JPH0621227B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION a. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition having a good balance of molding processability and impact resistance, and more specifically, a combination of a plurality of polycarbonates having different intrinsic viscosities and an aromatic vinyl compound resin. The present invention relates to a polycarbonate resin composition having a good balance of molding processability and impact resistance.

b. 2. Description of the Related Art In recent years, resin molded products such as polycarbonate / aromatic vinyl compound-based resin compositions are becoming more complicated and larger in size as their applications are diversified. There has been a demand for high-performance resin materials having excellent molding processability while maintaining high impact resistance.

c. DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention In the conventional polycarbonate / aromatic vinyl compound-based resin composition, when the impact resistance is attempted to be improved, the moldability is deteriorated, and when it is attempted to improve the moldability. There is a drawback that the impact resistance is deteriorated, and it cannot be used as a highly functional resin material. Therefore, it has been desired to provide a high-performance polycarbonate / aromatic vinyl compound-based resin composition having such excellent impact resistance and excellent moldability.

d. Means for Solving the Problems Therefore, as a result of intensive studies by the present inventors, the aromatic vinyl compound-based resin was blended in a specific ratio to a mixture of polycarbonates having different intrinsic viscosities to obtain excellent resistance to the above-mentioned purpose. The inventors have found that a high-performance polycarbonate / resin composition having both impact properties and excellent moldability can be obtained, and the present invention has been accomplished.

That is, the present invention relates to (A) a polycarbonate mixture comprising 60 to 99% by weight of a polycarbonate having an intrinsic viscosity of less than 0.5 (component a) and 40 to 1% by weight of a polycarbonate having an intrinsic viscosity of 0.5 or more (component b) of 10 to 90% by weight. , And (B) a rubbery polymer component and a resinous component obtained by polymerizing an aromatic vinyl compound, a vinyl cyanide compound and, if necessary, another vinyl monomer copolymerizable therewith. Aromatic vinyl compound resin consisting of 90 to 10% by weight, and (A) component and
The content of the rubbery polymer component in the total amount of the component (B) is 5 to 4
The present invention provides a polycarbonate resin composition characterized by being 0% by weight.

e. DETAILED DESCRIPTION OF THE INVENTION Polycarbonate Mixture Component Examples of the polycarbonate used as a constituent component of the polycarbonate resin composition of the present invention include aromatic polycarbonate, aliphatic polycarbonate, and aliphatic-aromatic polycarbonate. Generally 2,2-
Polymers or copolymers obtained by polymerizing bis (4-oxyphenyl) alkane-based, bis (4-oxyphenyl) ether-based, bis (4-oxyphenyl) sulfone sulfide or sulfoxide-based bisphenols And is a polymer using bisphenols substituted with halogen according to the purpose. For the types and manufacturing methods of polycarbonate, see the Nikkan Kogyo Shimbun (Showa
Those described in detail in "Polycarbonate resin" issued on September 30, 44) can be used.

As the polycarbonate used in the polycarbonate mixture component of the present invention, a polycarbonate having an intrinsic viscosity of less than 0.5 (component a) and a polycarbonate having an intrinsic viscosity of 0.5 or more (component b) are mixed with at least two types of polycarbonate having different intrinsic viscosities. It is important to use.

The amount of the above two types of polycarbonate blended in the polycarbonate resin composition of the present invention is such that the intrinsic viscosity is less than 0.5, preferably 0.45 or less of polycarbonate of 60 to 99.
In a polycarbonate resin composition, a polycarbonate mixture comprising 40% to 1% by weight, and preferably 30% to 5% by weight of a polycarbonate having an intrinsic viscosity of 0.5 or more, preferably 0.55 or more, is used. It is important to contain 10 to 90% by weight, preferably 30 to 70% by weight. Therefore, if a polycarbonate having an intrinsic viscosity of less than 0.5 is used in an amount of 60% by weight or less, the molding process will be deteriorated, and if it is used in an amount of more than 99% by weight, the impact property will be deteriorated. Further, if the content of the polycarbonate mixture in the polycarbonate resin composition is less than 10% by weight, the impact resistance will be poor, and if it exceeds 90% by weight, the moldability will be poor.

Polycarbonates having different intrinsic viscosities as described above are mixed in advance by using a mixing device or the like described below before the aromatic vinyl compound resin components described below are mixed, but those produced so that both components are included in the polycarbonate production process. It may be.

Aromatic Vinyl Compound Resin Component As the aromatic vinyl compound resin component used in the polycarbonate resin composition of the present invention, a rubbery polymer component and an aromatic vinyl compound, a vinyl cyanide compound, and optionally a copolymerizable with them An aromatic vinyl compound resin comprising a vinyl-based resinous component obtained by polymerizing another vinyl monomer.

Examples of the rubbery polymer component used in the aromatic vinyl compound resin component include ethylene and α such as ethylene-propylene random copolymers and block copolymers, ethylene-butene random copolymers and block copolymers. -Copolymer with olefin; Copolymer of ethylene and unsaturated carboxylic acid ester such as ethylene-methacrylate copolymer and ethylene-butyl acrylate copolymer; Ethylene and fatty acid vinyl such as ethylene-vinyl acetate copolymer Copolymer with ethylene; propylene-ethylidene norbornene copolymer, ethylene-propylene-
Ethylene-propylene-non-conjugated diene terpolymers such as hexadiene copolymers; polybutadiene, styrene-
Diene rubbers such as random copolymers and block copolymers of butadiene, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers; butylene-isoprene copolymers, etc.
A combination of two or more species can also be used.

Among these, ethylene-propylene-copolymer, as a rubbery polymer preferably used in terms of impact resistance,
Ethylene-propylene-non-conjugated diene terpolymer and diene rubber. Diene rubbers such as polybutadiene and styrene-butadiene copolymer are more preferable, and styrene-butadiene copolymer having a styrene content of 50% by weight or less is particularly preferable.

As the aromatic vinyl compound used for the aromatic vinyl compound resin component, styrene, α-methylstyrene,
Vinyl xylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, p-tert-
Butyl styrene, ethyl styrene, vinyl naphthalene,
O-methyl styrene, p-methyl styrene, dimethyl styrene, etc., and when two or more aromatic vinyl compounds are used in combination, it is preferable to use styrene in a proportion of 50% by weight or more.

The vinyl cyanide compound used as the aromatic vinyl compound resin component is acrylonitrile, methacrylonitrile, or the like, and preferably acrylonitrile.

Other vinyl monomers copolymerizable with the aromatic vinyl compound and the vinyl cyanide compound include methyl acrylate, ethyl acrylate, propyl acrylate,
Butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate and other acrylic acid alkyl esters, phenyl acrylate, benzyl acrylate, methyl methacrylate and other acrylic acid aryl esters, ethyl Methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, and other methacrylic acid alkyl esters, phenyl methacrylate, benzyl methacrylate, and other methacrylates. Examples thereof include unsaturated acids such as acid aryl ester anhydride, nurenic acid, itaconic anhydride, and citraconic anhydride. These may be used alone or in combination of two or more.

The other vinyl monomer capable of copolymerization is preferably 50% by weight or less in the vinyl-based resin component, more preferably
It is used in a proportion of 30% by weight or less.

The content of the rubbery polymer component in the aromatic vinyl compound resin is 80% by weight or less, preferably 5 to 70% by weight. Further, the content of each component in the vinyl resin component is 60 to 90% by weight of an aromatic vinyl compound, 10 to 0% by weight of a vinyl cyanide compound, and 50% by weight or less of another copolymerizable vinyl compound. preferable.

An example of a preferable production method using a rubbery polymer is an aromatic vinyl compound in the presence of 5 to 70 parts by weight of a rubbery polymer.
Obtained by graft polymerization of 95 to 30 parts by weight of a monomer consisting of 60 to 90% by weight, 10 to 40% by weight of a vinyl cyanide compound and 50% by weight or less of another vinyl compound capable of copolymerization (total 100 parts by weight). Or a graft copolymer obtained by the polymerization method and a vinyl compound copolymer produced by separately copolymerizing the vinyl compound used in the polymerization method. It is a thing.

The aromatic vinyl compound resin component thus produced is mixed in the polycarbonate resin composition in an amount of 90 to 10% by weight, preferably 70 to 30% by weight. If the content is less than 10% by weight, the moldability will be poor, and if it exceeds 90% by weight, the impact resistance will be reduced.

The aromatic vinyl compound resin component contains a total free polymer soluble in methyl ethyl ketone (hereinafter sometimes simply abbreviated as MEK), and the total free polymer of the MEK soluble component is extremely limited. Aromatic vinyl compound copolymer having a viscosity of 0.55 or less, preferably 0.5 or less is 60 to 100% by weight, preferably 6
0 to 99% by weight, more preferably 65 to 99% by weight, and an aromatic vinyl compound copolymer having an intrinsic viscosity of 0.6 or more 40 to 0% by weight, preferably 40 to 1% by weight, more preferably 35 to 1% by weight. And a mixture of 5 to 90% by weight of the aromatic vinyl compound resin component. If the content of the mixture is less than 5% by weight, moldability is deteriorated, and if it exceeds 90% by weight, impact resistance is deteriorated, which is not preferable. Also, the intrinsic viscosity is 0.55
If the amount of the aromatic vinyl compound copolymer is less than 60% by weight, the moldability is deteriorated, which is not preferable.

The target intrinsic viscosity of the mixture is adjusted by polymerizing a copolymer of an aromatic vinyl compound and a vinyl cyanide compound or by using a monomer such as an aromatic vinyl compound and a vinyl cyanide compound as a rubbery polymer component. When performing graft copolymerization,
This can be achieved by adjusting the method of adding the monomer and the amount of the molecular weight modifier used.

Further, it is preferable that the total free mixture, which is the MEK soluble product, contains 10 to 40% by weight of a vinyl cyanide compound.

Production of Polycarbonate Resin Composition The polycarbonate resin composition of the present invention is produced by mixing the above-mentioned polycarbonate mixture component aromatic vinyl compound resin component, and the specific method thereof includes the following methods.

A method of producing by dissolving and swelling each component in an organic solvent and then mixing them.

A method for producing a pelletized polycarbonate resin composition by mixing respective components with a mixer or the like and then melt-mixing with an extruder.

A method for producing a pelletized polycarbonate resin composition by melt-mixing a powder mixture recovered by using a non-solvent in the above method using an extruder.

The pellets or powders produced by any of the above-described methods 1 to 3 are used alone or in a mixture thereof, or after the above components are added to the pellets or a powder and mixed, the mixture is molded using an injection molding machine, and a polycarbonate resin. A method for producing a molded article of the composition.

As the mixer used in the above method, known mixing equipment such as Banbury and kneader can be used.

The amount of rubber in the composition of the present invention is preferably 5 to 40% by weight,
It is more preferably 6 to 35% by weight.

If it is less than 5% by weight, impact resistance is low, and if it is 40% by weight or more, moldability becomes poor.

In the polycarbonate resin composition of the present invention, other thermoplastic resin, polyphenylene ether, polyamide, acrylic resin, other polymers and the like are added and mixed,
It is also possible to obtain a polycarbonate resin composition by melt mixing with an extruder.

The polycarbonate resin composition of the present invention can be molded into various molded articles by injection molding, sheet extrusion, vacuum molding, profile molding, foam molding or the like.

Further, when the polycarbonate resin composition of the present invention is used, it is necessary to add known additives such as known antioxidants, ultraviolet absorbers, lubricants, flame retardants, antistatic agents, foaming agents, glass fibers, etc. You can

The polycarbonate resin composition of the present invention is highly practical because it has excellent molding processability and excellent impact resistance in a well-balanced manner, and is suitable for automobile parts, electrical products, household products, various industrial products, etc. Can be used.

f. EXAMPLES Next, the present invention will be specifically described with reference to production examples and examples, but these are merely examples and do not limit the content of the present invention. In the following examples and comparative examples, parts and% represent parts by weight and% by weight, respectively.

Examples 1 to 7 and Comparative Examples 1 to 9 Production of Polycarbonate Mixture Component (A) In order to produce the polycarbonate mixture components shown in Table-1, as a polycarbonate having an intrinsic viscosity of less than 0.5, the trade name BAYER MAKROLON of West Germany Bayer Co. : 0.44) and Mitsubishi Kasei Kogyo Co., Ltd. product name FN2200 (Intrinsic viscosity 0.4
9) and used as a polycarbonate with an intrinsic viscosity of 0.5 or more under the trade name FN3000 (Limited viscosity of Mitsubishi Kasei Kogyo Co., Ltd.)
0.59) was mixed with a Banbury mixer at a temperature of 280 ° C. for 10 minutes to produce a polycarbonate mixture component.

Production of Aromatic Vinyl Compound Resin Component (B) The aromatic vinyl compound resin shown in Table 1 was produced according to the following method.

(1) Production of AS resin A reactor was charged with 1.0 part of potassium oleate and 180 parts of water,
After purging with nitrogen, the temperature was raised to 60 ° C. After raising the temperature, sodium formaldehyde sulfoxylate 0.045 parts, ferrous sulfate 0.0
06 parts, 0.07 parts of ethylenediaminetetraacetic acid sodium salt were added, and further diisopropylbenzene hydroperoxide was added.
After adding 0.1 parts, styrene 68.5 parts, acrylonitrile 3
A mixture of 1.5 parts and an appropriate amount of t-dodecyl mercaptan was continuously added dropwise.

The dropping time was 2 hours, and the temperature was kept at 65 ° C during that period. After completion of dropping the monomer, the mixture was further stirred for 1 hour. The latex obtained is coagulated in a dilute aqueous solution of sulfuric acid, filtered, washed with water and dried, then 40 mmφ
AS resin was obtained by pelletizing with an extruder.

In addition, by using the amounts of styrene and acrylonitrile monomers shown in Table-1, another 2
A kind of AS resin was obtained.

(2) Manufacture of ABS resin (I) Polybutadiene latex A (solid content) 52 (part) Styrene 10.8 Acrylonitrile 65.1 t-Dodecyl mercaptan Appropriate amount Potassium rosinate 0.25 Potassium hydroxide 0.005 Ion-exchanged water 100 Jacket the above mixture (I) Then, after charging the reactor with a stirrer and replacing the internal air with nitrogen, while controlling the jacket to 70 ° C, the internal temperature was raised to 50 ° C and 0.3 parts of sodium pyrophosphate dissolved in 10 parts of water, dext Rose 0.35 part, ferrous sulfate 0.01 part and cumene hydroperoxide 0.1 part were added and reacted.

After 1 hour from the start of the reaction, the mixture of the following (II) was continuously added over 5 hours, and the mixture was further stirred at 1
The reaction continued for an hour. The polymerization was almost complete.

(II) Styrene 21.8 (parts) Acrylonitrile 10.3 Appropriate amount of t-dodecyl mercaptan Potassium rosinate 1.0 Potassium hydroxide 0.02 Cumene hydroperoxide 0.15 Ion-exchanged water 50 The graft polymer latex obtained has 2,6- After adding 1.0 part of di-tert-butylparacresol, sulfuric acid (2 parts to 100 parts of polymer) was added and coagulated. This is separated, washed with water, dehydrated, dried and then ABS
A resin was obtained.

Further, using the rubbery polymer and the monomer components shown in Table-1, another two kinds of ABS resins were obtained by the same method as the above method.

Production of Polycarbonate Resin Composition The polycarbonate mixture component and the aromatic vinyl compound resin component were mixed according to the composition ratios shown in Tables 1 and 2, and extruded at a temperature of 250 ° C. using an extruder to pelletize. Then, after sufficiently drying the pellets, a test piece was molded at a temperature of 250 ° C. using an injection molding machine. Tables 1 and 2 show the results of measuring the impact resistance and molding processability of these materials by the following method.

(1) Impact resistance It was measured according to ASTM D256 using a test piece with a 1/4 ″ notch in thickness.

(2) Molding processability (melt flow rate) Measured at 240 ° C and 10 kg according to JIS K7210.

(3) Intrinsic Viscosity [η] For a polycarbonate, methylene chloride was used as a solvent at 20 ° C., and for a styrene-based resin, methyl ethyl ketone was used as a solvent at 30 ° C. using a Webrohde viscometer.

As a result, it can be understood from the comparative example in Table 2 that:

Comparative Examples 1, 2, 4 and 7 (when only a polycarbonate resin having an intrinsic viscosity of less than 0.5 was used) were prepared as Examples-
Impact strength is worse than 1, 2, 4 and 7.

Comparative Example 3 (when only a polycarbonate resin having an intrinsic viscosity of 0.5 or more was used) had poor moldability. Comparative Examples 5 and 6 (40% polycarbonate resin having an intrinsic viscosity of 0.5 or more was added to the polycarbonate resin in the polycarbonate resin component).
If it is used in an amount of more than 1% by weight, the moldability is poor. Comparative Example 8 (90% by weight of the polycarbonate resin component in the composition
If it is used in an amount exceeding 1), the moldability is poor. Comparative Example 9 (when the polycarbonate resin component is used in the composition in a small amount of less than 10% by weight) has poor impact resistance.

f. EFFECTS OF THE INVENTION As is clear from the above examples and the like, the polycarbonate resin composition of the present invention is a well-balanced product having excellent molding processability and excellent impact resistance, which are improvements in the origin of the conventional polycarbonate resin composition. It is also a molding material, is an excellent composition having practical properties, and its industrial value is extremely large.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display area C08L 69:00) (56) References JP-A-51-128352 (JP, A) JP-A-60 -13844 (JP, A) JP 56-45945 (JP, A) JP 54-14463 (JP, A) JP 60-23444 (JP, A) JP 61-123660 (JP, A) )

Claims (3)

[Claims] 1. A polycarbonate having an intrinsic viscosity of less than 0.5.
10 to 90% by weight of a polycarbonate mixture comprising 60 to 99% by weight (a component) and 40 to 1% by weight of a polycarbonate having an intrinsic viscosity of 0.5 or more (component b), and (B) a rubbery polymer component and an aromatic vinyl. Aromatic vinyl compound resin consisting of a compound, a vinyl cyanide compound and a resinous component obtained by polymerizing another vinyl monomer copolymerizable with them, if necessary, consisting of 90 to 10% by weight, A polycarbonate resin composition, wherein the content of the rubbery polymer component in the total amount of the component (A) and the component (B) is 5 to 40% by weight. 2. The polycarbonate resin composition according to claim 1, wherein the polycarbonate used as the component a has an intrinsic viscosity of 0.49 or less. 3. The component soluble in methyl ethyl ketone contained in the component (B) is 60 to 100 wt% of an aromatic vinyl compound copolymer having an intrinsic viscosity of 0.55 or less and an aromatic vinyl compound copolymer having an intrinsic viscosity of 0.6 or more. Claims 1 or 2 characterized in that it is composed of a mixture with 40 to 0% by weight of the combined product, and the mixture contains 5 to 90% by weight in the component (B). The polycarbonate resin composition described.