JPH07102154A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin composition containing a specific aromatic polyester carbonate and a copolymerized polycarbonate, having excellent and balanced transparency, heat-resistance, impact resistance and flowability and useful for optical lens, prism, etc. CONSTITUTION:This thermoplastic resin composition contains (A) 99-1 pts.wt. of an aromatic polyester carbonate containing an aromatic dicarboxylic acid residue, an aromatic dihydroxy compound residue and a carbonic acid residue and (B) 1-99 pts. wt. of a copolymerized polycarbonate containing a structural unit of the formula I [R<4> and R<5> are halogen or univalent hydrocarbon group; B is (R<1>-)C(-R<2>) (R<1> and R<2> are H or univalent hydrocarbon group), C(=R<3>) (R<3> is bivalent hydrocarbon group), O, etc.; p and q are 0-4] and a structural unit of the formula II [R<6> is halogen or 1-10C (halogen-substituted) hydrocarbon group; n is 0-4] wherein the amount of the structural unit of the formula II is 2-90mol.% based on the sum of the structural units of the formula I and the formula II.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition containing an aromatic polyester carbonate and a copolycarbonate having resorcin or a derivative residue thereof.

[0002]

BACKGROUND OF THE INVENTION Aromatic polyester carbonates are excellent in transparency, heat resistance and impact resistance, and therefore, they are used in various fields including optical materials such as glass substitute materials such as lenses and prisms. There is. But,
Since the aromatic polyester carbonate has poor fluidity,
It has the drawback of poor moldability. On the other hand, the copolycarbonate having resorcin or its derivative residue has excellent transparency and impact resistance as well as good flowability, like the aromatic polyester carbonate.

[0003]

However, the copolymerized polycarbonate having resorcin or its derivative residue has a drawback that it has lower heat resistance than aromatic polyester carbonate.

Therefore, an object of the present invention is to provide a thermoplastic resin composition having excellent balance of transparency, heat resistance, impact resistance and fluidity.

[0005]

SUMMARY OF THE INVENTION The present inventors achieve the above object by blending an aromatic polyester carbonate with a copolycarbonate having a specific structure containing resorcin or its derivative residue. It was found that the present invention has been completed.

That is, the thermoplastic resin composition of the present invention is
(A) 99 to 1 parts by weight of an aromatic polyester carbonate containing an aromatic dicarboxylic acid residue, an aromatic dihydroxy compound residue and a carbonic acid residue, and (B) the following formula (Formula 3):

[0007]

[Chemical 3] And the following formula (Formula 4):

[0008]

[Chemical 4] (In the above formula, R ⁴ and R ⁵ are each independently a halogen atom or a monovalent hydrocarbon group, and B is — (R ^{1
-) C (-R 2) -} [ wherein, R ¹ and R ² are each independently a hydrogen atom or a monovalent hydrocarbon ^{group], - C (= R 3} ) - [ where R ³ is It is a divalent hydrocarbon group], -O-, -S-, -SO- or -SO.
_2- , R ⁶ is a hydrocarbon group having 1 to 10 carbon atoms or a halide thereof, or a halogen atom, and p, q
And n are each independently an integer of 0 to 4), and the amount of the structural unit of (Chemical Formula 4) is the sum of the structural units of (Chemical Formula 3) and (Chemical Formula 4). 2 to quantity
Copolymerized polycarbonate occupying 90 mol%
A thermoplastic resin composition including 1 to 99 parts by weight is provided.

The component (A) aromatic polyester carbonate used in the present invention is (a) an aromatic dicarboxylic acid and / or a derivative thereof, (b) an aromatic dihydroxy compound and / or a derivative thereof, and (c) a diaryl carbonate. Alternatively, it is obtained from phosgene.

Examples of the aromatic dicarboxylic acid (a) include terephthalic acid, isophthalic acid, methylterephthalic acid, methylisophthalic acid, diphenyletherdicarboxylic acid, diphenoxyethanedicarboxylic acid, naphthalenedicarboxylic acid, and ester-forming derivatives thereof. Examples thereof include lower alkyl ester, phenyl ester, acid halide and the like. You may use these 1 type (s) or 2 or more types.

(B) Aromatic dihydroxy compounds include hydroquinone, resorcin, 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A), 4,4'-dihydroxydiphenyl, 1,1-bis (4 -Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 4,4 Examples thereof include'-dihydroxydiphenyl sulfone, 1,2-bis (4-hydroxyphenyl) ethane and their ester-forming derivatives. You may use these 1 type (s) or 2 or more types. Of these, bisphenol A is particularly preferable.

As the (c) diaryl carbonate,
Examples thereof include diphenyl carbonate, dicresyl carbonate, di-β-naphthyl carbonate and bis (2-chlorophenyl) carbonate. You may use these 1 type (s) or 2 or more types.

Among these, terephthalic acid (or terephthalic acid diphenyl ester) and bisphenol A are particularly preferable.
A combination of and diphenyl carbonate is preferably used.

The aromatic polyester carbonate (A) used in the present invention comprises the above-mentioned (a), (b) and
It can be produced from the three components of (c) by any method such as bulk polycondensation, melt polycondensation, and interfacial polycondensation.

Next, the component (B) copolymerized polycarbonate used in the present invention must have the structural units represented by the above formulas (Formula 3) and (Formula 4). First,
The structural unit represented by (Chemical Formula 3) is composed of a diphenol component and a carbonate component. The diphenol that can be used to introduce the diphenol component is shown in the following formula (Formula 5).

[0016]

[Chemical 5] In the above formula, R ⁴ , R ⁵ , B, p and q have the same meaning as described above.

Examples of the diphenol effective in the present invention include bis (4-hydroxyphenyl) methane, 1,
1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-
Hydroxyphenyl) propane (so-called bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 2,
2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-1-methylphenyl) propane, 1,1-bis (4-hydroxy-t- Butylphenyl) propane, 2,2-bis (4-
Bis (hydroxyaryl) alkanes such as hydroxy-3-bromophenyl) propane; bis (hydroxyaryl) such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane ) Cycloalkanes; dihydroxyaryl ethers such as 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether; 4,4'-dihydroxydiphenyl sulfide, 4,4'-
Dihydroxy diaryl sulfides such as dihydroxy-3,3'-dimethyldiphenyl sulfide; 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-
Dihydroxy diaryl sulfoxides such as 3,3'-dimethyldiphenyl sulfoxide; Dihydroxy diaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone , But not limited to these. These can be used alone or in combination of two or more. Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferable.

Examples of the precursor for introducing the carbonate component include, for example, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate and dimethyl. Examples thereof include carbonic acid diesters such as carbonate, dibutyl carbonate and dicyclohexyl carbonate, and carbonyl halide compounds such as phosgene. These can be used alone or in combination of two or more. Diphenyl carbonate is particularly preferable.

Next, the structural unit represented by the above formula (Formula 4) comprises a diphenol component, resorcin and / or substituted resorcin component and a carbonate component. Regarding the introduction of the diphenol component, the same diphenol as described above can be used. As the carbonate component, the above-mentioned carbonic acid diester or phosgene can be used. To introduce the resorcin and / or the substituted resorcin component, the following formula (Formula 6):

[0020]

[Chemical 6] (Wherein R ⁶ and n have the same meanings as described above), and one or more compounds can be used in combination. Examples of such compounds include resorcin, 3-methylresorcin, 3-ethylresorcin,
3-propylresorcin, 3-butylresorcin, 3-t-butylresorcin, 3-phenylresorcin, 3-cumylresorcin, 2,3,4,6-tetrafluororesorcin, 2,3,4,6-tetrabromo Substituted resorcins such as resorcin are included. Of these, resorcin is particularly preferable.

The component (A) copolymerized polycarbonate is
It has the above-mentioned two types of structural units represented by (Chemical Formula 3) and (Chemical Formula 4) in the following proportions. That is, the amount of the structural unit represented by (Chemical Formula 4) is 2 times the total amount of (Chemical Formula 3) and (Chemical Formula 4).
˜90 mol%, preferably 2-40 mol%. If the amount of (Chemical Formula 4) is less than 2 mol%, the glass transition temperature (T
Since the decrease of g) is insufficient, the effect of improving the fluidity cannot be seen. On the other hand, if it exceeds 90 mol%, excellent physical properties equivalent to those of conventional polycarbonates, such as mechanical strength and heat resistance, cannot be obtained.

The weight average molecular weight of the component (A) copolymerized polycarbonate is usually 10,000 to 100,000, preferably 18,0.
It is from 00 to 40,000. With the weight average molecular weight here, using polystyrene corrected for polycarbonate,
It is measured by GPC (gel permeation chromatography). (It is also preferable that the intrinsic viscosity measured at 25 ° C in methylene chloride is 0.35 to 0.65 dl / g.) The component (A) copolymerized polycarbonate is a known polycarbonate production method, for example, an interface using phosgene. It can be produced by a polymerization method, a melt polymerization method, or the like. Particularly, the melt polymerization method does not use toxic substances such as phosgene and methylene chloride, and is therefore preferable from the viewpoint of environmental hygiene.

Conditions such as temperature and pressure at the time of the melt polymerization reaction are arbitrary, and known conventional conditions can be used.
Specifically, it is preferably 80 to 250 ° C, more preferably 1
At a temperature of 00 to 230 ° C., particularly preferably 120 to 190 ° C., preferably 0 to 5 hours, more preferably 0 to 4 hours, particularly preferably 0 to 3 hours under normal pressure, diphenol and the above formula The compound represented by 6) is reacted with carbonic acid diester. Then, the reaction temperature is raised while reducing the pressure of the reaction system to carry out the reaction between the diphenol and the compound represented by the above formula (Formula 6) and the carbonic acid diester, and finally the pressure is reduced to 5 mmHg or less, more preferably 1 mmHg or less. Under 240
At a temperature of ~ 320 ° C, diphenol and the above formula
It is preferable to carry out the reaction between the compound represented by and the carbonic acid diester.

The polycondensation reaction as described above may be carried out continuously or batchwise. Further, the reaction apparatus used when carrying out the above reaction may be of a tank type, a tube type, or a column type.

According to this melt polymerization method, the structural unit (Chemical formula 4) in the obtained copolycarbonate exceeds 90 mol% of the total of (Chemical formula 3) and (Chemical formula 4), that is, resorcin and Even if the substituted resorcinol is used in an amount exceeding 90 mols based on 100 mols of diphenol, the hue, water resistance, and heat resistance are excellent as compared with other methods such as the interfacial polymerization method. A copolycarbonate is obtained.

Further, the component (A) copolymerized polycarbonate has sufficient impact resistance even if its terminal is phenol, but pt-butylphenol, isononylphenol, isooctylphenol, m- or p-cumylphenol ( By introducing a bulkier end group such as preferably p-cumylphenol), a chromanyl compound, for example, chroman, a copolymerized polycarbonate excellent in low temperature impact resistance can be obtained.

The blending ratio of the above components (A) and (B) is such that (B) is 99-1 with respect to 1-99 parts by weight of (A).
Parts by weight, preferably 10 to 90 parts by weight of (A) (B)
90 to 10 parts by weight.

In addition to the above-mentioned components, the resin composition of the present invention may further contain other conventional additives such as pigments at the time of mixing the resin and molding, depending on the purpose, as long as the physical properties are not impaired. Dyes, reinforcing agents (glass fiber, carbon fiber, etc.), fillers (carbon black, silica, titanium oxide, etc.), heat-resistant agents, antioxidants, weathering agents, lubricants, release agents, plasticizers, flame retardants, flow A property improving agent, an antistatic agent, etc. can be added.

There is no particular limitation on the method for producing the resin composition of the present invention, and ordinary methods can be satisfactorily used. However, melt mixing is generally preferred. The use of small amounts of solvent is possible, but generally not required. Examples of the apparatus include extruders, Banbury mixers, rollers, and kneaders, which are operated batchwise or continuously. The order of mixing the components is not particularly limited.

[0030]

EXAMPLES The present invention will be described in more detail with reference to examples. In the examples, the following components were used. Component (A) Aromatic polyester carbonate: Aromatic polyester carbonate having isophthalic acid residue and terephthalic acid residue, bisphenol A residue and carbonic acid residue (80% by weight of ester component, 20% by weight of carbonate component, isophthalate: terephthalate = 93: 7), intrinsic viscosity 0.50 dl / g component (B) measured at 25 ° C in methylene chloride RS-PC: Copolymerized polycarbonate produced as follows; Bisphenol A (manufactured by Nippon GE Plastics Co., Ltd.) ) 0.22 kmole, resorcin 0.2
2 kmole and 0.44 kmole of diphenyl carbonate (Any Co.) were added to the first tank type agitator (capacity 25
(0 liter) and melted at 140 ° C. While maintaining this temperature, the resulting mixture was mixed with bisphenol A.
The solution was sent to a second tank-type stirrer (capacity: 50 liters) at a rate of 0.16 kmole per hour in terms of conversion. The temperature of the second tank stirrer was maintained at 180 ° C.

Tetramethylammonium hydroxide (0.04 mol / hr) and sodium hydroxide (0.00016 mol / hr) (1 × 10 ^-6 mol / mol-bisphenol A) were added as catalysts, and the residence time was 30 minutes. The time was adjusted so that

Next, this reaction solution was fed to a third tank-type stirrer (capacity: 50 liters) at a rate of 0.16 kmole per hour in terms of bisphenol A. The temperature of the third tank stirrer was 210 ° C. and the pressure was 200 mmHg. The time was adjusted so that the residence time was 30 minutes, and the mixture was stirred while extracting and removing phenol.

Next, this reaction liquid was fed to a fourth tank-type stirrer (capacity: 50 liters) at a rate of 0.16 kmole per hour in terms of bisphenol A. The temperature of the fourth tank stirrer was 240 ° C. and the pressure was 15 mmHg. The time was adjusted so that the residence time was 30 minutes, and the mixture was stirred while extracting and removing phenol. The intrinsic viscosity [η] of the reaction product obtained when the reaction became steady was 0.15 dl / g.

Next, the pressure of this reaction product is increased by a gear pump,
It was fed into a centrifugal thin-film evaporator at a rate of 0.16 kmol / hour in terms of bisphenol A to proceed the reaction. The temperature and pressure of the thin film evaporator are 270 ° C and 2 mm, respectively.
Controlled to Hg. Using a gear pump from the bottom of the evaporator, the reaction product was charged with bisphenol A in a biaxial horizontal stirring polymerization tank (L / D = 3, stirring blade rotating diameter 220 mm, internal volume 80 liters) controlled at 290 ° C. and 0.2 mmHg. Converted to 0 per hour.
It was fed at a rate of 16 kilomoles (about 40 kg / hour) and polymerized at a residence time of 30 minutes. The intrinsic viscosity [η] of the product at this time was 0.49 dl / g. The product is
It was a copolycarbonate having the following formulas (Formula 7) and (Formula 8) in a molar ratio of 50:50. In the following, this is R
Abbreviated as S-PC.

[0035]

[Chemical 7]

[0036]

[Chemical 8] The components of Examples 1 to 3 and Comparative Examples 1 and 2 were mixed in the ratios (weight ratios) shown in the table, and the mixture was mixed at 280 ° C. and 10
Pellets were prepared by extrusion with a single-screw extruder (65 mm) set at 0 rpm and 80 Kg / hour (extrusion speed). The melt index (MI) of this pellet was measured. Next, a test piece was molded from this pellet by injection molding, and the Izod impact strength, total light transmittance and heat distortion temperature (HDT) of this molded product were measured. The results are shown in Table 1.

The Izod impact strength is ASTM
According to D256, 1/8 inch notched Izod impact strength was measured. Total light transmittance is 50 x 50 x 3 using a haze meter (Model 1001DP, Nippon Denshoku Co., Ltd.)
The test piece of mm was measured. Heat distortion temperature is ASTM
According to D648, the load was measured at 18.6 Kg. The melt index was measured according to ASTM D1238.

[0038]

[Table 1] Table 1 ------------------------------------------ Example Comparative Example 1 2 3 1 2 --- −−−−−−−−−−−−−−−−−−−−−−−−−−−− Component (parts by weight) Aromatic polyester carbonate 80 50 20 100-RS-PC 20 50 80- 100 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Izod impact strength (Kg / cm-cm) 80 80 80 80 70 Total rays Transmittance (%) 90 90 90 90 90 HDT (° C) 155 140 127 165 120 MI (g / 10 min) 3 8 16 1 24 −−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−

[0039]

According to the present invention, the advantages of both the aromatic polyester carbonate and the copolycarbonate are utilized, and a thermoplastic resin composition having a good balance of transparency, heat resistance, impact resistance and fluidity is provided. Can be provided. Since the resin composition of the present invention is suitable for a wide range of uses, it is industrially highly useful.

Claims (1)

[Claims] 1. (A) 99 to 1 part by weight of an aromatic polyester carbonate containing an aromatic dicarboxylic acid residue, an aromatic dihydroxy compound residue and a carbonic acid residue, and (B) the following formula (Formula 1): 1] And the following formula (Formula 2): (In the above formula, R ⁴ and R ⁵ are each independently a halogen atom or a monovalent hydrocarbon group, and B is — (R ^{1
-) C (-R 2) -} [ wherein, R ¹ and R ² are each independently a hydrogen atom or a monovalent hydrocarbon ^{group], - C (= R 3} ) - [ where R ³ is It is a divalent hydrocarbon group], -O-, -S-, -SO- or -SO.
_2- , R ⁶ is a hydrocarbon group having 1 to 10 carbon atoms or a halide thereof, or a halogen atom, and p, q
And n are each independently an integer of 0 to 4), and the amount of the structural unit of (Chemical Formula 2) is the sum of the structural units of (Chemical Formula 1) and (Chemical Formula 2). 2 to quantity
Copolymerized polycarbonate occupying 90 mol%
A thermoplastic resin composition containing 1 to 99 parts by weight.