JPH04505628A - Molding compositions comprising a carbonate polymer, a rubber-modified vinyl aromatic nitrile graft copolymer, and a methyl (meth)acrylate-butadiene-styrene graft copolymer, and blow molding and thermoforming methods using such compositions. - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Carbonate polymer and rubber, vinyl fragrance, nitrile graft copolymer and methi Le metaacrylate-butadiene-styrene graft copolymer and 4-1 5 blowing methods and 5 heating methods The present invention provides a thermoplastic resin composition. In particular, carbonate polymers and core/seal graft copolymers rubber-modified vinyl aromatic acrylonitrile graft copolymer. Improved blends in which the rubber is a rubber other than a conjugated diene polymer and how to use this composition Regarding the law.

Particular embodiments of the invention include (1) one or more carbonate polymers; Ren-propylene-nonconjugated diene monomer (EPDM)-vinyl aromatic carbonization on one or more rubbery polymers of EPDM, including hydrogen copolymer rubber, or alkyl alkyl acrylate-vinyl aromatic hydrocarbon copolymer rubber on one or more rubbery polymers of rubber: or on both of these types of rubber. (3) one or more graft copolymers of aromatic nitrile copolymers; and (3) a core. for example butadiene-vinyl aromatic hydrocarbons or butadiene-vinyl aromatics Copolymers, including copolymers such as group hydrocarbon-alkyl acrylate copolymers. A rubbery polymer of rukyl acrylate or butadiene is converted into a vinyl aromatic hydrocarbon. An optional second inner shell phase of the polymer of monomers and an alkyl (meth)acrylate one or more core/shell graft copolymers with a toppolymer outer shell; molding compositions containing blends with

When the graft copolymer of the above component (2) is used with EPDM type polymer rubber, is commonly called AES, or uses alkyl acrylate type polymer rubber. In this case, it is commonly referred to as ASA. Core/shell graft copo of the above component (3) Remer is often called MBS rubber or resin, or butyl acrylate If alkyl acrylate polymer is grafted to the rubber core, butyl acrylate It is called rate core/shell rubber.

Polycarbonate blend compositions can be thermoplastically molded under a wide range of injection molding conditions Although it has been found possible, blow molding requires specific polycarbonate blanks. only suitable. The reason for this is due to the unique requirements of blow molding operations.

As taught in U.S. Patent Nos. 4.652.602 and 4.474.999 Typical blow molding operations, such as The parison can be extruded vertically downward into a mold. Next, the extrusion molded body Heat softened by pressing against the mold surface with a compressed gas stream (usually air or an inert gas) mold the resin.

As will be understood by those skilled in the art, successful molding of foot thermoplastics involves heat softening. It depends on many factors, including the characteristics and physical properties of the resin used. tube length and The diameter and amount of molding material in the tube determine the size of the object that can be molded by this method. is the limiting factor in determining the size and wall thickness. Obtained from polycarbonate blends Poor melt flowability or melt strength and mild extrudate swelling may result in blow molding. Its shape application is limited to relatively small, thin-walled parts. These elements alone, especially For the molding of large products, it is very important in the successful blow molding of resins. .

Resin compositions with good welding strength are linear polycarbonate resin, acrylonitrile Lyle-butadiene-styrene resin (ABS) and rubbery graft copolymer tree I Ii (MBS) can be obtained from a blend of Japanese Patent Publication No. JP58159. 258 (1983). This patent claims that only the ABS phase is modified and the external By using MBS resin containing 30-50% rubber and styrene for the shell. The added rubber helps to drive the MBS resin into the phase, and the added rubber prevents poor solubility of ABS. Helps improve tangential properties.

Furthermore, from U.S. Pat. No. 4,677,162, linear or branched polycarbonate nate resin (PC), acrylonitrile-butadiene-styrene resin (ABS ) and rubbery graft copolymer (MBS) with good impact resistance. It is known to be useful in forming products with high impact resistance and low gloss. but, Both of these references refer to ABS resin (based on butadiene polymer rubber) Use of AES or ASA to produce more environmentally stable resins using only It also suggests that the MBS rubber distribution If (pl acement) is controlled. Using these grafted polymers in carbonate polymer blends to control There is no indication that there is.

The present invention consists of the following components: (A) (i) Random branched carbonate polymer, (ti) linear carbonate polymer, and (iii) random branched carbonate polymer and linear carbonate. a carbonate polymer 2 selected from the group consisting of: 0 to 94% by weight, preferably 35 to 85% by weight, (B) vinyl aromatic-nitrile one or more copolymers and one or more rubbery polymers other than conjugated diene polymers. from 5 to 75% by weight, preferably at least 10% by weight of the above graft copolymer , more preferably at least 15% by weight and preferably up to 70% by weight. preferably up to 60% by weight, and (C) butadiene and/or alkyl as the core. Rubbery polymer of acrylate and alkyl (meth)acrylate outer shell Core/shell graft copolymer with polymer 0. 5-20% by weight, Preferably from at least 1% by weight, more preferably from at least 2% by weight. preferably up to 15% by weight (said weight% is based on components (A), (B) and (C)). 2. A moldable, thermoplastic blend composition comprising:

Another aspect of the present invention is a method for manufacturing a molded article using the above composition. Composition of the invention Products that are manufactured and/or molded using materials are components of automobiles, It is useful as an outer covering for molds, molds, etc.

Figures 1 and 2 are transmission electron microscopy (TEM) photographs of experimental compositions 1 and 4. Carbonate (PC) and rubber modified vinyl aromatic-nitrile graft copolymer A surprisingly light gray vinyl aromatic-nitrile copolymer phase blended with a dark gray MBS rubber present at the interface with the polycarbonate phase and within the polycarbonate phase. (black globules). Furthermore, these photographs show that vinyl aromatic- di As expected, rubber impact modifiers were present in the tolyl cobolymer (SAN) resin phase. Indicates that it exists.

The presence of rubber particles in both phases and at the interface of both phases results in high melt elasticity, elasticity, etc. yields a good combination of physical properties such as high zero shear viscosity and high zero shear viscosity.

These properties are especially important when blowing parisons weighing more than 0.9 kg (2 bonds). For shapes, high R-values (a measure of melt elasticity based on calculations using these values) are required. is particularly desirable and/or useful for thermoforming or blow molding of large parts. It is for use. As the rubber is now present in each phase of the multiphase polymer blend and at the interface Scales that control the placement of rubber are used in blow molding or thermoforming applications for large parts. It is desirable to increase the melt elasticity of the composition.

Carbonate polymers used in the present invention include, for example, US Pat. No. 3,036,036. , No. 3.036.037, No. 3.036,038 and No. 3.036. 03 Trityl diol carbonates such as those described in U.S. Pat. Disclosed in No. 999.835, No. 3.028.365 and No. 3.334.154 derivatives thereof, including aromatically and aliphatically substituted derivatives, such as (alhydroquinphenyl)-alkylidenes (often bisphenol A type diol), and as described in U.S. Pat. No. 3.169.121. carbonate polymers derived from other aromatic diols, such as Advantageously, it is a known aromatic carbonate polymer.

Carbonate copolymers or interpolymers other than homopolymers polycarbonate), if polycarbonate is desired (1) two or more types of From dihydric phenol or (2) dihydric phenol and glycol or hydroxy- It is of course understood that scales derived from acid-terminated polyesters or dibasic acids. It will be. Blends of any of the above carbonate polymers are also suitable for the practice of this invention. It's urgent. The term "carbonate polymer" is used in U.S. Pat.　169゜ No. 121: No. 4.156.069, No. 4.260.731, No. 4.330. No. 662: No. 4.360.656: No. 4.374.973: No. 4.388゜ No. 455: As stated in No. 4.355.150 and No. 4.105.633. Also included are ester/carbonate copolymers such as. Above carbonate poly Among the polymers, bisphenol A polycarbonate is preferred. Implementation of the invention Methods of making polymers for use in are well known. For example, some suitable methods is disclosed in the above patent.

Known random branched polycarbonates are also suitable for use in accordance with the present invention as monocarbonates. or as a blend with a certain amount of linear polycarbonate . The branched polycarbonate used in the present invention is disclosed in U.S. Patent No. 3.544.514. dihydric phenols in the presence of trihydric and/or tetrahydric phenols as shown in It is produced by the reaction between phosgene and phosgene.

Blow moldable resins and their preferred properties are known to those skilled in the art and are No. 4.652.602 and No. 4.474.999. US special No. 4,652,602 describes the following practical examples to illustrate the performance of the composition according to the invention. This is particularly appropriate because it defines R*, which is a measure of blow moldability used in experiments. .

The rubber modified vinyl aromatic-nitrile graft copolymer used in the composition of the present invention is Generally characterized as having a dispersed elastomeric phase and a rigid thermoplastic matrix phase. It is produced using emulsion polymerization, bulk polymerization, or suspension polymerization. as mentioned above , the rubber is selected from known rubbery polymers other than conjugated diene type rubbers. Main departure Rubber modified vinyl aromatic-nitrile graft copolymers for use by , has a Tg of less than 0°C, more preferably less than -20°C. The above types of rubber Examples are well known and include ethylene-propylene-nonconjugated diene monomers or alkyl and and acrylonitrile/styrene/acrylate (rubber) graft copolymer (A SA resin). Rubber modified vinyl aromatic-nitride for use in accordance with the present invention The graft copolymer component is a blend or combination of AES and ΔSA resin. It is also advantageous to have one.

AES resin is a matrix thermoplastic resin that is a vinyl aromatic-nitrile copolymer. Ethylene-propylene grafted with fat and dispersed in matrix thermoplastic resin - Characterized as a non-conjugated diene (EPDM) polymer rubber. AES type resin EPDM type rubber materials suitable for manufacture are well known and commercially available.

EPDM type rubber typically contains 5-40% by weight in the AES resin, preferably 10-3% by weight. 0% by weight, with the remainder typically 10-40% by weight of nitrile monomer residues. %, preferably from 15 to 30% by weight. Ru. Such AES resins are manufactured by Dow Chemical Company. Cal Company), for example, ROVEL 300 brand tree. It is commercially available as a fat and is also available in U.S. Patent No. 4,202.948. 3.642.950.

ASA resin is a matrix thermoplastic resin that is a vinyl aromatic-nitrile copolymer. Alkyl (meth)acrylate grafted with fat and dispersed in matrix thermoplastic resin. Characterized as a rylate polymer rubber. Alkyl (meth)acrylate polymer Limer rubber is an alkyl whose alkyl is a Cl-C1゜hydrocarbyl radical. Acrylate or alkyl methacrylate which is a C3-C2□hydrocarbyl radical rubbery polymers such as acrylonitrile, methacrylonitrile copolymers with other monomers such as styrene, styrene, α-methylstyrene, etc. include. Acrylate rubber materials suitable for use in the production of ASA type resins are well known. , addition of hard alkyl (meth)acrylates or vinyl aromatic-nitrile polymers. Typical by the emulsification process, loadings can still be advantageously grafted onto it during emulsification. Manufactured in The kraft rubber concentrate obtained by such a process typically contains 40 Contains more than % by weight of acrylate rubber? Subsequently, separately produced vinyl aromatic-2 Typically combined with an additional amount of tolyl copolymer, the desired acrylate rubber A final ASA type resin with a content of

Acrylate type rubber typically contains 5-40% by weight, preferably 10-30% by weight. amount used in the ASA resin, the balance typically being 10-40% by weight, preferably 15% by weight. Vinyl aromatic-nitrile copolymer containing ~30% by weight nitrile monomer residues It is. Acrylonitrile-styrene suitable for use in blend compositions according to the invention Ren-acrylate rubber graft copolymers are commercially available and It is well known from patent number 3.944.631.

Suitable rubber-modified vinyl aromatic-nitrile graft copolymers are available in latex form. Glazing the styrene-acrylonitrile (SAN) copolymer onto the desired rubber substrate. It can be manufactured by blowing. SAN in the rubber elastomer component Thermoplastic component grafted with copolymer and formed by ungrafted SAN dispersed as a discrete phase in These products are recovered from the aqueous phase and processed according to the invention. Advantageously, additional amounts of ungrafted SAN copolymer are used in blend compositions that Can be mixed.

Presence of a rubber substrate made of styrene monomer and acrylonitrile monomer monomers in which the monomers, rubber and SAN copolymer are at least partially soluble; - or other organic solvents or by swelling the rubber with such monomers or other organic solvents. Known bulk method, solution method, and bulk-solution method in which rubber is dissolved in a medium and copolymerized. It is also publicly known that resins such as 1. It is knowledge. This type of method produces styrene-acrylonitrile (SAN) The copolymer consists of rubber and the remainder of the matrix polymer of the graft copolymer component. Advantageously, both graft polymers are formed on all or part of the polymer.

Rubber modified vinyl aromatic-nitrile thermoplastic graft copolymer tree used in the present invention The rubber content of the fat is less than 40% by weight. The rubber content of this component is preferably low. 5% by weight, more preferably at least 10% by weight and preferably 30% by weight. % or less, more preferably 25% by weight or less. This is important in obtaining desirable properties. The graft copolymer according to the embodiment has a molecular weight, degree of grafting, rubber particle size and molar Along with the flexibility of changing morphology, As important as the exact vinyl aromatic monomer content and nitrile monomer content and can therefore be adjusted as known to those skilled in the art.

Generally, the rubber-modified vinyl aromatic-nitrile thermoplastic graft copolymer used in the present invention Remer resin is a rubber modified vinyl aromatic-nitrile thermoplastic graft copolymer resin. 10 to 40% by weight of nitrile monomer, more preferably 10 to 40% by weight, based on the total weight of fat. should contain 15-35% by weight. The nitrile content of this ingredient is 18% by weight. Within these ranges, further improved properties can be obtained if the It has also been found that it can be obtained. This is true for vinyl aromatic-nitrile thermoplastic resins. By giving the raft copolymer phase sufficient polarity and suitable solubility parameters, core/shell to the bonate polymer phase and its interface with the ABS type polymer. Facilitates placement of raft copolymers.

Thermoplastic vinyl aromatic-nitrile copolymers are nitrile monomers and vinyl aromatic Can be made from the monomers themselves or by combining other monomers with them (in part). (partially) or mixed with W. monomer mix changes in the monomer mix change the properties of the composite, while changes in the monomer mix change the properties of the rubber-modified thermoplastic. Basic substrate - graft - characteristic of plastic vinyl aromatic-nitrile copolymers Does not cause or is not intended to cause changes in matrix structure . However, monomer mixes (particularly nitrile monomers) are The carbonate polymer affects the solubility parameter and when blending the three species. used to introduce or place the core/shell graft copolymer component in the I can do it.

Preferred core/shell graft copolymers have a Tg of less than 0°C and a rubber of greater than 40%. It has a lum content. These are generally alkyl (meth)acrylates or diene obtained by polymerizing certain monomers in the presence of a polymeric rubber core. It will be done. The term diene polymer rubber suitable for use as a core rubber includes e.g. Carbon atoms such as tadiene, isoprene, piperylene, chlorobrene, etc. Homopolymers of useful dienes and combinations of such dienes with e.g. acrylonitrile, meth Acrylonitrile, butyl acrylate, methyl methacrylate, styrene, α- Less than 50% by weight, preferably 20% by weight of other monomers such as methylstyrene etc. more preferably less than 10% by weight. I mentioned above Sea urchin, an alkyl (meth)acrylate polymer rubber suitable for use as a core rubber. The term "em" refers to an alkyl group in which the alkyl is a C1-C1° hydrocarbyl radical. Alkylmethacrylate or Cl1-02°hydrocarbyl radical Homopolymers of rylates and such polymers such as acrylonitrile, methane, etc. Other monomers such as tacrylonitrile, styrene, α-methylstyrene etc.50 % by weight, preferably less than 20% by weight, more preferably less than 10% by weight. means a copolymer. The rubber core can be at least partially crosslinked; Preferably it is a latex polymer. Preferred alkyl (meth)acrylates Polymer rubbers include rubber polymers based on butyl acrylate.

Next, certain monomers are grafted onto the rubber core and one or more graftone polymers are added to the rubber core. and/or a small amount of non-grafted matrix polymer. This graft For example, vinyltoluene, α-methylstyrene, halogenated styrene, Vinyl aromatic compounds such as naphthalene: e.g. acrylonitrile, methacrylate Nitriles such as tolyle or α-halogenated acrylonitrile, e.g. 01-C8 acrylate such as rylate, ethyl acrylate or hexyl acrylate alkyl acrylates, such as methyl methacrylate, ethyl methacrylate, glycol C1-08 alkyl such as lycidyl methacrylate or hexyl methacrylate methacrylate: unsaturated carboxylic acid, such as acrylic acid or methacrylic acid Acids, including derivatives of such acids, such as anhydrides, or of the monomers mentioned above. A wide variety of monomers can be used, such as mixtures of two or more. degree of grafting is sensitive to the particle size of the substrate latex, and the particle size is determined by controlled agglomeration methods among other methods. influenced by law. When reaching excessively high graft levels The rubbery effect of relative substrate latex content is reduced.

Grafting monomers can be added to the reaction mixture simultaneously or sequentially; When added to a substrate latex, i.e. a layer, shell or wart-like layer around the core deposits are formed. The monomers can be added to each other in various ratios.

An example of a suitable graft copolymer of the core/shell type is methyl methacrylate/butylene. Gen/styrene graft copolymer (MBS rubber) and butyl acrylate copolymer It is a hard methyl methacrylate thermoplastic shell copolymer.

MBS type rubber is produced by polymerizing conjugated dienes or by combining conjugated dienes with, for example, styrene or acrylic. Monoolefins or polar vinyl, such as nitriles or methyl methacrylate The base latex or core is produced by copolymerization with a base latex or core compound.

The substrate latex typically contains up to 50-100% conjugated diene and up to 50% one type. It is composed of the above additional modiolefin or polar vinyl compound. one or more types The appropriate graft monomer described above is graft-polymerized onto the base latex. MBS Typical weight ratio of rubber is 60-80 parts by weight base latex, first graft monomer. -10 to 20 parts by weight and 10 to 2 parts by weight of the second graft monomer. M.B. The preferred composition of S rubber is about 71 parts of butadiene, about 3 parts of styrene, and about 4 parts of butanoene. 4111 parts and about 1 part divinylhenzene, and about 3 parts styrene. a second inner shell phase consisting of about 11 parts of methyl methacrylate and 1,3-butylene; a composition having an outer shell phase consisting of about 0.1 parts of gelicoldimethacrylate; (parts are by weight). Products with substantially such content are Rohm and Haas Company (Rohm and Haas Company) Lloyd (ParaloidT') EXL3607 Core/Shell MBS Po17? − It is commercially available. MBS rubber and its manufacturing method as described above No. 3.243.481, U.S. Pat. No. 3.287.443, U.S. Pat. No. 237, No. 3.657.391, No. 3.660.535, No. 4.180. No. 494, No. 4.221.833, No. 4.239.863 and No. 4.617 ．． No. 345 discusses this in more detail.

These compositions, as known to those skilled in this field of technology, such as UV stabilizers, antioxidant stabilizers, talc, reinforcing agents and mica. fillers such as glass fibers, ignition-resistant additives, pigments, dyes, antistatic agents, and release agents. Other ingredients can also be included, such as molding agents and the like. These compositions are injection molded , blow molding or aged mold applications. To further explain the invention, the following The experiment and control will be described below.

AES raft copolymer -・, 1 Linear polycarbonate [Caliber (Ca l b r e”) 300-1 0, Dow Chemical Compan y)] 11,300 weight, acrylonitrile-EPDM-styrene (AES) 7.0 parts by weight of copolymer, epoxidized soybean oil [Ferro Company (Ferr) Plas Chek key 7751 from ro Company 2 parts by weight and Irganox 1076 antioxidant [Chiha 14 parts by weight from CibaGeigy were mixed.

Blend the mixture evenly in a laboratory tumbler. Ta. Heating the blend to a heating set point of 270℃ 30 millimeter (mm) Werner-P f　Ieiderer) was introduced into a melt extrusion molding machine. Pelletize the extruded product , dried. Injecting 70 tons of pellets into Alburg (A r b u r g) 2.6 centimeters (am) x 2.25 cm, thickness 3. A 175 mm test piece was molded. Tests are carried out on molded bodies and their blow molding (R* value) and 0°025mm (10mi I) notched Izot value. It was measured.

Blow moldability was determined by the method generally described in U.S. Pat. No. 4,652,602. Measured by. This evaluation is based on two properties of the blow moldable resin: Reasonably low viscosity (moderate shear conditions) in the extrusion ring when extruding and suspension have sufficient melt strength and high viscosity (low shear conditions) to make the article moldable It is based on facts that require Based on this, the blow moldability value Has R* been experimentally determined to be sufficient to form a valid parison? Or at a shear rate of 100t$'-' (reciprocal 5econd) at a processing temperature calculated to be the temperature at which the material viscosity is 20,000 poise. It is defined as the ratio of viscosities at shear rates of 0, 1 s-1 and 100 s-1. child 8 of this and other experimental compositions, prepared below, according to the method of Measure this value.

The compositions of this and several other experimental blends are listed in Table 1 below. Ru. Each experimental composition was prepared using a core/shell graft copolymer according to the control method described above. By combining the specified amount of polymer with the rest of the composition in a tumble mixer. Manufactured by When used in the table below: rLin, PCJ is Dow Chemical Melt Flow Rate (MF), commercially available as Caliber 300-40 from R) linear polycarbonate with 10g/10min; rBran, P C” is commercially available as the Caliber 600 series from the Dow Chemical Company. Random branched polycarbonate with available 3MFR; rPar A3607J has a rubbery butadiene polymer as the core and styrene as the inner shell. loam with polymer and outer shell methyl methacrylate polymer Paraloid 3607 Methyl Methacrylate 1 - Styrenob from And Haas Tadiene (MBS) core/shell graft copolymer with over 70% by weight rPara3330J has a Tg of approximately -70℃; The rubbery butyl acrylate polymer of the outer shell is made of methyl methacrylate polymer. Paraloid 333 from Rohm and Haas with raft copolymer 0 core/' diel graft copolymer, containing more than 70% by weight of rubber, rAEsJ has a Tg of about -30°C; As Level (Rove l”) F-300 containing % by weight of acrylonitrile Acrylonitrile-EPD commercially available from The Dow Chemical Company M-styrene copolymer.

The test results are listed in Table 2 below. This can be seen from the combination of favorable physical properties. The compositions according to the invention are useful in injection molding, blow molding or thermoforming applications. . In Table 2 below, rlzodiJ is the direction of polymer flow at a specific temperature. in Joules/meter, measured according to ASTM D-256 perpendicular to means the notched isot impact strength value of means the value measured parallel to the direction of the “R*” is, as mentioned above, It refers to the viscosity ratio that gives a measure of blow moldability, with higher values indicating better blow moldability. suggest

Clothes”, P　C/A　E　5 Lin, PCBran, PCAES Para3607 Para3330 (heavy Weight parts (Weight parts) Weight parts (Weight parts (Weight parts) J weight scale J weight scale mm scale 11ν Control experiment 1300/65 0 700/35 0 0 Experiment 1 1240/62 0 640/32 126/6 0 Experiment 2 620/31 620/31 6 40/32. 126/6 0 Experiment 3 620/31 620/31 640/ 32 0 126/6 Table 7 Resin blend properties using AES resin Control experiment 13.7 416 85 562 133 Experiment 1 4.6 406 1 34 571 235 Experiment 2. 5.6 417 139 561 240 experiments 3 4.7 422 112 577 171 Control experiment 1 is based on the present invention. This is an example of a P C/A E S composition. Experiment 1, as seen in Figure 1 MBS is added to the polycarbonate phase and/or AE-3 resin. preferentially located at the interface with the vinyl aromatic-nitrile copolymer matrix In some cases, high R* values and good low-temperature isot impact values exceeding Control 1 can be obtained. Explain. Experiment 2 was conducted by using branched polycarbonate in the blend. Experiment 3 shows that a uniformly large increase in R* value is obtained with butyl acrylate. Other core/shell graft copolymers, such as rubber-based graft copolymers This shows that a high two-wire value and high impact resistance can be obtained even when using

Therefore, core/shell grafting is preferentially applied to each phase or interface of a multiphase polymer composition. It is desirable to arrange copolymer rubber. In this case, such a composition is Melt bullets at low shear rates desirable for improved blow molding or thermoforming applications It has a good combination of physical properties including increased physical properties.

ASA graft copolymer - 1.2 linear polycarbonate (Caliber 300 -10, Dow Chemical Company) 1300 parts by weight of acrylonitrile- 700 parts by weight of styrene-acrylate copolymer (ASA), epoxidized soybean oil [Plus Check 775 from Ferro Company] 2 parts by weight and Irganok 4 parts by weight of an anti-oxidant 1076111 agent (from Ciba Geigi) were mixed. blend and molded bodies were prepared and tested according to the methods of Control] and AES experiments described above.

The composition of each blend is listed in Table 3 below, and the test results are listed in Table 4 below.

The abbreviations used in the table below are the same as those used in Tables 1 and 2 above, and in addition to the above, “A SAJ contains 15% by weight of acrylate rubber and at least 20% by weight of acrylonitrile. Acrylonitrile-styrene-acrylate graft copolymer rubber containing means.

Table 3 - PC/ASA blend Lin-PCBran, PCASA Para3607 Para3330 ( Parts by weight (parts by weight) (parts by weight (parts by weight) 1 weight scale 1 weight scale 11 total mli 11 total control experiment 2 1300/65 Q 700/35 0' 0 experiment 4 1246/62 0 640/32 120/6 0 Control experiment 3 650/ 32.5 650/32.5 700/35 0 0 Experiment 4 620/31 6 20/31 640/32 120/6 0 Experiment 5 620/31 620/3 1 640/32 0 120/6 Experiment 6 460/23 460/23 10 00150 80/4 0 table Engineering 1 zod Nihon Suyu Engineering -29℃ Suyue -29℃ Control Experiment 2:16 443 58 560 101 Experiment 4 4.7 433 96 539 176 Experiment 3 4.6 192 37 512 69 Experiment 5 5-7 411 96 550 208 Experiment 6 5.0 438 69 619 144 Experiment 7 5.6 80 HA 187 NA control grain 1 is an example of a PC/ASA composition not according to the present invention It is. In Experiment 4, as shown in Figure 2, MBS was added and this MBS was – control experiments when preferentially located at the interface with the bonate phase and/or other phases. Explain that a high two-core value exceeding 2 and a good low-temperature Izotz impact value can be obtained. . Experiment 4 used only linear PC, which has a fairly low melt elasticity, and therefore PC Placing this rubber at the phase or interface allows for improved blow molding or thermoforming resins. The melt elasticity required for this purpose can be increased.

Another way to increase the melt elasticity of PC resin is to use branched polycarbonate!・Use It is. As expected, control experiment 3 increased R* by adding a branched resin. Although the value increases dramatically, by doing this the vertical impact is substantially reduced. This shows that the value decreases to . Experiments 5.6 and 7 were conducted using linear and/or branched polycarbonate. Core 2/Shell graft copolymer rubber blended with A-type resin and AS It is shown that the R* value and the impact value are again greatly improved by adding Mo. .

FIG.2 Corrected sound translation submission form (Article 184-8 of the Patent Act) September 9, 1991

Claims (11)

[Claims] 1. The following ingredients: (A) (i) Random branched carbonate polymer, (ii) linear carbonate polymer, and (iii) random branched carbonate polymer and linear carbonate. 20 carbonate polymers selected from the group consisting of: ~94% by weight, (B) Vinyl aromatic-nitrile copolymer and one or more other than conjugated diene polymer 5 to 75% by weight of one or more graft copolymers with the rubbery polymers above, and ( C) rubbery polymer of butadiene and/or alkyl acrylate as core with an outer shell alkyl (meth)acrylate polymer. Graft copolymer 0.5 to 20% by weight (the above weight% is for components (A), (B) and and (C)) A moldable composition comprising. 2. The rubberized polymer of the graft copolymer (B) is ethylene-propylene-noncovalent. one or more rubbery polymers of functional diene monomers or alkyl (meth)acrylates; - The moldable composition according to claim 1. 3. Graft copolymer (B) is ethylene-propylene-nonconjugated diene monomer 3. A moldable composition according to claim 2, comprising one or more rubbery polymers. 4. The graft copolymer (B) contains one or more alkyl (meth)acrylates. 3. A moldable composition according to claim 2, comprising a sticky polymer. 5. The following ingredients: (A) 35-85% by weight of carbonate polymer, (B) graft copolymer (B) ) 10 to 60% by weight, and (C) core-shell graft copolymer (C) 2 to 1 A moldable composition according to claim 2 comprising 5% by weight. 6. A claim in which the carbonate polymer comprises a randomly branched carbonate polymer. 1. The moldable composition according to 1. 7. A claim in which the carbonate polymer comprises a randomly branched carbonate polymer. Item 6. The moldable composition according to item 6. 8. The carbonate polymer is a random branched carbonate polymer with 20 to 80 weights. % and 80 to 20% by weight of linear carbonate polymer. A moldable composition as described. 9. Next step: (A) having high melt viscosity and melt strength; forming a composition; and (B) Molding including the step of thermoforming or blow molding the composition to form a molded object How the body is manufactured. 10. the carbonate polymer comprises a randomly branched carbonate polymer; 10. The method according to claim 9, wherein the molding method is a thermoforming method. 11. the carbonate polymer comprises a randomly branched carbonate polymer; 10. The method according to claim 9, wherein the molding method is a blow molding method.