THERMOPLASTIC RESINOUS COMPOSITION HAVING EXCELLENT MOLDING PROPERTIES

Abstract: Disclosed is a thermoplastic resinous composition hav­ ing excellent molding properties comprising ; (A) 100 parts by weight of an ABS resin, and (B) 0.5-10 parts by weight of a copolymer consisting of (a) 0.1-10 percent by weight of an acrylate or methacrylate containing epoxy groups, hydroxyl groups or alkoxy groups, (b) 20-99.9 percent by weight of an alkyl acrylate not con­ taining epoxy groups, hydroxyl groups or alkoxy groups, and (c) 0-79.9 percent by weight of other copolymerizable vinyl compounds.

Description: THERMOPLASTIC RESINOUS COMPOSITION HAVING EXCELLENT MOLDING PROPERTIES BACKGROUND OF THE INVENTION Field of the Invention: The present invention relates to a thermoplastic resinous composition having excellent thermal deformation resistance and impact resistance as well as molding properties. it refers More particularly,/to a new thermoplastic resinous composition comprising an ABS resin and a copolymer in less amounts which is composed of an acrylate or methacrylate containing epoxy groups1 hydroxyl groups or alkoxy group1 an alkyl acrylate not containing epoxy groups, hydroxyl groups or alkoxy groups, and other copolymerizable vinyl monomers. Description of the Prior Art: because ABS resins are good materials /of their excellent mechanical properties and their economy. But they have the disadvantage that they are difficult to mold. Especially. the melt the the viscosity of/resin upon molding is high because of/rubber components contained therein. For this reason, undesired results such as flow marks, setting and unevenness of color of welded portions appear on the surface of the molded articles Occasionally, a decrease in impact resistance. cracks etc. due to molding strain takesplace. in order to solve these problems, various processes have been used, for example reducing the molecular weight of the ABS resin1 lowering the melt viscosity of the ABS resin by decreasing the content of the rubber component, or adding large amounts 6f a lubricant. These processes, however, are not recommended since the former the two processes deteriorate/mechanical properties of the the ABS resins and the latter causes/deposition of the lubricant on the the metal mold and a decrease in/thermal deformation resistance and impact resistance. Moreover, recently, there has been an increasing need for materials having a higher heat distortion temperature, particularly in the field of automobile upholstery It is the usual practice to capolymerize alDhamethylstwrene in order to improve thermal deformation resistance of ABS resins. However, copolymerization of alphamethylstyrene increases the melt viscosity of resin even more, thus resulting in more frequent occurrence of the above mentioned inconveniences upon molding. SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic resinous composition a Sich is markedly inproved in molding properties and has excellent thermal deformation resistance, impact resistance and rigidity,by adding the specified modifying resin to the ABS resin. Other objects of the present invention together with advantages thereof will be apparent from the detailed description of the invention. DETALIED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resinous composition having excellent thermal deformation resistance and impact resistance as well as molding properties. it refers hore particularly,/to a new thermoplastic resinous composition comprising 100 parts by weight of an ABS resin (A) and 0.5-10 parts by weight of a copolymer (B) which is composed of 0.1-10 percent by weight of an acrylate or methacrylate containing epoxy groups, hydroxyl groups or alkoxy group, 20-99.9 percent by weight of an alkyl acrylate not containing epoxy groups hydroxyl groups or alkoxy groups, and 0-79.9 percent by weight of other copolymerizable vinyl monomers. The ABS resin (A) used in the present invention comprises a graft copolymer (a) obtained by polyeri2ing.in the presence of a conjugate diene rubber two or more compounds selected from the group consisting of vinyl cyanide compounds, aromatic vinyl compounds, methacrylates and acrylates. The ABS resin (A) may further contain a copolymer (b) obtained by copolymerizing two or more compounds selected from the group consisting of vinyl cyanide compounds, aromatic vinyl compounds and methacrylates. The proportion of the conjugate diene rubber of the graft copolymer (a) and the foregoing compounds is not limited specifically, but 5-85 parts by weight of the conjugate diene rubber and 95-15 parts by weight of the foregoing compounds are preferred. As the proportion of the foregoing compounds, 0-40 parts by weight of the vinyl cyanide compound, 30-80 parts by weight of the aromatic vinyl compound and 0-70 parts by weight of the methacrylate and / or acrylate are preferred. The average particle size of the conjugate diene rubber is not is limited specifically, but/preferably in the range of 0.05-1.5 pm. The proportion of the foregoing compounds forming the the copolymer (b) is preferably in / range of 0-35 parts by weight of the vinyl cyanide compound, 50-90 parts by weight of the aromatic vinyl compound and 0-40 parts by weight of the methacrylate and / or acrylate. The intrinsic viscosity of the ABS resin (A) is the preferably in / range of 0.25-1.2 [dl/g) (h', N ' -dimethyl formamide solution, 30c) in terms of methyl ethyl ketonesoluble components of the graft copolymer (a) and the copolymer (b). The conjugate diene rubber used in the present invention may include polybutadiene, butadien-styrene copolymers. butadiene-acrylonitrile copolymers, butadiene-butylacrylate copolymers etc. The vinyl cyanide compound may include acrylonitrile, methacrylonitrile etc. The aromatic vinyl compound may include styrene, alphamethylstyrene, vinyl toluene, methylstyrene, chlorostyrene etc. The methacrylate and acrylate may include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, hydroxyacrylate etc. The graft copolymer (a) and the copolymer (b) may be prepared by emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, emulsionsuspension polymerization, bulk-suspension polymerization etc. The copolymer (B) which is added to inprove molding properties of the foregoing ABS resin (A) is a copolymer comprising 0.1-10 percent by weight of the acrylate or methacrylate containing epoxy groups1 hydroxyl groups or alkoxy groups1 20-99.9 percent by weight of the alkyl acrylate not containing epoxy groups1 hydroxyl groups or alkoxy groups, and 0-19.9 percent by weight of other copolymerizable vinyl compounds. The acrylate or methacrylate containing epoxy groups1 hydroxyl group or alkoxy groups forming the copolymer (B) may include glycidyl acrylate, glycidyl methacrylate1 2hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2hydroxypropyl acrylate, 2-hYdroxypropyl methacrylate, methoxyethyl acrylate. methoxyethyl methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate etc. The alkyl acrylate not containing epoxy groups, hydroxyl groups or alkoxy groups forming the copolymer (B) may include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate etc.. the alkyl group of the alcohol residual group having 2-8 carbon atoms. The other copolymerizble vinyl compound may include alkyl methacrylates such as methyl methacrylate copolymerizable with alkyl acrylates; aromatic vinyl compounds such as styrene, alphamethylstyrene, nethylstyrene etc; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile etc. Those may be used singly or in combination of two or more. The intrinsic viscosity of the copolymer (B) is preferably in a range of 1.0 or less tdl/g) (N, N ' -dimethyl formamide solution. 30C), more preferably 0.5 or less (dl/g) In the case of more than 1.0 Edl/g) , the effect of improving molding properties is insufficient. The amount of the foregoing copolymer (B) is 0.5-10 parts by weight, preferably 1-5 parts by weight based on 100 parts by weight of the ABS resin (A). When the amount is less than 0.5 part by weight, a satisfactory effect is not obtained, while, when it is more than 10 parts by weight, impact resistance, rigidity, thermal deformation resistance etc. undesirably deteriorate. The copolymer (B) of the present invention may be obtained easily by normal emulsion polymerization using a water -soluble initiator such as potassium persulfate etc. or an oilsoluble initiator such as cumene hydroperoxide etc. In the polymerization of the copolymer (B), polymerizing aromatic vinyl monomers and vinyl cyanide monomers in the presence of the copolymer (B) or conducting the polymerization of the copolymer (B) in the presence of the ABS resin (A) for freely adjusting powder properties after drying are included in the present invention, too. As mentioned above, the present invention provides a resinous composition with markedly improved molding properties characterized in that the specified copolymer (B) is added as an essential component to the ABS resin (A). but the present composition may further contain antioxidants, heat stabilizers, lubricants, ultraviolet ray absorbers, pigments, antistatic agents, flame retardants, flame retarding assistants, fillers such as glass fibers etc. The resinous compositions of the present invention comprising the ABS resin (A) and the specified copolymer (B) provide molded articles superior in thermal deformation resistance. impact resistance as well as molding properties, as will be shown by examples. Hereinbelow the present invention will be explained in more detail by way of examples to which the present invention is in no way limited. EXAMPLES 1-5, COMPARATIVE EXAMPLES 1-4 A graft copolymer comprising 52 parts by weight of alphamethylstyrene, 10 parts by weight of styrene, 22 parts by weight of acrylonitrile and 16 parts by weight of polybutadiene, whose intrinsic viscosity of components soluble in methyl ethyl ketone is 0.60 (dllg) was used as the ABS resin (A). The copolymer (B) was prepared according to the following manner. Using 2 parts by weight of sodium dioctylsulfosuccinate as an emulsifying agent, 0.4 part by weight of sodium formaldehyde sulfoxylate and 0.5 part by weight of cumene hydroperoxide as a redox type polymerization initiator and 4 parts by weight of tertiary dodecyl mercaptan as a chain transfer agent, emulsion polymerization was performed at 60c to obtain a copolymer latex, The monomer mixture was composed of 2 parts by of glycidyl methacrylate 60 parts by weight of butyl acrylate, 25 parts by weight of styrene and 15 parts by weight of acrylonitrile. The obtained copolymer latex was salted out to give the copolymer (B) - I . The conversion was 98% and the intrinsic viscosity was 0.1 tdl/g) . Likewise, the monomer mixture composed of 1 part by weight of glycidyl methacrylate and 99 parts by weight of butyl acrylate was polymerized to obtain the copolymer (B) @ B. The conversion was 98% and the intrinsic viscosity was 0.06 (dl/g) . The so obtained (A) and (B) were blended in such amounts as set forth in Table 1 and the blends were pelletized. Using the obtained pellets, various kinds of test samples were made according to the usual manner and their physical properties and molding properties measured. The results are shove in Table 1. Table 1 EMI9.1 Examples <SEP> Comparative <SEP> Examples <tb> 1 <SEP> 2 <SEP> 3 <SEP> 4 <SEP> 5 <SEP> 1 <SEP> 2 <SEP> 3 <SEP> 4 <tb> ABS <SEP> resin(A) <SEP> (parts <SEP> by <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <tb> weight) <tb> Copolymer(B)- <SEP> I(") <SEP> 2 <SEP> 3 <SEP> 5 <SEP> 7 <tb> Copolymer(B)- <SEP> II(") <SEP> 3 <SEP> 15 <tb> EBS <SEP> (") <SEP> 2 <tb> Stearic <SEP> acid <SEP> (") <SEP> 3 <tb> Heat <SEP> distortion <SEP> temp. <SEP> ( C) <SEP> 112 <SEP> 112 <SEP> 111.5 <SEP> 110.5 <SEP> 112 <SEP> 112 <SEP> 108 <SEP> 108 <SEP> 106 <tb> Izod <SEP> strength <SEP> (kg.cm/cm) <SEP> 17.3 <SEP> 17.1 <SEP> 17.0 <SEP> 16.8 <SEP> 17.1 <SEP> 16.0 <SEP> 16.0 <SEP> 13.1 <SEP> 15.3 <tb> Tensile <SEP> strenght <SEP> (kg/cmê) <SEP> 520 <SEP> 516 <SEP> 510 <SEP> 508 <SEP> 514 <SEP> 523 <SEP> 581 <SEP> 480 <SEP> 473 <tb> Spiral <SEP> flow <SEP> (mm) <SEP> 595 <SEP> 635 <SEP> 675 <SEP> 740 <SEP> 665 <SEP> 510 <SEP> 535 <SEP> 795 <SEP> 540 <tb> Flow <SEP> mark <SEP> # <SEP> # <SEP> # <SEP> # <SEP> # <SEP> x <SEP> x <SEP> # <SEP> x <tb> NOTE EBS : Ethylene bisstearylamide Heat distortion temperature : ASTM-D-648 18.6 kg/cmê load Izod strength : ASTM-D-256 with notch, 23 C Tensile strength : ASTM-D-636, 23 t Spiral flow : 3-ounce injection molding machine, nozzle temperature 250 C C, injection pressute 900 kg/cmZ, mold temperature 40-T Flow mark : A box-type molded article with a length of 180 rrrn, a width of 100 mm, a depth of 40 mm and a thickness of 3 mm was prepared by injection molding and its appearance was studied. The results are shown according to the criteria: 0 ... substantially inconspicuous # ... somewhat remarkable x ... remarkable

Claims: WHAT WE CLAIM IS 1. A thermoplastic resinous composition having excellent molding properties comprising (A)100 parts by weight of an ABS resin, and (B) 0.5-10 parts by weight of a copolymer consisting of (a) 0.1-10 percent by weight of an acrylate or methacrylate containing epoxy groups, hydroxyl groups or alkoxy groups (b) 20-99.9 percent by weight of an alkyl acrylate not containing epoxy groups, hydroxyl groups or alkoxy groups, and (c) 0-79.9 percent by weight of other copolymerizable vinyl compounds. 2. Rne thermoplastic resinous composition of Claim 1, wherein the intrinsic viscosity of the ABS resin is in a range of 0.25-1.2 (dI/g) (N, N ' -dimethyl formamide solution. 30 C) in terms of its components 'soluble in methyl ethyl ketone. 3. The thermoplastic resinous composition of Claim 1, wherein the intrinsic vicosity of the copolymer is 1.0 or less (dl/g) (N, N ' -dimethyl formamide solution, 30t). 4. The thermoplastic resinous composition of Claim 1, wherein the ABS resin comprises a graft copolymer obtained by polymerizing in the presence of a conjugate diene rubber two or more compounds selected from the group consisting of vinyl cyanide compounds1 aromatic vinyl compounds, methacrylates and / or acrylates. wherein 5.The thermoplastic resinous composition of Claim 4, the ABS resin comprises 5-85 parts by weight of the conjugate diene rubber and 95-15 parts by weight of the compounds consisting of 0-40 parts by weight of the vinyl cyanide compound, 30-80 parts by weight of the aromatic vinyl compound and 0-70 parts by weight of the methacrylate and / or acrylate. 6.The thermoplastic resinous composition of Claim 4, wherein the ABS resin further contains a copolymer obtained by polymerizing two or more compounds selected from the group consisting of vinyl cyanide compounds, aromatic vinyl compounds and methacrylates and / or acrylates. 7.The thermoplastic resinous composition of Claim 6. wherein the copolymer comprises 0-35 parts by weight of the vinyl cyanide compound, 50-90 parts by weight of the aromatic vinyl compound and 0-40 parts by weight of the methacrylate and / or acrylate.

Inventors: MATSUMOTO, SHIGEMI, MISHIMA, IKUHIRO, NAGOSHI, FUMIYA, NISHIMOTO, KENJI
Applicants: KANEGAFUCHI KAGAKU KOGYO KABUSHIKI KAISHA
Application year: 1986
Main classification: C08L55
IPC codes: C08L21, C08L7, C08L33, C08L51, C08L55