Weather-resistant thermoplastic resin composition

Abstract: A weather-resistant thermoplastic resin composition excellent in processing stability is provided which comprises 100 parts by weight of a mixture of 40 - 100 parts by weight of a vinyl chloride polymer and 0 - 60 parts by weight of a polymer containing no chlorine and having a glass transition temperature of 100 - 200 °C; 4 - 25 parts by weight of an impact strength modifier containing no double bond; and 0.1 - 1.0 part by weight of a hindered amine light stabilizer. Molded articles made from this composition are especially excellent in weather resistance and are useful as pipes outdoors or building materials.

Description: The present invention relates to a thermoplastic resin composition of improved weather resistance. Vinyl chloride resin articles have problems of impact resistance and heat resistance and many attempts have been made to improve these properties. One approach to improving impact resistance is to blend chlorinated polyethylene, ethylene-vinyl acetate copolymer to which vinyl chloride is grafted or impact strength modifiers such as acrylic rubber with the resin articles, taking into consideration the desired weather resistance. Another approach for improving impact resistance as well as heat resistance is to blend with vinyl chloride resin the above impact strength modifier and a heat resistance modifier such as α-methylstyreneacrylonitrile copolymer. However, although these vinyl chloride resin articles have improved impact resistance or both impact resistance and heat resistance and are somewhat improved in weather resistance, the improvement is not satisfactory yet. When the articles are in the shape of pipes or building materials and are used outdoors under relatively severe conditions for a long time, they undergo photo-deterioration with lapse of time, resulting in reduction of impact strength. Hithereto, in order to prevent vinyl chloride resin compositions from photo-deterioration and in order to stabilize them, proposals have been made to add so-called light screens which intercept light or to add ultraviolet absorbers which absorb undesirable light and convert it to harmless heat energy. However, in order to sufficiently improve weather resistance by adding fillers such as carbon black, TiO 2 and ZnO as light screens, they must be used in a large amount. As a result, the amount of pigments which have to be used for colour matching is naturally increased and deterioration of properties occurs due to excess lubrication caused by dispersant contained in the pigments and besides cost is also high. Further, addition of ultraviolet absorbers such as salicylic esters, benzophenones and benzotriazoles is also not satisfactory yet to improve weather resistance. On the other hand, light stabilizers made from hindered amine which trap radicals produced by heat or light energy do not perform sufficiently as light stabilizers for vinyl chloride resins. An object of the present invention is to provide a vinyl chloride resin composition having improved impact resistance or both the impact resistance and heat resistance and enhanced weather resistance without damaging the excellent processing stability and mechanical strengths. As a result of the inventors' intensive research, it has been found that hindered amine light stabilizers which do not exhibit sufficient effect as light stabilizers for vinyl chloride resins markedly improve weather resistance of a polymer mixture which comprises a vinyl chloride polymer or a mixture of a vinyl chloride polymer and a polymer containing no chlorine and having a glass transition temperature of 100 - 200°C and an impact strength modifier containing no double bond which consists of an ethylene/methyl methacrylate copolymer on which vinyl chloride is grafted and an acrylic rubber. JP-A-55050047 quoted in Patent Abstracts of Japan page 99 column 15 reveals a composition containing a vinyl chloride polymer and a second polymer containing no chlorine, an impact strength modifier and a benzotriazole or a benzophenone light stabilizer. According to the present invention there is provided a thermoplastic resin composition superior in weather resistance which comprises (1) 100 parts by weight of a mixture comprising 100 - 40, preferably 40 to 95, parts by weight of a vinyl chloride polymer and 0 - 60, preferably 5 to 60, parts by weight of a second polymer containing no chlorine and which has a glass transition temperature of 100 - 200°C, (2) 4 - 25 parts by weight of an impact strength modifier and (3) 0.1 - 1.0 part by weight of a hindered amine light stabilizer, characterised in that the impact strength modifier contains no double bonds and consists of an ethylene/methyl methacrylate copolymer on which vinyl chloride is grafted and an acrylic rubber and in that the hindered amine light stabilizer is bis-(2,2,6,6,-tetramethyl-4-piperidinyl) sebacate, or is of the formula: and has an average molecular weight of 2500 or more. When a vinyl chloride polymer is used alone, dynamic heat stability is superior and processing stability is high. When the vinyl chloride polymer is mixed with chlorinated vinyl chloride polymer, heat resistance and mechanical strength are improved. Furthermore, when an impact strength modifier containing no double bond and which consists of an ethylene/methyl methacrylate copolymer on which vinyl chloride is grafted and an acrylic rubber, is added to vinyl chloride polymer, impact resistance is markedly improved. When an impact strength modifier containing no double bond and which consists of an ethylene/methyl methacrylate copolymer on which vinyl chloride is grafted and an acrylic rubber, is added to a mixture of vinyl chloride polymer and a polymer containing no chlorine and having a glass transition temperature of 100-200°C, not only impact resistance is improved, but also heat resistance and mechanical strength becomes higher. Component (1) The component (1) comprises vinyl chloride polymers. They include vinyl chloride homopolymer and copolymers comprising at least 90% by weight of a vinyl chloride monomer and up to 10% by weight of a monoolefin copolymerizable with the vinyl chloride monomer, for example, vinyl acetate or vinylidene chloride. The polymers may be produced by suspension polymerization, bulk polymerization, emulsion polymerization, etc. The chlorinated vinyl chloride polymers used in the present invention may be produced by known process, for example, by suspending in water a vinyl chloride polymer with or without a chlorinated hydrocarbon solvent, and then applying chlorine-addition thereto. This chlorinated vinyl chloride polymer is added preferably in an amount of 5 - 50%, more preferably 10 - 40% by weight of vinyl chloride polymer. If the amount is less than 5% by weight, improvement of heat resistance is not sufficient and if more than 50% by weight, processing stability is insufficient. The second polymers containing no chlorine and having a glass transition temperature of 100 - 200 ° C which may be used as one of the components in the vinyl chloride mixture (1) are those which enhance heat resistance of vinyl chloride resins. They are, for example, poly α-methylstyrene, copolymers mainly formed of α-methylstyrene such as α-methylstyrene/acrylonitrile copolymer, imide polymers such as poly N-phenylmaleimide or polyglutarmaleimide, and styrene/maleic anhydride copolymer. Preferred are α-methylstyrene/acrylonitrile copolymer, polyglutarmaleimide and styrene/maleic anhydride copolymer, taking into consideration their compatibility with vinyl chloride polymer and enhancement of heat resistance. The glass transition temperature is the point at which the gradient of the volume-temperature curve according to dilatometer measurements abruptly changes and if this is lower than 100°C, enhancement of heat resistance is insufficient and if this is higher than 200°C, processing temperature is naturally high and processing stability of the vinyl chloride resin composition is inferior. With reference to the mixing ratio of the vinyl chloride polymer and the second polymer which contains no chlorine and which has a glass transition temperature of 100 - 200 ° C, the amount of the latter polymer, i.e., that containing no chlorine, should preferably be 0 - 60 parts by weight for every 100 parts by weight of (1). In order to improve heat resistance, in particular, the latter polymer should be 5 - 60 parts, preferably 20 - 60 parts. If more than 60 parts by weight is used, impact resistance decreases. Component (2) The impact strength modifier should be added in an amount of 4 - 25 parts, preferably 5 - 20 parts by weight every 100 parts by weight of component (1). If it is less than 4 parts by weight, improvement of impact resistance is lower and if more than 25 parts by weight, mechanical strength is lower. Component (3) The hindered amine stabilizer is added in an amount of 0.1 - 1.0 parts, more preferably 0.2 - 0.8 parts, by weight on the basis of 100 parts by weight of component (1) above. If the amount is less than 0.1 part by weight, improvement of weather resistance is insufficient and even if it is more than 1.0 parts by weight, the effect is not increased so much. Processing For processing of the composition of the present invention, there may be optionally added known stabilizers, lubricants, ultraviolet ray absorbers, antioxidants, pigments, etc. which are commonly used for processing of vinyl chloride resins and furthermore, if necessary, fillers may also be used. Components (1) - (3) above may be mixed by roll mills, ribbon blenders, Henschel mixers, Banbury mixers, etc. and may be processed into desired molded articles by known molding machines such as extruders, injection molding machines or calendering machines. The resulting molded articles are of high mechanical strength and excellent impact resistance and heat resistance and besides have improved weather resistance. Therefore, they are useful as rigid articles such as pipes and building materials. The present invention will be explained by the following nonlimiting examples. Properties were measured by the following methods. Parts and percents in the examples are by weight. Evaluation of impact resistance: Charpy impact strength measured in accordance with JIS K7111. Evaluation of weather resistance: Charpy impact strength measured in accordance with JIS K7111 on a sample subjected to exposure for 300 hours under the conditions of black panel temperature of 63°C and spraying of 18 min/120 minutes using a sunshine weatherometer type accelerated weathering apparatus specified in JIS A1415. Furthermore, retention of Charpy impact strength is obtained by the following formula. Charpy impact strength after exposure for 300 hr x 100 Charpy impact strength before exposure Evaluation of heat resistance: Vicat softening point measured under a load of 5 Kgf in accordance with JIS K7206. Evaluation of mechanical strength: Resin composition was filled in mixer head of roller mixer W50H type and kneaded at 200°C and 50 rpm and time required for the composition beginning to decompose was measured by plasticorder-PLV151 of Brabender Co. Example 1 To a resin composition comprising a polymer mixture of polyvinyl chloride having an average polymerization degree of 1100 (100 parts; "Sumilit"® SxllF of Sumitomo Chemical Co., Ltd.), graft polymer A (6 parts) prepared by the following process and acrylic rubber (6 parts; Kane Ace FM of Kanegafuchi Chemical Industry Co., Ltd.), were added a lead stabilizer (3 parts), a metallic soap lubricant (1 part), a processability modifier (1.5 parts), a pigment (0.8 part) and a hindered amine stabilizer (0.3 part; Chimassorb 944LD of Ciba-Geigy Corp.). The blend was kneaded and extruded to shape pipes by a different direction twin-screw extruder Mitsubishi Kraus KMD-60K at 25 rpm under the following temperature conditions: cylinders: C 1 165°C, C 2 160°C, C 3 170°C and C 4 175°C, adapter: Ad 170°C, dies: D 1 160°C, D 2 153°C, D 3 167°C and D 4 180°C. Mechanical strength, heat resistance, weather resistance and impact resistance of the resulting pipes were measured. Separately, dynamic heat stability of the above composition was also measured by the above mentioned method. The properties are shown in Table 1B. Preparation of graft copolymer A: Dionized water (100 parts), ethylene/methyl methacrylate copolymer (50 parts; "Acryft" ® WM-305 of Sumitomo Chemical Co., Ltd.), hydroxypropylmethyl cellulose (0.2 part; "Metholose"® 65SH-50 of Shinetsu Chemical Co., Ltd.), α,α'-azobisisobutyronitrile (0.08 part), and diallyl phthalate (0.5 part) were charged in a stainless steel autoclave, which was then evacuated to 30 mmHg. Then, vinyl chloride monomer (50 parts) was charged therein and polymerization was started by heating to 60°C with stirring. After 6 hours, polymerization was discontinued and unreacted vinyl chloride monomer was purged and the content was taken out and dehydrated and dried to obtain graft polymer A, which contained 59% of ethylene/methyl methacrylate copolymer and had 43% of gel content insoluble in tetrahydrofuran. Example 2 Example 1 was repeated except that Kane Ace FM (6 parts) was used in place of the graft copolymer A (6 parts). The properties are shown in Table 1B. This is a comparison example. Example 3 Example 1 was repeated except that 20 parts of "Sumilit" R SxllF (100 parts) was replaced by chlorinated vinyl chloride polymer (heat resistance Kanevinyl of Kanegafuchi Chemical Industry Co., Ltd.). The properties are shown in Table 1B. Example 4 Example 1 was repeated except that hindered amine stabilizer Sanol LS-770 (Sankyo Co., Ltd.) was used in place of the Chimassorb 944LD. The properties are shown in Table 1B. Examples 5 - 8 Example 1 was repeated except that amounts of Sumilit Sx11F, the graft copolymer A, Kane Ace FM, and Chimassorb 944LD were changed as shown in Table 1. The properties are shown in Table 1B. All of the resin compositions in Examples 1 - 8 have improved dynamic heat stability. Molded articles made from these resin compositions are superior in tensile strength and impact resistance as well as in Charpy impact strength retention percentage after exposure for 300 hrs in weather resistance test. Comparative Example 1 Example 1 was repeated, except that a benzotriazole ultraviolet ray absorber (Sumisorb 300 of Sumitomo Chemical Co., Ltd.) was used in place of the Chimassorb 944LD. The properties are shown in Table 1B. Comparative Example 2 Example 1 was repeated except that amount of the pigment (0.8 part) was changed to 3.0 parts and TiO 2 (2.0 parts) was used in place of Chimassorb 944LD. The properties are shown in Table 1B. Comparative Examples 3 - 5 Example 1 was repeated except that amounts of the Sumilit SxllF, graft polymer A, Kane Ace FM and Chimassorb 944LD were changed. The properties are shown in Table 1B. Comparative Example 6 Example 1 was repeated except that 80 parts of the Sumilit Sx11F (100 parts) was replaced by chlorinated vinyl chloride polymer. The properties are shown in Table 1B. Samples of Comparative Example 1 are lower in weather resistance and those of Comparative Example 2 are higher in lubrication and impact resistance is lower because a large amount of pigment is added for colour matching. Samples of Comparative Example 3 are lower in tensile strength and Vicat softening point and those of Comparative Example 4 are lower in Charpy impact strength. Samples of Comparative Example 5 are lower in weather resistance and those of Comparative Example 6 are lower in dynamic heat resistance and in processing stability. Example 9 Example 1 was repeated except that a polymer mixture comprising Sumilit Sx11F (55 parts), α-methylstyrene/acrylonitrile copolymer (45 parts, monomer ratio = 70 : 30), graft polymer A (5 parts) and Kane Ace FM (10 parts) was used as resin composition. The properties are shown in Table 2A1 and 2A2. Example 10 Example 9 was repeated except that the graft polymer A (5 parts) was changed to Kane Ace FM, namely, Kane Ace (15 parts) was used. The properties are shown in Table 2A1 and 2A2. This is a comparison example. Example 11 Example 9 was repeated except that 15 parts of the Sumilit Sx11F (55 parts) was replaced by heat resistant Kanevinyl. The properties are shown in Table 2A1 and 2A2. Examples 12 - 16 Example 9 was repeated except that amounts of the polymer and Chimassorb 944LD to be added were changed. The properties are shown in Table 2A1 and 2A2. Example 15 is a comparison example. The resin compositions of Examples 9 - 16 all show good dynamic heat stability and molded articles obtained from these resin compositions not only have high Charpy impact strength retention after being subjected to the weathering test for 300 hours, but also are superior in mechanical strength, impact resistance and heat resistance. Comparative Example 7 Example 9 was repeated except that Sumisorb 300 was used in place of the Chimassorb 944LD. The properties are shown in Table 2B1 and 2B2. Comparative Example 8 Example 9 was repeated except that the amount of the pigment (0.8 part) was increased to 3.0 parts and TiO 2 (2.0 parts) was used in place of the Chimassorb 944LD. The properties are shown in Table 2B1 and 2B2. Comparative Examples 9 - 13 Example 9 was repeated except that amounts of the polymer and light stabilizer Chimassorb 944LD to be added were changed. The properties are shown in Table 2B1 and 2B2. Comparative Example 14 Example 9 was repeated except that 40 parts of the Sumilit SxllF (55 parts) was replaced by heat resistant Kanevinyl. The properties are shown in Table 2B1 and 2B2. Samples of Comparative Example 7 are of lower weather resistance and those of Comparative Example 8 are higher in lubrication and impact resistance is lower because a large amount of pigment is added for colour matching. Samples of Comparative Example 9 are lower in tensile strength, Vicat softening point and Charpy impact strength and those of Comparative Examples 10 and 11 are lower in Charpy impact strength and that of Comparative Example 12 is lower in tensile strength and Vicat softening point. Samples of Comparative Example 13 are lower in weather resistance and those of Comparative Example 14 are lower in dynamic heat resistance and in processing stability. As explained above, the thermoplastic resin composition of the present invention is superior processing stability and molded articles made therefrom show markedly excellent weather resistance and superior mechanical properties represented by tensile strength, flame retardance and chemical resistance and besides are improved in impact resistance or heat resistance and impact resistance. The compositions may be used as pipes or building materials which are subjected to severe conditions, in view of the features above. More specific uses are electric wires and underground pipes. Formulae I available from Nihon Chiba-Geigy Co. as CHIMASSORB 944LD (Registered Trade Mark). It has an average molecular weight of 2500 or more, the formula is: Formula II is available from Sankyo Co. as SANOL L770 (Registered Trade Mark). It is bis-(2,2,6,6-tetramethyl-4-piperidinyl) sebacate namely:

Claims: A weather-resistant thermoplastic resin composition which comprises (1) 100 parts by weight of a mixture of 40 - 100 parts by weight of a vinyl chloride polymer and 0 - 60 parts by weight of a second polymer which contains no chlorine and has a glass transition temperature of 100 - 200°C; (2) 4 - 25 parts by weight of an impact strength modifier and (3) 0.1 - 1.0 parts by weight of a hindered amine light stabilizer, characterised in that the impact strength modifier contains no double bonds and consists of an ethylene/methyl methacrylate copolymer on which vinyl chloride is grafted and an acrylic rubber and in that the hindered amine light stabilizer is bis-(2,2,6,6,-tetramethyl-4-piperidinyl) sebacate, or is of the formula: and has an average molecular weight of 2500 or more. A weather-resistant thermoplastic resin composition as claimed in claim 1 which comprises (1) 100 parts by weight of a vinyl chloride polymer or of a mixture of 95 - 40 parts by weight of a vinyl chloride polymer and 5 - 60 parts by weight of a second polymer which contains no chlorine and has a glass transition temperature of 100 - 200°C; (2) 5 - 20 parts by weight of an impact strength modifier and (3) 0.1 - 1.0 parts by weight of a hindered amine light stabilizer, characterised in that the impact strength modifier contains no double bonds and consists of an ethylene/methyl methacrylate copolymer on which vinyl chloride is grafted and an acrylic rubber and in that the hindered amine light stabilizer is bis-(2,2,6,6,-tetramethyl-4-piperidinyl) sebacate, or is of the formula: and has an average molecular weight of 2500 or more. A weacher-resistant thermoplastic resin composition according to Claim 1 or Claim 2 wherein the vinyl chloride polymer mixture comprises 80 - 40 parts by weight of the vinyl chloride polymer and 20 - 60 parts by weight of the second polymer. A weather-resistant thermoplastic resin composition according to Claim 1, 2 or 3 wherein the vinyl chloride polymer is a polymer mixture of 5 - 50% by weight of a chlorinated vinyl chloride polymer and 95 - 50% by weight of a vinyl chloride polymer. A weather-resistant thermoplastic resin composition according to Claim 1, 2, 3 or 4 wherein the second polymer is α-methylstyrene/acrylonitrile copolymer, polyglutarmaleimide or styrene/maleic anhydride copolymer. A molded article obtained from the weather-resistant thermoplastic resin composition of any one of Claims 1 - 5.

Inventors: IGARASHI TOSHIO, MARUYAMA HIROAKI, NAKATSUJI YOSHIHIRO, YOSHIHARA MASAYUKI, IGARASHI, TOSHIO, MARUYAMA, HIROAKI, NAKATSUJI, YOSHIHIRO, YOSHIHARA, MASAYUKI
Applicants: SUMITOMO CHEMICAL CO, SUMITOMO CHEMICAL COMPANY LIMITED
Application year: 1989
Main classification: C08K5
IPC codes: C08L27, C08L25, C08L35, C08L33, C08L51, C08K5