Title of Invention

THERMOPLASTIC RESIN COMPOSITION WITH LOW COEFFICIENT OF LINEAR THERMAL EXPANSION

Abstract

The thermoplastic resin composition according to the present invention comprises (A) a diene graft polymer prepared by grafting in emulsion polymerization 100 parts by weight of monomer mixture comprising 20-30% by weight of vinyl cyanide compound and 70-80% by weight of vinyl aromatic compound to 40-60 parts by weight of diene rubber; (B) a vinyl cyanide- vinyl aromatic copolymer having a weight-average molecular weight (Mw) of 100,000~200,000 prepared by copolymerizing 20~40 parts by weight of vinyl cyanide compound and 80~60 parts by weight of vinyl aromatic compound; (C) a vinyl cyanide- vinyl aromatic copolymer having a weight-average molecular weight(Mw) of 200,000~600,000 prepared by copolymerizing 20~40 parts by weight of vinyl cyanide compound and 80~60 parts by weight of vinyl aromatic compound; and (D) a N-substituted maleimide copolymer prepared by copolymerizing 20~60 parts by weight of a mixture of maleic anhydride and N-substituted maleimide and 40~80 parts by weight of a vinyl aromatic compound and/or a vinyl cyanide compound, wherein (A) is 15~30 parts by weight, (B)+(C) is 40~85 parts by weight, (D) is 0~30 parts by weight, and (B) : (C) is from 0 : 100 to 80 : 20. The thermoplastic resin composition of the present invention has low coefficient of linear thermal expansion.

Full Text

FORM 2 THE PATENTS ACT, 1970 (39 of 1970) & THE PATENTS RULES, 2003 COMPLETE SPECIFICATION [See section 10, Rule 13] THERMOPLASTIC RESIN COMPOSITION WITH LOW COEFFICIENT OF LINEAR THERMAL EXPANSION; CHEIL INDUSTRIES INC, A CORPORATION ORGANIZED AND EXISTING UNDER THE LAWS OF KOREA, WHOSE ADDRESS IS 290 GONGDAN-DONG, GUMI-SI, GYEONGSANGBUK-DO 730-710, KOREA THE FOLLOWING SPECIFICATION PARTICULARLY DESCRIBES THE INVENTION AND THE MANNER IN WHICH IT IS TO BE PERFORMED. l Field of the Invention The present invention relates to a thermoplastic resin composition having a low coefficient of linear thermal expansion. More particularly, the present invention relates to a styrenic thermoplastic resin composition that comprises a diene graft polymer, two kinds of vinyl cyanide-vinyl aromatic copolymers different in the range of weight-average molecular weight and a N-substituted maleimide copolymer in a specific ratio which has a low coefficient of linear thermal expansion, a decreased volatile organic compound (VOC) content and shows good impact strength and heat resistance. Background of the Invention A styrenic thermoplastic resin is excellent in impact resistance, mechanical strength, appearance and mold processability, therefore, the resin has been widely applied to electric/electronic appliances, interior/exterior parts of automobiles and household products. In particular, when a resin is used for interior/exterior parts of automobiles, especially for exterior parts which is exposed to the outside where temperature and weather are extremely changeable, used to be made for relatively large-sized parts of automobiles and mainly connected to metal parts, not only the above properties such as impact resistance, mechanical strength but also good heat resistance and dimensional stability are required. When the heat resistance is insufficient, the molded article of the resin composition tends to be deformed and crooked at high temperature. And when the dimensional stability is insufficient, the molded article of the resin composition does not fit to other parts during assembly and tends to be deformed and distorted, or cracks may sometimes take place under highly changeable temperature. Therefore, heat resistance and dimensional stability are highly required for use in the parts of automobiles. Especially, the moled articles assembled to the metal parts tend to be deformed after assembly according to the change in temperature even though it fits to other parts at the time of 2 assembly. The reason for this is that the coefficient of linear thermal expansion of the resin is about 4-8 times higher than that of metal. Accordingly, if the coefficient of linear thermal expansion of the resin gets close to that of the metal, the resin the resin may be used in various application even which has been limited. In order to achieve a low level of coefficient of linear thermal expansion of resin, inorganic fillers such as calcium carbonate, talc, and so forth have been used. Japanese Patent Laid-open No. 10-265644 discloses an ABS resin composition with low level of coefficient of linear thermal expansion by using an ultrafine particulate calcium carbonate as a filler. However, in this patent, although the coefficient of linear thermal expansion of the resin is somewhat improved, such a composition is limited in the range of utilization, because of poor impact strength and surface appearance. Accordingly, the present inventors have developed a thermoplastic resin composition having a low coefficient of linear thermal expansion and a decreased volatile organic compound (VOC) content as well as good impact strength and heat resistance by using diene graft polymer, two kinds of vinyl cyanide-vinyl aromatic copolymers and N-substituted maleimide copolymer in a specific ratio Objects of the Invention An object of the present invention is to provide a styrenic thermoplastic resin composition having a low coefficient of linear thermal expansion without using inorganic filler. Another object of the present invention is to provide a styrenic thermoplastic resin composition having good impact strength and heat resistance as well as low coefficient of linear thermal expansion and a decreased volatile organic compound (VOC) content. A further object of the present invention is to provide a styrenic thermoplastic resin composition having good dimensional stability. Other objects and advantages of this invention will be apparent from the ensuing disclosure and appended claims. 3 Summary of the Invention The thermoplastic resin composition according to the present invention comprises (A) a diene graft polymer prepared by grafting in emulsion polymerization 100 parts by weight of a monomer mixture comprising 20-30% by weight of a vinyl cyanide compound and 70-80% by weight of a vinyl aromatic compound to 40-60 parts by weight of a diene rubber; (B) a vinyl cyanide- vinyl aromatic copolymer having a weight-average molecular weight (Mw) of 100,000-200,000 prepared by copolymerizing 20-40 parts by weight of a vinyl cyanide compound and 80-60 parts by weight of a vinyl aromatic compound; (C) a vinyl cyanide- vinyl aromatic copolymer having a weight-average molecular weight(Mw) of 200,000-600,000 prepared by copolymerizing 20-40 parts by weight of a vinyl cyanide compound and 80-60 parts by weight of a vinyl aromatic compound; and (D) an N-substituted maleimide copolymer, wherein (A) is 15-30 parts by weight, (B)+(C) is 40-84 parts by weight, (D) is 1-30 parts by weight, and (B): (C) is from 0 : 100 to 80 : 20. The components (A), (B), (C) and (D) will be described in detail hereinafter. Detailed Description of the Invention (A) Diene graft polymer The diene graft polymer of the present invention is prepared by mixing 100 parts by weight of a monomer mixture of a vinyl cyanide compound and a vinyl aromatic compound and 40-60 parts (on the basis of solids content) by weight of diene rubber, and by grafting in a conventional emulsion polymerization the monomer mixture to the diene rubber. The monomer mixture consists of 20-30 % by weight of a vinyl cyanide compound and 80-70 % by weight of a vinyl aromatic compound. In the present invention, the graft ratio of grafting the polymer matrix onto the diene rubber is preferably 40-70 % based upon the weight of the diene graft polymer. If the graft ratio is less than 40 %, it is difficult to obtain uniform particle sized white powder during coagulation and drying process and the glossy appearance is deteriorated due to fish eye, pinhole or sandsurface formation. Further, if the graft ratio is more than 70 %, the resulting product tends to be inferior in impact strength, flowability and glossy appearance. 4 The diene rubber to be used for the preparation of the diene graft polymer (A) includes polybutadiene, polyisoprene, polychloroprene, a butadiene-styrene copolymer, and a butadiene-acrylonitrile copolymer and so forth. Among them, polybutadiene, a butadiene-styrene copolymer, and a butadiene-acrylonitrile copolymer may be preferably used. The average rubber particle size of the diene rubber is preferably in the range of 0.1-0.6 [M, more preferably 0.2-0.5 ;m. If the average rubber particle size is less than 0.1 lm, the resin composition cannot provide a sufficient impact strength. On the other hand, if the average rubber particle size exceeds 0.6 //m, the glossy appearance is deteriorated. Examples of the vinyl cyanide compound for preparing the diene graft polymer (A) include acrylonitrile, methacrylonitrile and the like. These vinyl cyanide compounds can be used alone or in combination. Examples of the vinyl aromatic compound for preparing the diene graft polymer (A) include styrene, a -methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, vinyltoluene and the like. These vinyl aromatic compounds can be used alone or in combination. (B) Vinyl cyanide-vinyl aromatic copolymer having a weight-average molecular weight (Mw) of 100,000-200,000 The vinyl cyanide-vinyl aromatic copolymer (B) of the present invention is prepared by conventional polymerization such as emulsion, suspension, solution or bulk polymerization using 20-40 parts by weight of a vinyl cyanide compound and 80-60 parts by weight of a vinyl aromatic compound. The weight average molecular weight of the vinyl cyanide-vinyl aromatic copolymer (B) is preferably in the range of 100,000-200,000. If the weight average molecular weight of the copolymer is less than 100,000, although the flowability of the resin composition is improved, the resin composition cannot obtain sufficient impact strength and the product appearance is deteriorated due to pinholes and sandsurface formation. Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile 5 and the mixture thereof. These vinyl cyanide compounds can be used alone or in combination. Examples of the vinyl aromatic compound include styrene, a -methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, vinyltoluene and the mixture thereof. These vinyl aromatic compounds can be used alone or in combination. (C) Vinyl cyanide-vinyl aromatic copolymer having a weight-average molecular weight(Mw) of 200,000-600,000 The vinyl cyanide- vinyl aromatic copolymer (C) of the present invention is prepared by conventional polymerization such as emulsion, suspension, solution or bulk polymerization using 20-40 parts by weight of a vinyl cyanide compound and 80-60 parts by weight of a vinyl aromatic compound. The weight average molecular weight of the vinyl cyanide-vinyl aromatic copolymer (C) is preferably in the range of 200,000-600,000. If the weight average molecular weight of the copolymer is more than. 600,000, there is a difficulty in injection molding process due to a poor fluidity, and the value as a commercial product may be impaired. Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile and the mixture thereof. These vinyl cyanide compounds can be used alone or in combination. Examples of the vinyl aromatic compound include styrene, a -methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, vinyltoluene and the mixture thereof. These vinyl aromatic compounds can be used alone or in combination. (D) N-substituted maleimide copolymer The N-substituted maleimide copolymer (D) of the present invention is a copolymer prepared by copolymerizing 20-60 parts by weight of a mixture of maleic anhydride and N-substituted maleimide and 40-80 parts by weight of a vinyl aromatic compound and/or a vinyl cyanide compound. If the amount of the mixture of maleic anhydride and N-substituted maleimide is less than 20 parts by weight, the glass transition temperature of N-substituted maleimide 6 is lowered, accordingly, the resin composition is not sufficiently improved in impact strength. On the other hand, if the amount of a mixture of maleic anhydride and N-substituted maleimide is more than 60 parts by weight, the glass transition temperature become so high that the molding processing is difficult. Examples of the N-substituted maleimide include N-methyl maleimide, N-ethyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide and the mixture thereof. These N-substituted maleimides can be used alone or in combination. Examples of the vinyl aromatic compound include styrene, a -methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, vinyltoluene and the mixture thereof. These vinyl aromatic compounds can be used alone or in combination. Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile and the mixture thereof. These vinyl cyanide compounds can be used alone or in combination. The N-substituted maleimide (D) can be used in the amount of 1—30 parts by weight. If the amount is more than 30 parts by weight, a flowability of the resin composition is decreased, so that the practical application is limited. On the other hand, if the amount is less than 1 part by weight, volatile organic compound (VOC) content may be increased and the resin composition cannot obtain sufficient heat resistance. In the present invention, (A) is 15-30 parts by weight, (B)+(C) is 40-84 parts by weight, (D) is 1-30 parts by weight, and (B): (C) is from 0 : 100 to 80 : 20. If the amount of diene graft polymer (A) exceeds 30 parts by weight, the coefficient of linear thermal expansion of the resin composition is increased, so that the desired properties are not obtained. And if the amount of diene graft polymer (A) is less than 15 parts by weight, the impact strength is reduced, so that the resin composition is not suitable for use. The ratio by weight of (B) to (C) is from 0: 100 to 80 : 20. If the ratio by weight of (B) is more than 80, the impact resistance of the resin composition is reduced. Other additives may be contained in the resin composition of the present invention. The additives include an oxidation inhibitor, a lubricant, an impact modifier, a light stabilizer, a filler, an inorganic additive, pigment and/or dye. The invention may be better understood by reference to the following examples 7 which are intended for the purpose of illustration and are not to be construed as in any way limiting the scope of the present invention, which is defined in the claims appended hereto. In the following examples, all parts and percentage are by weight unless otherwise indicated. EXAMPLES Each component of (A), (B), (C) and (D) used in Examples and Comparative Examples was prepared as follow: (A) Diene graft polymer 58 parts by weight of butadiene rubber was added to 100 parts by weight of monomer mixture consisting of 25 % by weight of acrilonitrile and 75 % by weight of styrene, followed by grafting in emulsion polymerization to obtain graft ABS resin of core-shell type with a rubber particle size of 0.3 pm. (B) Vinyl cyanide-vinyl aromatic copolymer having a weight-average molecular weight (Mw) of 100,000-200,000 a -methylstyrene-acrylonitrile coplymer consisting of 28 % by weight of acrilonitrile and 72 % by weight of a -methylstyrene, and having a weight average molecular weight of 120,000 was used. (C) Vinyl cyanide- vinyl aromatic copolymer having a weight-average molecular weight(Mw) of 200,000-600,000 styrene-acrylonitrile coplymer consisting of 28 % by weight of acrilonitrile and 72 % by weight of styrene, and having a weight average molecular weight of 300,000 was used. (D) N-substituted maleimide copolymer 8 N-substituted maleimide copolymer consisting of 50 % by weight of styrene, 49 % by weight of N-phenyl maleimide and 1 % by weight of maleic anhydride, and having a weight average molecular weight of 160,000 was used. Example 1~4 The components as shown in Table 1 were mixed and the mixture was extruded together with 0.1 part by weight of octadecyl-3-(4-hydroxy-3,5-di-tert-butylphenyl) propionate as an antioxidant, 0.3 parts by weight of calcium stearate as a lubricant and 0.02 parts by weight of dimethyl polysiloxane as an impact modifier through a twin screw extruder with L/D=29 and Comparative Example 1 Comparative Example 1 was conducted in the same manner as in Example 1 except that the content of the diene graft polymer (A) was changed to 13 parts by weight and that of component (C) was changed to 32 parts by weight. Comparative Example 2 Comparative Example 2 was conducted in the same manner as in Example 1 except that the content of diene graft polymer(A) was changed to 32 parts by weight and that of component (C) was changed to 13 parts by weight. Comparative Example 3 Comparative Example 3 was conducted in the same manner as in Example 1 except that the content of component (B) was changed to 65 parts by weight and that of Component (C) was changed to 5 parts by weight. 9 Comparative Example 4 Comparative Example 4 was conducted in the same manner as in Example 1 except that the content of N-substituted maleimide copolymer (D) was changed to 35 parts by weight and that of component (B) was changed to 20 parts by weight. Comparative Example 5 Comparative Example 5 was conducted in the same manner as in Example 1 except that N-substituted maleimide copolymer (D) was not used and the content of component (B) was changed to 55 parts by weight. Table 1 (A)Diene graft polymer (B)a-methylstyrene-acrylonitrilecopolymer (C)styrene-acrylonitrile copolymer (D) N-substituted maleimide copolymer Examples 1 20 45 25 10 2 25 45 20 10 3 20 30 40 10 4 20 45 20 15 Comparative Examples 1 13 45 32 10 2 32 45 13 10 3 20 65 5 10 4 20 20 25 35 5 20 55 25 - The mechanical properties of the test specimens of Examples 1-5 and Comparative Examples 1-5 were measured as follow: (1) The notch Izod impact strength was measured in accordance with ASTM 10 D256(l/4" notched, 23 °C). (2) The melt flow index was determined in accordance with ISO 1133(10 kg, 220 °C). (3) The heat distortion temperature (HDT) was measured according to ASTM D648 (1/4", 120 °C/hr) under 18.5 kgf/cm2. (4) The coefficient of linear thermal expansion was measured by thermomechanical analyzer (TMA), varying the temperature from 30 to 80 °C at the rate ofl0°C/min. (5) total content of volatile organic compound (TVOC) was measured by using gas chromatography in accordance with VDA 277. The test results of Examples 1-5 and Comparative Examples 1-5 are shown in Table 2. Table 2 Izod impactstrength (kgf.cm/cm) melt flow index (g/l0min) HDT(0C) coefficient oflinear thermalexpansion(/lm)/m. °C) TVOC(ppm) Examples 1 10 3.0 100 68 209 2 14 2.8 99 71 215 3 11 3.0 100 67 172 4 9 2.5 102 70 164 Comparative Examples 1 5 3.5 101 64 198 2 19 2.0 97 79 212 3 7 3.1 102 70 295 4 6 1.5 112 67 157 5 8 2.7 95 68 314 As shown in Table 2, the composition of Comparative Example 1 which contained the diene graft polymer (A) less than 15 parts by weight showed a low coefficient of linear thermal expansion but exhibited poor impact strength. The 11 composition of Comparative Example 2 which contained the diene graft polymer (A) more than 30 parts by weight showed high coefficient of linear thermal expansion and good impact strength. The composition of Comparative Example 3 in which the ratio of (B): (C) fell outside the claimed range showed a poor impact strength. The composition of Comparative Example 4 which contained N-substituted maleimide copolymer (D) more than 30 parts by weight showed both impact strength and flowability were inferior. And, the composition of Comparative Example 5 not using N-substituted maleimide copolymer (D) showed inferior heat resistance and increased volatile organic compound content. The present invention can be easily carried out by an ordinary skilled person in the art. Many modifications and changes may be deemed to be with the scope of the present invention as defined in the following claims. 12 WE CLAIM 1. A thermoplastic resin composition comprising: (A) a diene graft polymer prepared by grafting in emulsion polymerization 100 parts by weight of a monomer mixture comprising 20-30% by weight of a vinyl cyanide compound and 70-80% by weight of a vinyl aromatic compound to 40-60 parts by weight of a diene rubber; (B) a vinyl cyanide-vinyl aromatic copolymer having a weight-average molecular weight (Mw) of 100,000-200,000 prepared by copolymerizing 20-40 parts by weight of a vinyl cyanide compound and 80-60 parts by weight of a vinyl aromatic compound; (C) a vinyl cyanide-vinyl aromatic copolymer having a weight-average molecular weight(Mw) of 200,000-600,000 prepared by copolymerizing 20-40 parts by weight of a vinyl cyanide compound and 80-60 parts by weight of a vinyl aromatic compound; and (D) an N-substituted maleimide copolymer; wherein (A) is 15-30 parts by weight, (B)+(C) is 40-84 parts by weight, (D) is 1-30 parts by weight and (B): (C) is from 0 : 100 to 80 : 20. 2. The thermoplastic resin composition as defined in claim 1, said N-substituted maleimide copolymer is prepared by copolymerizing 20-60 parts by weight of a mixture of maleic anhydride and N-substituted maleimide and 40-80 parts by weight of a vinyl aromatic compound and/or a vinyl cyanide compound. 3. The thermoplastic resin composition as defined in claim 1, wherein said diene rubber has an average particle size of 0.1-0.6 pm. 4. The thermoplastic resin composition as defined in claim 1, wherein said diene rubber is selected from the group consisting of polybutadiene, polyisoprene, polychloroprene, a butadiene-styrene copolymer, and a butadiene-acrylonitrile copolymer; said vinyl cyanide compound is selected from the group consisting of acrylonitrile, methacrylonitrile and the mixture thereof; said vinyl aromatic compound is selected from the group consisting of styrene, a -methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, 13 vinyltoluene and the mixture thereof; said N-substituted maleimide is selected from the group consisting of N-methyl maleimide, N-ethyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide. 5. The thermoplastic resin composition as defined in claim 1, wherein said graft polymer has a graft ratio of 40-70 % of grafting the polymer matrix of a vinyl cyanide-vinyl aromatic copolymer onto the acrylic rubber. 6. The thermoplastic resin composition as defined in claim 1, which further comprises an oxidation inhibitor, a lubricant, an impact modifier, a light stabilizer, a filler, an inorganic additive, a pigment and/or a dye. Dated this 10th day of November, 2006 FOR CHEIL INDUSTRIES INC By their Agents (GIRISH VIJAYANAND SHETH) KRISHNA &SAURASTRI 14 ABSTRACT The thermoplastic resin composition according to the present invention comprises (A) a diene graft polymer prepared by grafting in emulsion polymerization 100 parts by weight of monomer mixture comprising 20-30% by weight of vinyl cyanide compound and 70-80% by weight of vinyl aromatic compound to 40-60 parts by weight of diene rubber; (B) a vinyl cyanide- vinyl aromatic copolymer having a weight-average molecular weight (Mw) of 100,000-200,000 prepared by copolymerizing 20-40 parts by weight of vinyl cyanide compound and 80-60 parts by weight of vinyl aromatic compound; (C) a vinyl cyanide- vinyl aromatic copolymer having a weight-average molecular weight(Mw) of 200,000-600,000 prepared by copolymerizing 20-40 parts by weight of vinyl cyanide compound and 80-60 parts by weight of vinyl aromatic compound; and (D) a N-substituted maleimide copolymer prepared by copolymerizing 20-60 parts by weight of a mixture of maleic anhydride and N-substituted maleimide and 40-80 parts by weight of a vinyl aromatic compound and/or a vinyl cyanide compound, wherein (A) is 15-30 parts by weight, (B)+(C) is 40-84 parts by weight, (D) is 1-30 parts by weight, and (B) : (C) is from 0 : 100 to 80 : 20. The thermoplastic resin composition of the present invention has low coefficient of linear thermal expansion. 15

Documents:

1330-MUMNP-2006-ABSTRACT(4-12-2008).pdf

1330-mumnp-2006-abstract(complete)-(10-11-2006).pdf

1330-mumnp-2006-abstract(granted)-(30-3-2009).pdf

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1330-mumnp-2006-claims(granted)-(30-3-2009).pdf

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1330-MUMNP-2006-CORRESPONDENCE(10-11-2006).pdf

1330-mumnp-2006-correspondence(27-4-2007).pdf

1330-MUMNP-2006-CORRESPONDENCE(4-12-2008).pdf

1330-MUMNP-2006-CORRESPONDENCE(IPO)-(1-2-2008).pdf

1330-mumnp-2006-correspondence(ipo)-(31-3-2009).pdf

1330-mumnp-2006-description (complete).pdf

1330-mumnp-2006-description(complete)-(10-11-2006).pdf

1330-MUMNP-2006-DESCRIPTION(COMPLETE)-(4-12-2008).pdf

1330-mumnp-2006-description(granted)-(30-3-2009).pdf

1330-MUMNP-2006-FORM 1(10-11-2006).pdf

1330-MUMNP-2006-FORM 1(18-1-2007).pdf

1330-MUMNP-2006-FORM 18(13-11-2006).pdf

1330-mumnp-2006-form 2(4-12-2008).pdf

1330-mumnp-2006-form 2(complete)-(10-11-2006).pdf

1330-mumnp-2006-form 2(granted)-(30-3-2009).pdf

1330-MUMNP-2006-FORM 2(TITLE PAGE)-(4-12-2008).pdf

1330-mumnp-2006-form 2(title page)-(complete)-(10-11-2006).pdf

1330-mumnp-2006-form 2(title page)-(granted)-(30-3-2009).pdf

1330-mumnp-2006-form 3(12-2-2007).pdf

1330-MUMNP-2006-FORM 3(14-2-2007).pdf

1330-mumnp-2006-form 3(27-4-2007).pdf

1330-mumnp-2006-form-1.pdf

1330-mumnp-2006-form-18.pdf

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1330-mumnp-2006-form-3.pdf

1330-mumnp-2006-form-5.pdf

1330-mumnp-2006-form-pct-ipea-409.pdf

1330-mumnp-2006-form-pct-ipea-416.pdf

1330-mumnp-2006-pct-search report.pdf

1330-mumnp-2006-power of attorney(13-3-2007).pdf

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1330-mumnp-2006-wo international publication report(10-11-2006).pdf