JP2586025B2 - Graft polycarbonate resin composition. - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method in which an aromatic polycarbonate resin having at least one unsaturated end group per one molecule and a styrene-based monomer are formed into a bulk in the presence of a molecular weight regulator. It is intended to obtain a composition having excellent compatibility including both grafts obtained by polymerization, and excellent transparency, fluidity, and simple operation.
And a composition having reduced optical distortion, and can be suitably used for optical disks, optical lenses, and the like.

[Conventional method and its problems]

Conventionally, as a material for an optical transparent molded product, an acrylic resin has been known as a material for an optical transparent molded product due to its characteristics of transparency, fluidity, and low birefringence (Japanese Patent Application Laid-Open No.
−131654 and others). However, acrylic resin has heat resistance of about 70
° C, low impact resistance, and easy occurrence of warpage due to moisture.

To eliminate the above disadvantages, the viscosity average molecular weight is 15,000-1
The use of 8,000 polycarbonate resins as molding materials for disks, lenses, etc. is being studied (Japanese Patent Application Laid-Open No. 58-180553), but the fluidity is still insufficient and the emphasis on birefringence is large. And its use is limited.

For the above reasons, methods for maintaining the excellent characteristics of the aromatic polycarbonate resin and eliminating optical distortion have been studied.

From the viewpoint of improvement in fluidity, a composition comprising an aromatic polycarbonate resin and a vinyl aromatic polymer is well known, but there are difficulties in compatibility, and various methods for improving the compatibility have been studied. Method for copolymerizing with dihydric phenols (J. Polymer Sci. Pt. A-1, vol. 7, 13
39-1347 (1969)), a method of polymerizing a dihydric phenol in the presence of a phenolic hydroxyl group-containing modified polystyrene, a method of solution-polymerizing a modified polycarbonate resin and a styrene monomer (Japanese Patent Publication No. 48-25076, JP-A-55-50009).

These methods are excellent, but the use of solvents such as methylene chloride and chlorobenzene is essential, and the separation of unreacted styrene and dihydric phenol from the solvent and their recycle are necessary. However, in the case of the method disclosed in JP-A-55-50009, the reaction between the raw material polycarbonate and the styrene-based monomer is problematic in that the solvent used is highly likely to be mixed into the product. When the concentration in the system is 30% by weight or more, there is a disadvantage that physical properties such as transparency of the obtained resin are deteriorated.

[Means for solving the problem]

The present inventors have intensively studied a method for improving the above-mentioned disadvantages, and found a method of performing bulk polymerization of an aromatic polycarbonate resin having an unsaturated terminal group and a styrene-based monomer in the presence of a molecular weight regulator, The present invention has been completed.

That is, the present invention relates to a styrene-based polymer characterized by being formed by bulk polymerization of an aromatic polycarbonate resin having at least one unsaturated terminal group per average molecule and a styrene-based monomer in the presence of a molecular weight regulator. It is a graft polycarbonate resin composition containing a graft with an aromatic polycarbonate resin.

 Hereinafter, the configuration of the present invention will be described.

The process for preparing aromatic polycarbonates having at least one unsaturated end group per average molecule of the present invention comprises the use of a monofunctional compound having an unsaturated double bond as a molecular weight regulator or a terminator, Other than using in combination with a terminal stopper, the same manufacturing method as the conventional aromatic polycarbonate resin, an interfacial polymerization method, a pyridine method, is manufactured by a solution method such as a chloroformate method, the viscosity average molecular weight 2,000 ~ 100,000, preferably 5,000-50,000, especially
6,000 to 30,000.

Preferred examples of the dihydric phenol compound used in the production of the polycarbonate resin unit of the present invention include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether and 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-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-
Hydroxyphenyl) -1-phenylethane, bis (4
-Hydroxyphenyl) diphenylmethane is exemplified.

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

The polycarbonate resin of the present invention is produced by essentially including the above-mentioned components. The branching agent is used in an amount of 0.01 to 3 mol%, especially 0.1 to 3 mol% based on the above-mentioned dihydric phenol compound.
A branched polycarbonate can be used in combination within the range of from about 1.0 mol%. Such branching agents 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 (4-hydroxyphenyl) benzol, 1,1,1
-Tri (4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphphenol, α, α ′, α ″ -tri (4-hydroxyphenyl) -1, Polyhydroxy compounds exemplified by 3,5-triisopropylbenzene and the like, and 3,3-bis (4
-Hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin, 5,7-dichlorisatin, 5-bromoisatin and the like.

The styrene monomer of the present invention specifically includes styrene, O-methylstyrene, P-methylstyrene, α-methylstyrene, O-butylstyrene, P-butylstyrene, chlorostyrene, bromostyrene, and 2,4- And dimethylstyrene.

The amount ratio of the aromatic polycarbonate resin having a terminal unsaturated group to the styrene monomer is not particularly limited, but usually, the weight ratio of the aromatic polycarbonate resin: styrene monomer = 5: 95 to 70 : 30, preferably 10:90 to 65:35, more preferably 15:85 to 69:40.

In the present invention, other vinyl monomers, such as methyl methacrylate, ethyl methacrylate, butyl acrylate,
Acrylates such as n-hexyl acrylate and cyclohexyl methacrylate; cricidyl methacrylate, acrylic acid, acrylamide, methacrylamide, N-methoxymethacrylamide, acrylonitrile, methacrylonitrile, maleic anhydride, maleimide and the like may be used in combination. it can.

Next, the molecular weight modifier of the present invention is used to obtain a desired molecular weight at the time of bulk polymerization of the unsaturated terminal group-containing aromatic polycarbonate and the styrene-based monomer described above, It has a molecular weight and has an extremely small amount of by-product gel. Suitable molecular weight regulators include organic sulfur compounds, which are aliphatic or aromatic compounds having 1 to 30 carbon atoms, specifically n-butyl mercaptan, imebutyl mercaptan, n-octyl mercaptan, Primary, secondary and tertiary mercaptans such as n-dodecyl mercaptan, sec-butyl mercaptan, sec-dodecyl mercaptan, tert-butyl mercaptan; aromatic mercaptans such as phenyl mercaptan, thiocresol, 4-tert-butylthiocresol; Thioglycolic acid and esters thereof; mercaptans having 3 to 18 carbon atoms such as ethylenethioglycol; and among these compounds, n-butyl mercaptan, tert-butyl mercaptan and n-octyl mercaptan are most preferable; The amount used depends on the terminal unsaturated group used. In the range of 0.0001 to 5% by weight, preferably 0.0004 to 1% by weight of the total amount of the aromatic polycarbonate resin having styrene monomer and the styrene-based monomer. It is not preferable because by-products and the like occur and the molding processability and the like of the obtained resin composition are deteriorated. When used in excess of 5% by weight, the degree of polymerization is reduced, and the mechanical properties and the like are reduced. It is not preferable.

According to the conditions of the bulk polymerization of the present invention, by-products of the gelled product are extremely small by the above-mentioned molecular weight regulator, but by using a small amount of a ketone as an auxiliary agent, the gelled product is substantially reduced. It is preferable to use ketones in combination, since it is possible to completely prevent the by-products. Examples of such ketones include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and the like, and the amount of the ketones used is an aromatic polycarbonate resin having a terminal unsaturated group to be used and a styrene monomer. In the range of 0.001 to 30% by weight, preferably 0.004 to 20% by weight of the total amount of
If the amount is less than 30% by weight, the effect of suppressing the by-product of the gelled product is insufficient, and the obtained resin composition may become cloudy. Is not improved because the load for recovering ketones is only increased.

Using the components described above, the polymerization conditions for bulk polymerization are conditions under which the raw materials used can maintain a molten or plasticized state, and the temperature is 40 to 250 ° C, preferably 60 to 180 ° C, particularly
A temperature of 70 to 150 ° C. within 10 hours, preferably 0.5 to 6 hours is suitable.

A polymerization initiator can be used in the bulk polymerization described above. Examples of such a polymerization initiator include, for example, di-tert.
-Butyl peroxide, dinolyl peroxide, methyl ethyl ketone peroxide, di-tert-butyl diperphthalate, lauroyl peroxide, di-tert
-Amyl peroxide, dicumyl peroxide, tert
Organic peroxides such as -butyl mill peroxide and benzoyl peroxide; 2,2-azobisisobutyronitrile, 1,1-azobiscyclohexanecarbonitrile,
And azo compounds such as -cyano-2-propylazoformamide.
It is in the range of 1% by weight.

Further, in the above-mentioned bulk polymerization, a stabilizer can be used for the purpose of preventing decomposition or yellowing due to heat or oxidation during the reaction. As such a stabilizer, butylated hydroxytoluene (BHT), 4-hydroxymethyl-2,6-di-tert-butylphenol, 2,6-di-tert-butyl-
4-ethylphenol, butylated hydroxyanisole and the like can be mentioned, and the amount of use is generally 0.01 to 0.1.
It is in the range of 5% by weight.

The polymer obtained by bulk polymerization by the above method contains unreacted styrenic monomers and ketones, and these are conventionally known devolatilization methods, usually 280 ° C. or lower, preferably 2 ° C. or less.
It is treated under a reduced pressure of 5 to 500 mmHg abs. At a temperature of 60 ° C. or less to obtain a polycarbonate resin composition of the present invention. The polycarbonate resin composition of the present invention produced by the above method,
It is composed of a graft polycarbonate resin grafted with a styrene-based monomer and a styrene-based resin.These further comprise a so-called “IPN” of a polymer network in which the constituent units of the styrene-based resin and the constituent units of the aromatic polycarbonate have mutually entered. It is inclusive.

According to the method of the present invention, the polycarbonate resin composition can be obtained by a simple process of bulk polymerization-purification-devolatilization treatment, so that it is easy to prevent and control the entry of fine dust into polycarbonate. When the polycarbonate resin composition of the present invention is used for optical applications, etc., if necessary, it is possible to purify and use the raw materials prior to the reaction, and to remove fine ducts from the produced polymer. To
A suitable solvent may be used, and a means such as microfiltration or centrifugation may be used.

Although the polycarbonate composition of the present invention is as described above, if necessary, other resins, antioxidants, light stabilizers, coloring agents, inorganic or organic fillers, carbon fibers,
A reinforcing agent such as glass fiber, a lubricant, an antistatic agent, and the like may be appropriately used in combination.

〔Example〕

 Hereinafter, specific examples will be described.

The viscosity average molecular weight in Examples and the like is determined by the following method.

(1), Measurement of solution viscosity Sample solution: methylene chloride solution with a concentration of g / 100 ml Viscometer: Improved Ubbelohde viscometer using methylene chloride alone with a flow time of 72.36 seconds. Measurement temperature: 20 ° C ± 0.01 ° C. By this measurement, the flow time at a concentration of 0.6 g / 100 ml is measured, and η _reL is determined.

(2), wherein the calculation above measured eta _REL, more calculates the [eta], obtaining the M _v from (equation Schnell).

η _SP = T / T _O −1, η _reL = T / T _O ... η _SP : Specific viscosity. T: Flow time of the sample solution. To: Flow time of solvent only. η _SP / C = [η] + k ′ [η] ² C [η]: Ultimate (intrinsic) viscosity C: Sample solution concentration (g / 100 ml) k ′: Huggins constant (k ′ = 0.45) _{) [η] = K m M} v ...... Km: 1.23 × 10 -4 α: 0.83 reference example 1-3 sodium hydroxide 220g was dissolved in water 2.65, while maintaining the 20 ° C., 2,2-bis (4 -Hydroxyphenyl) propane (= BPA) (456 g) and hydrosulfite (0.5 g) were dissolved.

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

After phosgene blowing was completed, the reaction solution was vigorously stirred to emulsify the reaction solution. After emulsification, 30 ml of a 1% triethylamine in methylene chloride solution was added, and stirring was continued for about 1 hour to carry out polymerization.

The polymer solution was separated into an aqueous phase and an organic phase, and after neutralizing the organic phase with phosphoric acid, repeating washing with water several times, then dropping into methanol to precipitate a copolymer, followed by filtration and drying, and drying was performed in white. A powder was obtained.

The viscosity average molecular weight of the methylene chloride solution of this powder measured from viscosity was 16,000.

Similarly, a terminal unsaturated polycarbonate having a viscosity average molecular weight of 9,800 and 25,100 was obtained in the same manner except that the amount of the terminal stopper used was changed.

Hereinafter, in order from those having a lower viscosity average molecular weight,
Call them PC1, PC2 and PC3.

Reference Examples 4 and 5 In Reference Example 1, acrylic acid chloride and the same molar mixture of P-isopropenyl phenol and P-tert-butylphenol were used instead of P-isopropenyl phenol, respectively. Average molecular weight 2
4,000 and 15,500 terminally unsaturated polycarbonates were obtained (hereinafter referred to as PC4 and PC5).

Example 1 25 g of PC1 synthesized in Reference Example 1, 100 g of styrene monomer (hereinafter, referred to as St), methyl ethyl ketone (hereinafter, MEK)
7.9 g was placed in a pressure-resistant glass container, and after purging with nitrogen, the temperature was raised to 120 ° C. with stirring, and 25 g of a styrene monomer solution containing 0.47 g of n-dodecyl mercaptan (hereinafter referred to as NDS) was added. While reacting for 2 hours.

After completion of the reaction, the mixture was cooled and the product was added to methanol and precipitated to obtain 41 g of a 6: 4 PC: PS polymer.

Using this polymer, a flow tester manufactured by Shimadzu, CFT-5
According to 00, the flow value (hereinafter referred to as Q value, unit: 10 ⁻² ml / s) at 260 ° C. was measured with a load of 100 kg, a nozzle of 1 mmφ and 10 mmL.

Hydraulic molding machine TT made by Toho International Co., Ltd.
A molded product having a thickness of 2.5 mm was obtained at -2004A, and after standing for 24 hours, the total light transmittance (hereinafter referred to as _ID ) and the haze value were measured. In addition, the birefringence of the molded article was measured for reference. The method is as follows: a 3 mm thick molded product is manufactured using a vertical compact molding machine SAV-30-30 manufactured by Yamashiro Seiki, and after 48 hours, a polarizing microscope (OPTIPHOT, manufactured by Nippon Kogaku Co., Ltd.) is used. The H-
Absolute value of 4000 (gate entrance, then 4,6,8cm average 53n
m) as a percentage. The results are shown in Table 1.

Examples 2 to 15 and Comparative Examples 1 to 3 According to Example 1, except that the type of polycarbonate resin used and other conditions were changed as shown in Table 1,
Table 1 shows the results of the preparation of the kneaded material, the production of molded articles and the measurement.

In addition, the same results were obtained for the physical properties of P-tert-butylphenol-terminated BPA polycarbonate resin (manufactured by Mitsubishi Gas Chemical Company, Inc., trade name: Iupilon H-400, viscosity average molecular weight 15,000, hereinafter referred to as PCO). The results are shown in Table 1.

 The description in Table 1 is as follows.

* 1 Additives (= molecular weight regulator and polymerization initiator) [Molecular weight regulator] NDS: n-dodecyl mercaptan. NOS: n-octyl mercaptan. -TDS: tert-dodecyl mercaptan. [Polymerization initiator] ABIN: azobisisobutyronitrile. Example 16 30 g of the polymer of PC: PS = 6: 4 obtained in Example 1, 18 g of a polycarbonate resin (H-4000) and polystyrene (produced by Mitsubishi Monsanto Kasei Co., Ltd., trade name: GP polystyrene HH-1)
02) 12 g was kneaded with a Labo Plastomill for 5 minutes in a nitrogen stream at 240 ° C. under stirring at 50 rpm to obtain a uniform composition. This composition was tested in the same manner. As a result, the total light transmittance was 89% and the haze was
1.8%, the Q value was 70.5 × 10 ^-2 ml / s, and the birefringence was 15% with respect to Iupilone H-4000.

[Operation and Effect of the Invention] The composition of the present invention can provide a composition having significantly improved optical properties as compared with a molten mixture of a polycarbonate resin having no unsaturated terminal group and a styrene-based polymer. This is due to the formation of a component obtained by graft polymerization of a styrene monomer to the unsaturated terminal group of the polycarbonate resin.
It is estimated that the compatibility was greatly improved. In addition, it can be seen that a molded article having excellent fluidity and the like and 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.

 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-54-64590 (JP, A) JP-A-52-104553 (JP, A) JP-B-46-14912 (JP, B1)

Claims (8)

(57) [Claims] 1. A styrene-based polymer obtained by subjecting an aromatic polycarbonate resin having at least one unsaturated end group per average molecule to a styrene-based monomer to bulk polymerization in the presence of a molecular weight regulator. A graft polycarbonate resin composition containing a graft with an aromatic polycarbonate resin. 2. The graft polycarbonate resin composition according to claim 1, wherein said molecular weight modifier is an organic sulfur compound. 3. The graft polycarbonate resin composition according to claim 2, wherein said organic sulfur compound is an aliphatic or aromatic compound having 1 to 30 carbon atoms. 4. The graft polycarbonate resin composition according to claim 3, wherein the concentration of the organic sulfur compound is 0.001 to 5% by weight. 5. The graft polycarbonate resin composition according to claim 1, wherein the polymerization is carried out by using a small amount of a ketone as an auxiliary agent. 6. The graft polycarbonate resin composition according to claim 5, wherein said ketone is in the range of 0.1 to 30% by weight based on the total amount of said aromatic polycarbonate resin and said styrenic monomer. 7. The graft polycarbonate resin composition according to claim 1, wherein the weight ratio of said aromatic polycarbonate resin to said styrene monomer is 5:95 to 60:40. 8. The graft polycarbonate resin composition according to claim 1, wherein the aromatic polycarbonate resin has a viscosity average molecular weight in the range of 5,000 to 50,000.