JPH0380822B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a heat-resistant and impact-resistant resin composition. More specifically, the present invention relates to a resin composition comprising a rubber-modified unsaturated dicarboxylic acid anhydride resin, a polycarbonate, and a modified polyolefin, which has significantly improved thermal decomposition resistance, and has excellent heat resistance and impact resistance. <Prior art> Conventionally, copolymers made of styrene and unsaturated dicarboxylic anhydrides, such as maleic anhydride, have higher heat resistance than other styrene resins, such as polystyrene and styrene-acrylonitrile copolymers. However, like other styrenic resins, it has poor impact resistance, so there are various restrictions on its range of use. For this reason, a method of polymerizing maleic anhydride and styrene in the presence of rubber (Japanese Unexamined Patent Application Publication No. 48-1989)
42091), and a composition obtained by mixing polycarbonate (Japanese Patent Publication No. 57-27133), or a rubber-modified unsaturated dicarboxylic acid polymer obtained by polymerizing maleic anhydride, styrene, etc. in the presence of rubber and polycarbonate. A composition obtained by mixing
28339), Special Publication No. 57-27134, USP3966842) have been proposed. <Problems to be Solved by the Invention> However, in polymers containing maleic anhydride as one component, the maleic anhydride easily undergoes a decarboxylation reaction due to heat during granulation or molding, resulting in thermal decomposition. do. For this reason, the impact resistance of the polymer itself and the effect of improving impact resistance by blending polycarbonate and introducing rubber components are reduced. Further, since the melt viscosity of polycarbonate is high, the processing temperature of such a composition is high, and the temperature range is narrow, so processing conditions for obtaining a good product are severe. Note that if the maleic anhydride content is suppressed in order to suppress the decarboxylation reaction, not only heat resistance but also compatibility with polycarbonate deteriorates, and even impact resistance deteriorates. Moreover, when the rubber content is increased, the balance between heat resistance and processability deteriorates. <Means for Solving the Problems> The present inventors have improved the thermal decomposition resistance of a composition consisting of a rubber-modified unsaturated dicarboxylic anhydride resin and polycarbonate without sacrificing the heat resistance and impact resistance. As a result of intensive research for improvement, it was discovered that the desired composition could be obtained by blending a specific polymer into such a composition, and the present invention was achieved based on this finding. That is, the present invention provides (A) an unsaturated dicarboxylic anhydride (a-2), an aromatic vinyl compound, an unsaturated nitrile compound, and an unsaturated carboxylic acid ester compound in the presence of a rubbery polymer (a-1). A rubber-modified unsaturated dicarboxylic acid anhydride resin obtained by polymerizing one or more compounds (a-3) selected from (A) and (B) a polycarbonate, and (C) a modified polyolefin. Composition ratio with (B) is 10:90-90:
10 (weight ratio), and the blending amount of (C) is 0.1 to 100 parts by weight per 100 parts by weight of (A) and (B), which has significantly improved heat decomposition resistance. The present invention provides a resin composition with excellent heat resistance and impact resistance. The composition of the present invention will be explained in detail below. The rubber-modified unsaturated dicarboxylic acid anhydride resin (A) used in the present invention is a rubbery polymer (a
-1), an unsaturated dicarboxylic anhydride (a-2) and one or more compounds selected from aromatic vinyl compounds, unsaturated nitrile compounds, and unsaturated carboxylic acid ester compounds (a-3). be. As the rubbery polymer (a-1), conjugated diene rubbery polymers such as polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer,
Ethylene-propylene polymers such as ethylene-propylene-non-conjugated diene copolymers containing non-conjugated dienes such as dicyclopentadiene and ethylidenenorbornene, (meth)acrylic ester polymers such as butyl methacrylate polymers, and chlorinated Examples include polyethylene, ethylene-vinyl acetate copolymer, etc., and one or more types can be used. Examples of the unsaturated dicarboxylic anhydride (a-2) include maleic anhydride, itaconic anhydride, citraconic anhydride, and aconitic anhydride, and one or more of them can be used. Maleic anhydride is particularly preferred. Examples of aromatic vinyl compounds include styrene, α-
Methylstyrene, P-methylstyrene, p-t-
Examples include butylstyrene, dimethylstyrene, halogenated styrene, etc., and one or more types can be used. Styrene is particularly preferred. Examples of the unsaturated nitrile compound include acrylonitrile, methacrylonitrile, maleonitrile, etc., and one or more types can be used. Acrylonitrile is particularly preferred. Examples of the unsaturated carboxylic acid ester compound include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc., and one or more of them may be used. I can do it. Particularly preferred is methyl methacrylate. The compound (a-3) constituting the resin (A) together with the unsaturated dicarboxylic anhydride (a-2) is one selected from the above-mentioned aromatic vinyl compounds, unsaturated nitrile compounds, and unsaturated carboxylic acid ester compounds. These are the above compounds. Particularly preferred is an aromatic vinyl compound alone or a combination of an aromatic vinyl compound and another compound. There is no particular restriction on the composition ratio (weight ratio) of the rubbery polymer (a-1), the unsaturated dicarboxylic anhydride (a-2), and the compound (a-3) constituting the resin (A). From the viewpoint of heat resistance, impact resistance, etc. of the composition, 5 to 25% by weight of the rubbery polymer (a-1), 5 to 30% by weight of the unsaturated dicarboxylic anhydride (a-2) and the compound (a- 3) It is preferably 50 to 90% by weight. The resin (A) can be prepared by a known polymerization method, such as a bulk polymerization method,
It can be obtained by solution polymerization method, bulk-suspension polymerization method, etc. Polycarbonate (B) used in the present invention
Examples include aromatic polycarbonate, aliphatic polycarbonate, and aliphatic-aromatic polycarbonate. Among them, 2,2-bis(4-oxyphenyl)alkane, bis(4-
Aromatic polycarbonates comprising bisphenols such as oxyphenyl)ether, bis(4-oxyphenyl)sulfone, sulfide or sulfoxide are preferred. Furthermore, polycarbonate resins made of bisphenols substituted with halogen can also be used, if necessary. There are no restrictions on the molecular weight of polycarbonate (B), but it is generally 10,000 or more, preferably 20,000 to 40,000. Furthermore, the modified polyolefin (C) used in the present invention includes an epoxy group-containing olefin polymer (C-1), which is a polyolefin containing an unsaturated epoxy compound as one component, and an unsaturated carboxylic acid or acid anhydride as one component. An unsaturated carboxylic acid-modified olefin polymer (C-2) containing an unsaturated carboxylic acid ester as one component and an unsaturated carboxylic acid ester-olefin copolymer containing an unsaturated carboxylic ester as one component (C-2)
-3), and one or more types can be used. Particularly preferred is the epoxy group-containing olefin polymer (C-1) alone or a combination of the epoxy group-containing olefin polymer (C-1) and other polymers (C-2 and/or C-3). The epoxy group-containing olefin polymer (C-1) is a polymer consisting of an unsaturated epoxy compound and olefin, or these and other ethylenically unsaturated compounds. There is no particular restriction on the composition ratio of the epoxy group-containing olefin polymer, but the epoxy compound 0.05
~95% by weight, 5 to 99.95% by weight of olefins and 0 to 50% by weight of other ethylenically unsaturated compounds. The unsaturated epoxy compound is a compound having an epoxy group and an unsaturated group copolymerizable with an olefin and an ethylenically unsaturated compound in the molecule. For example, the following general formulas (), () and ()
These are unsaturated epoxy compounds such as unsaturated glycidyl esters, unsaturated glycidyl ethers, epoxy alkenes, and P-glycidyl styrenes. (R is a _C2-18 hydrocarbon group having an ethylenically unsaturated bond.) (R is a _C2-18 hydrocarbon group having an ethylenically unsaturated bond. X is _-CH2 -O-,

[expression] or

[Formula]. ) (R is a _C2-18 hydrocarbon group having an ethylenically unsaturated bond. R' is hydrogen or a methyl group.) Specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butene carboxyl acid esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-P-glycidyl ether,
3,4-epoxybutene, 3,4-epoxy-3
-Methyl-1-butene, 3,4-epoxy-1-
Examples include pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, and P-glycidylstyrene. Epoxy group-containing olefin polymers can be made by various methods. For example, an unsaturated epoxy compound and an olefin, in some cases an ethylenically unsaturated compound, are combined in the presence of a radical generator at a temperature of 50 to 4000
Examples include a method of contacting at atmospheric pressure at 40 to 300°C, and a method of mixing an unsaturated epoxy compound with polyolefin and irradiating it with gamma rays under high vacuum to prepare a polymer. Unsaturated carboxylic acid modified olefin polymer (C-
2) is a polymer consisting of an unsaturated carboxylic acid and/or its anhydride and an olefin or these and other ethylenically unsaturated compounds. There is no particular restriction on the composition ratio of the unsaturated carboxylic acid-modified olefin polymer;
~10% by weight and 0 other ethylenically unsaturated compounds
~50% by weight is particularly preferred. Examples of unsaturated carboxylic acids and/or anhydrides include monocarboxylic acids such as acrylic acid and methacrylic acid, dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, and dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride. Dicarboxylic acids and dicarboxylic anhydrides are particularly preferred. Unsaturated carboxylic acid modified olefin polymer (C-
2) can be made in various ways. For example, it can be obtained by mixing and heating an unsaturated carboxylic acid and/or anhydride with an olefin or a polymer consisting of an olefin and another ethylenically unsaturated compound. The unsaturated carboxylic acid ester-olefin copolymer (C-3) is a copolymer consisting of an unsaturated carboxylic acid ester and an olefin, or these and other ethylenically unsaturated compounds. There is no particular restriction on the composition ratio of the unsaturated carboxylic acid ester-olefin copolymer (C-3), but 5 to 70% by weight of the unsaturated carboxylic acid ester, 30 to 95% by weight of the olefin, and other ethylenically unsaturated Preferably, it is 0 to 20% by weight of the compound. Examples of the unsaturated carboxylic acid ester compound include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc., and one or more of them may be used. I can do it. Particularly preferred is methyl methacrylate. Examples of the olefin which is an essential component in the above-mentioned modified polyolefin (C) include ethylene, propylene, butene-1, 4-methylpentene-1, etc., and one or more of them can be used. Particularly preferred are ethylene and propylene. Other ethylenically unsaturated compounds that can be used in the modified polyolefin (C) include olefins, vinyl esters containing C _{2 to 6} in the saturated carboxylic acid component, and C _{1 to 8} in the saturated alcohol component. Examples include acrylic and methacrylic esters, maleic esters, vinyl halides, vinyl ethers, N-vinyl lactams, and carboxylic acid amides. Rubber modified unsaturated dicarboxylic acid anhydride resin (A),
Polycarbonate (B) and modified polyolefin (C)
The composition ratio of (A) and (B) is 10:90 ~
90:10 (weight ratio), and the blending amount of (C) is (A)
The amount is 0.1 to 100 parts by weight per 100 parts by weight of (B).
In particular, the blending amount of (C) is per 100 parts by weight of (A) and (B).
It is preferably 0.1 to 40 parts by weight. Rubber modified unsaturated dicarboxylic acid anhydride resin (A),
Polycarbonate (B) and modified polyolefin (C)
Examples of the mixing method include known methods using a Banbury mixer, a single-screw extruder, a twin-screw extruder having a kneading block, and the like. In addition, there is no restriction on the mixing order, and the three components can be mixed at once.
Only two of the components may be mixed in advance, and then the remaining one component may be added and mixed. Furthermore, during mixing, it is possible to add other resins such as polyamide, polyester, polysulfone, etc., as well as known dyes and pigments, antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, fillers, etc. The present invention will be specifically explained below using Examples, but the present invention is not limited thereto. Examples and Comparative Examples Based on the compounding ratios shown in Tables 1 and 2, rubber-modified unsaturated dicarboxylic acid anhydride resin, polycarbonate, and modified polyolefin were mixed together, and then melt-mixed in a single-screw extruder to form a composition. Obtained. The properties of the obtained composition are shown in Tables 1 and 2. -Rubber-modified unsaturated dicarboxylic acid anhydride resin- Resin (A-) obtained by polymerizing maleic anhydride and styrene in the presence of polybutadiene rubber according to the bulk-suspension polymerization method (polybutadiene rubber
15% by weight, maleic anhydride (15% by weight, styrene 70% by weight)) A resin (A-) obtained by polymerizing maleic anhydride, styrene, and acrylonitrile in the presence of polybutadiene rubber according to a bulk polymerization method. (10% by weight of polybutadiene rubber, 15% by weight of maleic anhydride, 60% by weight of styrene, 15% by weight of acrylonitrile) -Polycarbonate- Polycarbonate (B) with a molecular weight of approximately 25,000 consisting of bisphenol-A -Modified polyethylene- According to the bulk polymerization method An epoxy group-containing olefin polymer (C-) obtained by polymerizing ethylene and glycidyl methacrylate. (Ethylene 90% by weight,
Glycidyl methacrylate 10% by weight) An epoxy group-containing olefin polymer (C-) obtained by polymerizing ethylene, glycidyl methacrylate, and vinyl acetate according to a bulk polymerization method. (85% by weight of ethylene, 10% by weight of glycidyl methacrylate, 5% by weight of vinyl acetate) Unsaturated carboxylic acid-modified olefin polymer obtained by mixing polyethylene and maleic anhydride and then melt-kneading with two heated rolls. (C-) (100 parts by weight of polyethylene, 1 part by weight of maleic anhydride) An unsaturated carboxylic acid alkyl ester-olefin copolymer (C-) obtained by polymerizing ethylene and ethyl acrylate according to a bulk polymerization method. (10% by weight of ethyl acrylate, 90% by weight of ethylene)

【table】

[Table] -Test method- 1 Heat decomposition resistance Falling ball impact strength after retention (Kg cm) Resin inside the injection molding machine cylinder (resin temperature
270℃) for 15 minutes, injection time:
10 seconds, cooling time: 60 in a 20 second molding cycle
Create a flat plate of mm x 60 mm x 3 mm. After creation,
Inject the resin in the cylinder, let it stay for another 15 minutes, and create a flat plate using the above molding cycle. Create a total of 10 flat plates in the same way. 23℃
The impact strength was measured by dropping a 1Kg steel ball in a constant temperature room. Weight reduction (weight%) Using Parking Elmer's DSC-,
The weight loss was determined when the resin was allowed to stay at a temperature of 280°C for 15 minutes. Silver (with or without) Using an injection molding machine (resin temperature 270℃), 10 flat plates of 90mm x 150mm x 3mm were continuously created using a molding cycle of injection time: 10 seconds and cooling time: 3 minutes 50 seconds. The presence or absence of silver on the surface of the flat plate was determined with the naked eye. In this case, the resin remained in the cylinder for 4 minutes. 2 Heating deformation temperature (℃) ASTM D-648 1/4 inch thickness, 18.6Kg/cm ² load, no annealing 3 Notched Izotsu impact strength ASTM D-256 (resin temperature 250℃, injection 10 seconds,
Cooling 20 seconds) 1/4 inch thickness, 23℃ 4 Workability Koka type flow tester (nozzle: 1 mm diameter,
Length 10mm) 230℃, 60Kg/cm ² load <Effects of the invention> The composition of the present invention has excellent heat decomposition resistance compared to the conventionally proposed compositions consisting of rubber-modified unsaturated dicarboxylic acid anhydride resin and polycarbonate. This solves various conventional problems caused by thermal decomposition during molding. In addition, it is excellent not only in notched isot impact strength but also in weld part strength.

Claims (1)

[Claims] 1 (A) In the presence of a rubbery polymer (a-1), an unsaturated dicarboxylic anhydride (a-2), an aromatic vinyl compound, an unsaturated nitrile compound, and an unsaturated carboxylic ester (A) consisting of a rubber-modified unsaturated dicarboxylic acid anhydride resin obtained by polymerizing one or more compounds (a-3) selected from the compounds, (B) polycarbonate, and (C) modified polyolefin; The composition ratio of and (B) is 10:90-90:
10 (weight ratio), and the blending amount of (C) is 0.1 to 100 parts by weight per 100 parts by weight of (A) and (B) in total. .