JPH07196906A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having excellent balance of transparency, heat resistance, impact resistance and fluidity, comprising a polycarbonate resin and a copolymer polycarbonate prepared by copolymerizing a bisphenol, resorcinol, etc., with diphenyl carbonate. CONSTITUTION:This thermoplastic resin composition useful for a substitute material for glass, optical uses, etc., is obtained by blending (A) 99-1 pt.wt. of a polycarbonate resin with (B) 1-99 pts.wt. of a copolymer polycarbonate prepared by copolymerizing a bisphenol (e.g. bisphenol A) resorcinol with diphenyl carbonate and having a structure unit of formula I [R<4> and R<5> each is a halogen or a monofunctional hydrocarbon; B is a group of the formula (R<1>-)C(-R<2>) (R<1> and R<2> are H or a monofunctional hydrocarbon), a group of formula C(=R3) (R3 is a bifunctional hydrocarbon), O, S, SO or SO2; p and q each is 0-4) and formula II (R<6> is a 1-10C hydrocarbon or a halogen; n is 0-4] in which the amount of the structural unit of formula II amounts to 2-90mol% total amount of the structural units of formula I and formula II.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition containing a polycarbonate resin and a copolymerized polycarbonate having resorcin or a derivative residue thereof.

[0002]

2. Description of the Related Art Polycarbonate resins are excellent in transparency, heat resistance and impact resistance, and are therefore used in various fields including optical materials such as glass substitute materials such as lenses and prisms. Has been done.

However, since the polycarbonate resin is inferior in fluidity, it has a drawback of poor moldability. If the fluidity is merely improved, the molecular weight of the polycarbonate resin may be lowered, but in that case, the impact strength of the molded product is lowered, which is not preferable.

On the other hand, the copolycarbonate having resorcin or its derivative residue has excellent transparency and impact resistance as well as the polycarbonate resin, and has good fluidity. However, the copolymerized polycarbonate having the resorcin or its derivative residue has a drawback that it has lower heat resistance than the polycarbonate resin. 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]

The present inventors have found that the above object can be achieved by blending a polycarbonate-based resin with a copolymerized carbonate resin having a specific structure, and completed the present invention. .

That is, the thermoplastic resin composition of the present invention is
(A) Polycarbonate resin 99 to 1 part by weight, 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%
It is characterized by containing 1 to 99 parts by weight.

As the component (A) polycarbonate resin used in the present invention, known resins can be used.

[0010]

[Chemical 5] In the above formula, R ⁴ , R ⁵ , B, p and q have the same meanings as defined above, and consist of a diphenol component derived from diphenol and a carbonate component. In the above formula, when R ⁴ and R ⁵ are halogen atoms, examples thereof include chlorine atom and bromine atom. Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkaryl group.

Further, B is-(R ^1- ) C (-R ² )-
Or -C (= R ³⁾ - in the case of a group represented by the
Alkylene group, alkylidene group, cycloalkylene group,
Alternatively, it is a cycloalkylidene group or the like.

Specific examples of diphenols include diphenol; 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A); 2,2-bis (3,5-dibromo-4-hydroxyphenyl). Propane: 2,2-bis (3,
5-Dimethyl-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (4 -Hydroxyphenyl) decane; 1,4-bis (4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclododecane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) Cyclododecane; 4,4-
And dihydroxydiphenyl ether; 4,4-thiodiphenol; 4,4-dihydroxy-3,3-dichlorodiphenyl ether; and 4,4-dihydroxy-2,5-dihydroxydiphenyl ether. In addition, the diphenols described in U.S. Pat. Nos. 2,999,835, 3,028,365, 3,334,154 and 4,131,575 can be used. Such a polycarbonate can be produced by a known interfacial polymerization method using phosgene, a melt polymerization method, or the like.

The polycarbonate may be branched. Such branched polycarbonates are obtained as branched thermoplastic random branched polycarbonates by reacting polyfunctional aromatic compounds with diphenol and / or carbonate precursors.

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 the diphenol represented by the formula (Formula 5) 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 precursors for introducing the carbonate component include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, 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):

[0018]

[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 (B) 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 (B) 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 (B) copolymerized polycarbonate can be produced by a known method for producing a polycarbonate, for example, an interfacial polymerization method using phosgene or a melt polymerization method. 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 (B) 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 compounding ratio of the above components (A) and (B) is such that the ratio of (B) is 99 to 1 with respect to 1 to 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 resin mixing 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.

[0029]

EXAMPLES The present invention will be described in more detail with reference to examples. In the examples, the following components were used. Ingredient (A) PC: Polycarbonate of bisphenol A, trademark LEXA
Intrinsic viscosity measured at 25 ° C in N (manufactured by Nippon GE Plastics Co., Ltd.), methylene chloride
0.50 dl / g component (B) RS-PC: Copolycarbonate 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 thereto 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, the reaction solution 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.

[0034]

[Chemical 7]

[0035]

[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). Next, spiral flow molding (thickness: 3 mm) was performed under the conditions of a set temperature of 280 ° C., a mold temperature of 80 ° C., and an injection pressure of 900 Kg / cm ² , and the flow length during the spiral flow molding was measured. further,
The Izod impact strength, total light transmittance, heat distortion temperature (HDT) and melt index (MI) of the obtained molded product were measured, and the results are shown in the table.

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.

[0037]

[Table 1]

[0038]

According to the present invention, the advantages of both the polycarbonate resin and the copolycarbonate resin are utilized, and a thermoplastic resin composition having excellent balance of transparency, heat resistance, impact resistance and fluidity is provided. can do. Since the resin composition of the present invention is suitable for a wide range of uses, it is industrially highly useful.

Claims (2)

[Claims] 1. A polycarbonate resin (A) 99-1
Parts by weight, and (B) the following formula (Formula 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. 2. In the component (B), B in the formulas (Formula 1) and (Formula ² ) is-(R ^1- ) C (-R ² )-(R ¹
And R ² have the same meanings as defined above).