useful as an engineering plastic and as a material for various molded products.

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X and Y are single bonds, ether bonds, thioether bonds, or ▲ There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R^3 and R^4 are hydrogen atoms, alkyl groups with 1 to 5 carbon atoms, or phenyl groups, respectively), ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (however, n is an integer from 2 to 10) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (however, n' is an integer from 4 to 8). ,X=Y
However, X≠Y may be satisfied, R^1 and R^2 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and l and m are each an integer of 1 to 4. 50 to 97 parts by weight of a polycarbonate copolymer having repeating units, and 3 to 97 parts by weight of a styrene polymer.
A thermoplastic resin composition characterized in that it contains 50 parts by weight.