Low-gloss thermoplastic resin compositions

Abstract: A thermoplastic resin composition comprising (A) 100 parts by weight of : (1) 99-70 wt% of polycarbonate resin, and (2) 1-30 wt% of an addition polymer containing units derived from glycidyl (meth)acrylate, and (B) 0.001-1 part by weight of an organic acid, phosphoric acid, phosphorous acid, hypophosphoric acid and/or a compound other than an organic acid that has one or more functional groups selected from among carboxyl, amino, hydroxyl, acid anhydride and thiol groups. The compositions have low-gloss properties as well as excellent mechanical strength and weatherability.

Description: The present invention relates to aromatic polycarbonate resin compositions, and more specifically to aromatic polycarbonate resin compositions having a low gloss and also an excellent mechanical strength and weatherability. Aromatic polycarbonates are widely used because of their excellent mechanical strength, weatherability, light stability and heat resistance. However, molded pieces made of these often have luster. Having a luster is desirable in a number of applications. However, a delustered or non-glossy surface is often desirable in products such as computer terminal housings, typewriters, various electric appliances and certain kinds of automotive components. The removal of luster by surface embossing requires a separate step, which increases costs. Moreover, there is a possibility that the surface that has been delustered by embossing will vanish due to subsequent wear, leading to the reappearance of a luster. The addition of delustering agents such as finely divided silica, silicates, alumina and other mineral fillers often has an adverse influence on such physical characteristics as the impact strength. Efforts to add polymer-based delustering agents frequently have an adverse influence not only on the impact strength, but also on other important characteristics such as the heat distortion temperature, weatherability and light stability. Compositions in which butadiene rubber polymers and other components are blended are known from Japanese Published Unexamined Patent Applications [Kokai] Nos. 59-193.950 (1984), 60-20,955 (1985). 61-174,257 (1986) and 63-156.851 (1988) as aromatic polycarbonate resin compositions having low luster and excellent mechanical strength and heat resistance. However, polycarbonate resin compositions which contain butadiene rubber polymers exhibit inadequate weatherability, and so are not suited to applications that require high weatherability. Hence, in prior-art polycarbonate resin composition, it has been difficult to achieve excellent mechanical properties, excellent weatherability and low luster at the same time. The object of this invention is to provide low-gloss polycarbonate resin compositions that have excellent mechanical properties and weatherability. The inventors discovered that when glycidyl (meth)-acrylate polymer and an organic acid, phosphoric acid, phosphorous acid, hypophosphoric acid and/or a compound other than an organic acid containing one or more functional groups selected from among carboxyl, amino, hydroxyl, acid anhydride and thiol groups is added to the aromatic polycarbonate resin composition, the luster can be decreased without compromising the properties of the aromatic polycarbonate resin composition. That is, the present invention is a thermoplastic resin composition comprising : (A) 100 parts by weight of a component comprising (1) 99 to 70 weight percent of an aromatic polycarbonate, and (2) 1 to 30 weight percent of a glycidyl (meth)acrylate polymer, and (B) 0.001 to 1 part by weight of a component selected from acetic acid, propionic acid, malonic acid, succinic acid, stearic acid, maleic acid, fumaric acid, itaconic acid, citric acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, benzenesulfonic acid, toluenesulfonic acid, each of the foregoing being unsubstituted or substituted with other functional groups selected from acid anhydride, phosphoric acid, phosphorous acid, hypophosphoric acid, hydroxyethyl methacrylate, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride and dodecylsuccinic anhydride. The use of above component (B) here is an important component of the present invention. By using this component, the luster of the resin composition can be greatly decreased. This was entirely unexpected. The polycarbonate resin which serves as component (A-1) in the present invention is an aromatic polycarbonate that has been prepared by a known phosgene process or a melt process (e.g., see Kokai Nos. 63-215.763 (1988) and 2-124.934 (1990)). The polycarbonate resin consists of a carbonate component and a diphenol component. Phosgene and diphenyl carbonate may be cited as examples of precursors for introducing carbonate components. Examples of suitable diphenols that may be cited include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)decane, 1,4-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(3.5-dimethyl-4-hydroxyphenyl)cyclododecane, 4.4-dihydroxydiphenyl ether, 4,4-thiodiphenol, 4,4-dihydroxy-3.3-dichlorodiphenyl ether and 4,4-dihydroxy-2,5-dihydroxydiphenyl ether. These can be used alone or as combinations. In addition, it is also possible to use compounds having three or more phenolic hydroxyl groups. Next, there is component (A-2) used in the present invention. In this invention, the addition polymer containing units derived from glycidyl (meth)acrylate that serves as component (A-2) encompasses all polymers that contain units derived from glycidyl (meth)acrylate; aside from homopolymers of glycidyl methacrylate (GMA) or glycidyl acrylate, and copolymers of both, these may also be copolymers with other monomers. When component (A-2) is a copolymer, it is preferable that this copolymer contain at least 10 wt% of units derived from glycidyl (meth)acrylate, and it is even more preferable that these be copolymers or terpolymers with compounds selected from among aromatic vinyl compounds such as styrene, vinyl cyanide compounds such as acrylonitrile. unsaturated carboxylic acids such as (meth)acrylic acid, or their alkyl esters such as methyl methacrylate or methyl acrylate. It is even more preferable that GMA-styrene copolymers and GMA-styrene-acrylonitrile copolymers be used as component (A-2). These components (A-2) are compounded in an amount of 1-30 wt% with respect to 99-70 wt% of component (A-1), and preferably in an amount of 3-15 wt% with respect to 97-85 wt% of component (A-1). When the amount of component (A-2) is less than 1 wt%, the luster does not decrease by very much; on the other hand, when this is more than 30 wt%, the mechanical strength of the composition decreases. The compound used as component (B) is selected from acetic acid, propionic acid, malonic acid, succinic acid, stearic acid, maleic acid, fumaric acid, itaconic acid, citric acid, benzoic acid, phthalic acid, isophthalic acid and terephthalic acid; sulfonic acids such as benzenesulfonic acid and toluenesulfonic acid, phosphoric acid, phosphorous acid and hypophosphoric acid, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride and dodecylsuccinic anhydride. Component (B) is included in the resin composition of the present invention in an amount of 0.001-1 part by weight, and preferably 0.01-0.5 part by weight, per 100 parts by weight of component (A) (that is, the sum of components (A-1) and (A-2)). When the amount of component (B) is less than 0.001 part by weight, the luster of the composition is not sufficiently reduced; when this exceeds 1 part by weight, declines occur in such properties of the composition as the mechanical strength and heat resistance. In addition, other resins, and especially rubbery substances, as well as conventional additives such as pigments, dyes, reinforcing agents, fillers, heat resisting agents, antioxidants, anti-weathering agents. lubricants, parting agents, crystal nucleating agents, plasticizers, flowability enhancers, and antistatic agents may be added when the resin is mixed or during molding, provided that doing so does not mar the properties of the resin compositions of the present invention. The reinforcing fillers may be selected from among finely-ground aluminum, iron or nickel, metal oxides, non-metals such as carbon filament, silicates such as mica and aluminum silicate (clay), talc, asbestos, titanium dioxide, wollastonite, novaculite, potassium titanate and titanate whiskers, glass flakes, glass beads, glass fibers and polymer fibers. The reinforcing fillers may be used in an amount capable of exhibiting reinforcing effects, this normally being 1-60 wt%, and preferably 5-50 wt%, of the composition. The preferable reinforcing material is glass. In cases where the composition of the present invention includes a polycarbonate consisting of brominated bisphenol, an inorganic or organic antimony compound can also be formulated into the composition of the present invention in order to synergistically increase the flame retardancy achieved in this way. Hindered phenols, phosphites, metal phosphates, and metal hypophosphites can be admixed as stabilizers and antioxidants. When producing the resin compositions of the present invention, various components can be mixed by means of a method known to the prior art. For example, suit able use can be made of a melt kneading process using an extruder, a Banbury mixer, or rollers following dispersion and mixing of the various components in a high-speed mixer such as a tumbling mixer or Henschel mixer, ribbon blender or super mixer. Examples The following were used as the components in the examples of the invention and the comparative examples described below. Component (A-1): Aromatic polycarbonate: Lexan 141 (trademark, General Electric Co.; prepared from bisphenol A and phosgene; intrinsic viscosity at 25° C in methylene chloride, 0.51 dL/g) Component (A-2): G-1005SA (trademark, Nippon Oil & Fats Co.; 5 wt% GMA-containing styrene-acrylonitrile copolymer) G-1005S (trademark, Nippon Oil & Fats Co.; 5 wt% GMA-containing styrene copolymer) Component B Citric acid Hypophosphoric acid Maleic anhydride Other Components (used in comparative examples): ABS resins: "Bretex"* 301 [tradename, Borg-Warner Chemical; a powdered ABS copolymer (rubber content, 34%) containing about 24% of acrylonitrile monomer units, 34% of butadiene monomer units and 422 of styrene monomer units; most likely produced essentially by the emulsion polymerisation process cited in U.S. Patent No. 3,238,275]. Examples 1-6, Comparative Examples 1-5 The components in the proportions (weight ratios) indicated in Table 1 were melt-kneaded in a 50-mm twinscrew extruder at a kneading temperature of 260° C and a rotational speed of 290 rpm, and pellets formed. Using these pellets, molded pieces were fabricated at a temperature setting of 260 o C and a mold temperature of 60 o C, and the physical properties were measured in general accordance with the following criteria. Notched Izod impact strength -- ASTM D256 Tensile strength and tensile elongation -- ASTM D638 Flexural strength and flexural modulus -- ASTM D790 The results are presented in Table 1. The surface gloss of the molded pieces (50x50x3mm square sheets) was measured using a digital varied-angle glossmeter (UGV-40, made by Suga Shikenki KK). Those results are also given in Table 1. In addition, using a weatherometer (model Ci35 made by Atlas Co.), molded pieces (50x50x3mm square sheets; fabricated in the same manner as the molded pieces used in the measurement of gloss) that had been colored gray were irradiated with a xenon arc lamp having a radiation wavelength of 340 nm and a radiation illuminance of 0.39 W/m 2 at a black panel temperature of 63 o C and a humidity of 50%. After this, the initial hue and the color difference ( E) were measured using a spectrophotometer (model CA35, made by Murakami Shikisai Gijutsu Kenkyujo). The results are presented in Table 1. Advantages of the Invention The present invention provides aromatic polycarbonate resin compositions having a sufficiently low luster as well as excellent mechanical strength and weatherability.

Claims: A thermoplastic resin composition comprising (A) 100 parts by weight of a component comprising (1) 99 to 70 weight percent of an aromatic polycarbonate, and (2) 1 to 30 weight percent of a glycidyl (meth)acrylate polymer, and (B) 0.001 to 1 part by weight of a component selected from acetic acid, propionic acid, malonic acid, succinic acid, stearic acid, maleic acid, fumaric acid, itaconic acid, citric acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, benzenesulfonic acid, toluenesulfonic acid, phosphoric acid, phosphorous acid, hypophosphoric acid, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride and dodecylsuccinic anhydride. The resin composition of Claim 1 wherein component (B) is citric acid. The resin composition of Claim 1 wherein component (B) is hypophosphoric acid. The resin composition of Claim 1 wherein component (B) is maleic anhydride.

Inventors: FUJIGUCHI TOMOHIDE, ITOI HIDEYUKI, SAITO AKIHIRO, FUJIGUCHI, TOMOHIDE, ITOI, HIDEYUKI, SAITO, AKIHIRO
Applicants: GE PLASTICS JAPAN LTD, GE PLASTICS JAPAN LIMITED
Application year: 1992
Main classification: C08L69
IPC codes: C08K5, C08K3, C08L69