JPH0778106B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention is based on the fact that an aromatic polycarbonate resin having an average of at least one unsaturated terminal group per molecule and a styrenic polymer are mixed by heating to obtain a graft product of both. It is intended to obtain a composition having an excellent compatibility with a composition, which can provide a composition having excellent transparency, fluidity, and reduced optical strain by a simple operation, an optical disc,
It can also be suitably used for optical lenses and the like.

[Conventional method and its problems]

Conventionally, as a material for an optical transparent molded article, an acrylic resin has been known as a material for an optical transparent molded article because of its characteristics such as transparency, fluidity and small birefringence (JP-A-56-1).
No. 31654 and others). However, the heat resistance of acrylic resin is about 70 ℃.
It has low defects, low impact resistance, and tends to warp due to moisture.

To eliminate the above drawbacks, the viscosity average molecular weight is 15,000 to 18,0
The use of 00 polycarbonate resin as a molding material for discs, lenses, etc. has been studied (Japanese Patent Laid-Open No. 58-180).
No. 553), however, has the drawbacks of insufficient fluidity and large birefringence, which is regarded as important, and its use is limited.

For the above reasons, a method of maintaining excellent characteristics such as transparency of an aromatic polycarbonate resin and eliminating optical distortion has been investigated.

From the viewpoint of fluidity improvement, a composition obtained by blending an aromatic polycarbonate resin and a vinyl aromatic polymer is well known, but there is a difficulty in compatibility, and various methods of this improvement have been investigated, for example, modified polystyrene. Method of copolymerizing with divalent phenols (J. Polymer Sci. Pt. A-1, vol.7,13
39-1347 (1969)), a method of polymerizing a divalent phenol in the presence of a modified polystyrene containing a phenolic hydroxyl group, a method of solution polymerizing a modified polycarbonate resin and a styrene monomer (Japanese Patent Publication No. 48-25076). ).

These methods are excellent, but methylene chloride,
It is essential to use a solvent such as chlorobenzene, it is necessary to separate unreacted styrene and dihydric phenol from the solvent and to recycle them, and the solvent used may be mixed in the product. There are problems such as being large.

[Means for solving problems]

As a result of intensive studies on a method for improving the above-mentioned drawbacks, the present inventors have found a method using an aromatic polycarbonate resin having an unsaturated terminal group, and arrived at the present invention.

That is, the present invention is characterized in that an aromatic polycarbonate resin having an average of at least one unsaturated terminal group per molecule and a styrenic polymer are mixed with a free radical initiator, if necessary, and heated and mixed. A polycarbonate resin composition containing a graft product of a styrene polymer and an aromatic polycarbonate resin.

The configuration of the present invention will be described below.

The process for producing an aromatic polycarbonate having at least one unsaturated end group per molecule of the present invention comprises a monofunctional compound having an unsaturated double bond or a conventional end-capping compound as a molecular weight controlling agent or a terminal terminating agent. Other than using together with a terminator, it is produced by the same production method as conventional aromatic polycarbonate resin, interfacial polymerization method, pyridine method, solution method such as chloroformate method, and viscosity average molecular weight.
2,000 to 100,000, preferably 5,000 to 50,000.

Preferred examples of the dihydric phenol compound used for producing the polycarbonate resin unit of the present invention include bis (4-hydroxyphenyl) methane and bis (4).
-Hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,
1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4
-Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-)
3,5-Dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-
Hydroxyphenyl) diphenylmethane is exemplified.

Further, as the monofunctional compound having an unsaturated double bond for introducing an unsaturated terminal group, acrylic acid chloride,
Acid chlorides and chloroformates such as methacrylic acid chloride, soribine chloride, allyl alcohol chloroformate, isopropenylphenol chloroformate and hydroxystyrene chloroformate; isopropenylphenol, hydroxystyrene, hydroxyphenylmaleimide, allyl hydroxybenzoate Examples thereof include phenols having an unsaturated group such as esters and methylallyl benzoate. These compounds may be used in combination with a conventional terminal stopper and are used in the range of 1 to 25 mol%, preferably 1.5 to 10 mol% based on 1 mol of the above dihydric phenol compound. .

The polycarbonate resin of the present invention is produced by essentially including the above components, but the branching agent is used in an amount of 0.01 to 3 mol%, particularly 0.1 to 3 mol% based on the dihydric phenol compound.
A branched polycarbonate can also be used in combination within the range of 1.0 mol%. Examples of such a branching agent include phloroglysin, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,4,6-dimethyl-2,4,6-
Tri (4-hydroxyphenyl) heptene-2,1,3,5
-Tri (2-hydroxyphenyl) benzol, 1,1,1
-Tri (4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, α, α ', α "-tri (4-hydroxyphenyl) -1, Polyhydroxy compounds exemplified by 3,5-triisopropylbenzene and 3,3-bis (4
-Hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin bisphenol, 5,7-dichloroisatin bisphenol, 5-bromoisatin bisphenol and the like are exemplified.

Next, the styrene-based polymer of the present invention is a polymer having a styrene unit in the molecular chain, such as polystyrene, styrene-methyl methacrylate copolymer, acrylonitrile-styrene copolymer, maleic anhydride-styrene copolymer. , Maleimide-styrene copolymer, acrylonitrile-fudadiene-styrene and the like are preferable.

The composition of the present invention is produced by heating and mixing the unsaturated terminal group-containing aromatic polycarbonate and the styrene-based polymer described above, and a structural unit of the styrene-based polymer and a structural unit of the aromatic polycarbonate. Includes a composition having a chemical bond and a so-called “IPN” of interpenetrating polymer network.

The ratio of the unsaturated end group-containing aromatic polycarbonate to the styrenic polymer is not particularly limited, but the former: the latter = 9
5: 5 to 5:95, preferably 90:10 to 20:80, especially 90:10 to 30: 7
The range is 0.

The heating and mixing conditions are such that the raw materials used can maintain the molten or plasticized state, and the temperature is 100 to 350 ° C, preferably 15
0 ~ 300 ℃, especially 180 ~ 280 ℃ within 1 hour, preferably 3 ~
30 minutes is preferred.

Dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylperoxylaurate, t-butylperoxybenzoate were used as free radical initiators in the above heat mixing. , Di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, organic peroxides such as t-butylperoxyisopropyl carbonate, ozone, oxygen treatment, or heat A depolymerization reaction can be used. In the case of an organic peroxide, 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, is used with respect to 100 parts by weight of the raw material.

The composition of the present invention obtained by heating and mixing by the above method,
It has excellent transparency as compared with the case of using an aromatic polycarbonate having no unsaturated terminal.

The polycarbonate composition of the present invention is as described above, but if necessary, other resins, antioxidants, light stabilizers, colorants, inorganic or organic fillers, carbon fibers, gas fibers, etc. Reinforcing agents, lubricants, antistatic agents and the like may be used in combination.

〔Example〕

 Hereinafter, specific examples will be described.

The viscosity average molecular weight in the examples and the like is obtained by the following method.

(1), measurement of solution viscosity Sample solution: methylene chloride solution with concentration g / 100ml Viscometer: capillary type improved Ubbelohde viscometer with flow time of 72.36 seconds only for methylene chloride Measurement temperature: 20 ℃ ± 0.01 ℃ By this measurement, Measure the flow time at a concentration of 2 g / 100 ml to obtain η _rel .

(2), Calculation [η] is calculated from the expression measured from η _rel, and Mv is calculated from (Schnell's expression).

η _sp = T / T _o −1, η _rel = T / T _o ... η _sp : specific viscosity, T: sample solution flow time To: solvent only flow time η _sp / C = [η] + k ′ [η] ² C ... [η]: Ultimate (intrinsic) viscosity C: Concentration of sample solution (g / 100 ml) k ′: Huggins constant (k ′ = 0.45) [η] = K _{mm V} ^α … Km: 1.23 × 10 ^-4 α: 0.83 Reference Examples 1-3 Sodium hydroxide 220 g was dissolved in water 2.65 l and kept at 20 ° C, 2,2-bis (4-hydroxyphenyl) propane (= BPA) 456 g, hydrosal Dissolve 0.5 g of fight.

To this, 1.5 l of methylene chloride was added, and phosgene was blown thereinto with stirring. After 30 minutes, 1250 g of methylene chloride containing 19.5 g of P-isopropenylphenol was added, and phosgene was further blown in in minutes.

After the completion of blowing phosgene, the reaction solution was emulsified by vigorous stirring. After emulsification, 30 ml of a 1% triethylamine methylene chloride solution was added, and stirring was continued for about 1 hour for polymerization.

The polymerization liquid was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphorus 3, and then repeatedly washed with water several times, and then dropped into methanol to precipitate the copolymer, which was filtered and dried. A white powder was obtained.

The viscosity-average molecular weight of the powder obtained by measuring the viscosity of a methylene chloride solution was 16,000.

Similarly, terminally unsaturated polycarbonates having viscosity average molecular weights of 9,800 and 25,100 were obtained in the same manner, except that the amount of the terminal stopper used was changed.

In the following, these are listed in order of decreasing viscosity average molecular weight, PC
Called 1, PC2, PC3.

Reference Examples 4 and 5 In Reference Example 1, instead of P-isopropenylphenol, acrylic acid chloride, an equimolar mixture of P-isopropenylphenol and P-tert-butylphenol was used, and the viscosity average in accordance with Reference Example 1 was used. Molecular weight 24,000, 15,5
A terminal unsaturated polycarbonate of 00 was obtained (hereinafter referred to as
Called PC4, PC5).

Example 1 25 g of PC1 synthesized in Reference Example 1, polystyrene (manufactured by Mitsubishi Monsanto Kasei Co., Ltd., trade name; GP polystyrene HH102) 25
g, dicumyl peroxide 0.24 g under a nitrogen stream at 240 ° C, 5
The mixture was kneaded with a Labo Plastomill for 13 minutes while stirring at 0 rpm.

Using this kneaded product, a flow value (hereinafter referred to as Q value, unit: 10 ^-2 ml / s) at 260 ° C was measured by a Shimadzu flow tester, CFT-500, with a load of 100 kg, a nozzle of 1 mmφ and 10 mmL. .

Also, hydraulic molding machine TT-2 manufactured by Toho International Co., Ltd.
Give 3mm thick molded article 004A, after standing 24 hours, the total light transmittance (hereinafter referred to as 1 _D), were measured Kumoka. The birefringence of the molded product was measured for reference. The method is to manufacture a 3 mm thick molded product using a vertical compact molding machine SAV-30-30 manufactured by Yamashiro Seiki, and after 48 hours, use a polarizing microscope (Nippon Optical Co., Ltd.).
Manufactured by OPTIPHOT), and expressed as a percentage with respect to the absolute value of H-4000 (gate entrance, average 53 nm of 4,6,8 cm from the gate entrance) obtained in the same manner. The results are shown in Table 1.

Examples 2 to 11 and Comparative Examples 1 and 2, except that the kind of the polycarbonate resin used and other conditions are changed as shown in Table 1, a kneaded product is prepared, a molded article is manufactured and The results of the measurement are shown in Table 1.

For comparison, P-tert-butylphenol-terminated BPA polycarbonate resin (Mitsubishi Gas Chemical Co., Ltd., trade name; Iupilon H-4000, viscosity average molecular weight 15,000, PCO
The same applies to a single product (Comparative Example 1) and a kneaded product (Comparative Example 2) in which 25 g of this H-4000 and 25 g of polystyrene (HH102) were kneaded with a Labo Plastomill for 5 minutes under stirring at 250 ° C. and 50 rpm. The results are also shown in Table 1.

Example 12 Polycarbonate and styrene copolymer obtained by bulk polymerization of PC2 and styrene (PC: PS = 6: 4, hereinafter referred to as PC6) 25 g and PC2 25 g under nitrogen stream at 240 ° C., 50 rpm The mixture was kneaded with a Lapoplast mill for 5 minutes with stirring. The test results of this kneaded product are also shown in Table 1.

In addition, the description in Table 1 is as follows.

* 1 Initiator PO-1: Dicumyl peroxide. PO-2: t-butyl hydroperoxide. * 2 Other additives AA1: Mn = 860 styrene oligomer. AA2: Antioxidant (Irganox B-2
20) [Operations and Effects of the Invention] The composition of the present invention provides a composition having significantly improved optical properties as compared with a melt mixture of a polycarbonate resin having no unsaturated terminal group and a styrene-based polymer. It is presumed that this is because the compatibility was drastically improved by melt-mixing the unsaturated terminal group of the polycarbonate resin and the styrene-based polymer to generate a component grafted with both. Further, it can be seen that a molded product having excellent fluidity and the like and having reduced birefringence can be obtained. Therefore,
The composition of the present invention is suitably used for producing precision molded products such as optical disk substrates and optical lens materials.

Claims (3)

[Claims] 1. A styrene characterized in that an aromatic polycarbonate resin having an average of at least one unsaturated terminal group per molecule and a styrenic polymer are mixed with a free radical initiator, if necessary, and heated and mixed. A polycarbonate resin composition containing a graft product of a base polymer and an aromatic polycarbonate resin. 2. The polycarbonate resin composition according to claim 1, wherein the free radical initiator to be blended as required is an organic peroxide. 3. The polycarbonate resin composition according to claim 1 or 2, wherein the blending ratio of the aromatic polycarbonate resin and the styrenic polymer is 95: 5 to 5:95.