JPH0558022B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a resin composition having high rigidity, excellent mechanical properties and moldability, and high impact resistance. <Prior art> Among styrene resins, ABS or MBS resins, which are made up of a resin phase and a rubber phase, are particularly strong and have excellent impact resistance and mechanical properties, as well as high rigidity and chemical resistance. Furthermore, it has good workability and can be metal plated. Therefore, automotive applications,
Demand is increasing for electrical applications, but its applications are limited due to its limited impact resistance. <Problems to be Solved by the Invention> The purpose of the present invention is to solve the above-mentioned drawbacks and to impart a high degree of impact resistance to ABS and MBS resins, which have high rigidity, excellent mechanical properties, and moldability. do. <Means for Solving the Problems> The above object of the present invention is to provide at least one selected from aromatic vinyl (a), acrylic ester (b) and methacrylic ester (c) and vinyl cyanide. Random copolymer (polymer A) derived from (d) and rubbery polymer (e)
A graft copolymer (polymer B) in which vinyl cyanide (d) is graft-polymerized with at least one selected from aromatic vinyl (a), acrylic ester (b), and methacrylic ester (c). For an amount exceeding 60 parts by weight but less than 99 parts by weight of at least one kind of polymer selected from the following, aminocarboxylic acids or lactams having 6 or more carbon atoms, or diamines and dicarboxylic acids having 6 or more carbon atoms. A polyether ester amide (polymer C) derived from an acid salt (f), a poly(alkylene oxide) glycol (g) having a number average molecular weight of 300 to 6000, and a dicarboxylic acid having 4 to 20 carbon atoms (h) This can be achieved by creating a resin composition containing more than 1 part by weight and less than 40 parts by weight. The configuration, embodiments, and effects of the present invention will be described in detail below. Examples of the aromatic vinyl (a) of the polymer A in the present invention include styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, and pt-butylstyrene, with styrene and α-methylstyrene being particularly preferred. These can also be used together. Examples of the acrylic ester (b) and methacrylic ester (c) include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate, with methyl methacrylate being preferably used. Examples of vinyl cyanide (b) include acrylonitrile and methacrylonitrile. The appropriate copolymerized amount of vinyl cyanide (d) in Polymer A is 3 to 50% by weight. The polymerization method for polymer A is not particularly limited, and includes bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization.
Known methods such as suspension polymerization can be used. The rubbery polymer (e) of polymer B in the present invention includes diene rubbers such as polybutadiene rubber, styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber (NBR), polyacrylic acid Examples include acrylic rubbers such as butyl and polyolefin rubbers such as ethylene-propylene-nonconjugated diene terpolymer rubber (EPDM). A preferred rubbery polymer is polybutadiene. Examples of the aromatic vinyl (a), acrylic ester (b), methacrylic ester (c) and vinyl cyanide (d) include those explained in connection with the polymer A above. The copolymerization amount of rubbery polymer (e) in polymer B is 5
~80% by weight is preferred. In the graft component, the total of one or more selected from aromatic vinyl (a), acrylic ester (b), and methacrylic ester (c) is 50 to 97
% by weight, and vinyl cyanide (d) is preferably 3 to 50% by weight. The polymerization method for polymer B is not particularly limited, and includes bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization.
Known methods such as suspension polymerization can be used. Examples of the aminocarboxylic acid or lactam having 6 or more carbon atoms or the diamine and dicarboxylic acid salt (f) having 6 or more carbon atoms in the polyether ester amide (polymer C) of the present invention include ω-aminocaproic acid, ω-aminocaproic acid, Aminocarboxylic acids such as enanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, or caprolactam, enantholactam, capryllactam, laurolactam, etc. lactams and diamines such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate, hexamethylenediamine-isophthalate, undecamethylenediamine-adipate, 4,4'-diaminodicyclohexylmethane-dodecanedioate Although there are salts of -dicarboxylic acids, 11-aminoundecanoic acid and 12-aminododecanoic acid are particularly preferred, and these can also be used in combination depending on the purpose and use. It is also permissible to use other amide-forming components as copolymerization components in small amounts for the purpose of lowering the melting point of polyether ester amide or increasing adhesiveness. The poly(alkylene oxide) glycol (g) having a number average molecular weight of 300 to 6000 in the polyether ester amide (polymer C) of the present invention includes:
Polyethylene glycol, poly(1,2- and 1,3-propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide, ethylene oxide and tetrahydrofuran Block or random copolymers of
Poly(tetramethylene oxide) glycol is preferably used because of the excellent physical properties of polyether ester amide, such as elastic recovery. The number average molecular weight of poly(alkylene oxide) glycol can be used in the range of 300 to 6000, but a molecular weight range that does not cause coarse phase separation during polymerization and has excellent low temperature properties and mechanical properties is selected, and this optimum molecular weight range is selected. varies depending on the type of poly(alkylene oxide) glycol. For example, in the case of polyethylene glycol, it is 300 to 6000, particularly preferably 1000 to
When 4000 is poly(propylene oxide) glycol, 300 to 5000, particularly preferably 500 to 3000,
In the case of poly(tetramethylene oxide) glycol, those having a molecular weight in the range of 500 to 3,000, particularly preferably 500 to 2,500 are preferably used. The dicarboxylic acids (h) having 4 to 20 carbon atoms in the polyether ester amide (polymer C) of the present invention include terephthalic acid, isophthalic acid, naphthalene-
Aromatic dicarboxylic acids such as 2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, sodium 3-sulfoisophthalate, 1,4- cyclohexanedicarboxylic acid,
Alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid, and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, and dodecanedioic acid (decanedicarboxylic acid). Acids may be mentioned. In particular, dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone, and physical properties of the polymer. In order for the effects of the present invention to be exhibited most significantly, the copolymerization amount of poly(alkylene oxide) glycol (g) in the polyether ester amide (polymer C) is preferably 5 to 90% by weight. If the copolymerization amount is less than 5% by weight, flexibility and elastic recovery properties will be lost, and if it exceeds 90% by weight, high temperature properties and mechanical properties will be insufficient. The method for polymerizing polyether ester amide (polymer C) is not particularly limited, and any known method can be used. For example, an aminocarboxylic acid or lactam (f) is reacted with a dicarboxylic acid (h) to create a polyamide prepolymer with carboxylic acid groups at both ends, and this is then injected with poly(alkylene oxide) glycol (g).
A method of reacting under vacuum, or (f) above,
The compounds (g) and (h) are charged into a reaction tank and reacted by heating at high temperature in the presence or absence of water to produce a carboxylic acid-terminated polyamide prepolymer, and then heated under normal pressure or reduced pressure. Methods for advancing polymerization are known. In addition, the compounds (f), (g), and (h) above are charged into a reaction tank at the same time, and after melt polymerization,
There is also a method of proceeding with polymerization all at once under high vacuum, but this method is preferable since it causes less coloring of the polymer. In the present invention, the blending ratio of at least one or more polymers selected from Polymer A and Polymer B and Polymer C is less than 40 parts by weight and more than 1 part by weight, preferably less than 40 parts by weight. The amount must exceed 5 parts by weight. If the amount of polymer C is 40 parts by weight or more, the rigidity of the ABS or MBS resin will be impaired, and if it is less than 1 part by weight, the high impact resistance of the present invention cannot be sufficiently imparted. The resin composition of the present invention is preferably melt-kneaded, and known methods can be used for melt-kneading. For example, the resin composition can be prepared by melt-kneading using a Banharry mixer, a rubber roll machine, a single-screw or twin-screw extruder, etc., usually at a temperature of 100 to 300°C. When polymer A and polymer B are used together and blended with polymer C, the order of blending is not particularly limited. For example, polymer A, polymer B, and polymer C may be blended simultaneously, or polymer A and polymer C may be blended together. After blending the polymer B, the polymer C can also be blended therewith. The resin composition of the present invention also includes known antioxidants, thermal decomposition inhibitors, ultraviolet absorbers, hydrolysis resistance improvers, colorants (pigments, dyes), antistatic agents, conductive agents, flame retardants, and reinforcing agents. Agents, fillers, lubricants, nucleating agents, mold release agents, plasticizers, adhesion aids, adhesives, etc. can be optionally contained. The present invention will be explained below with reference to Examples. In the examples, unless otherwise specified, parts mean parts by weight. <Example> Polymer A The copolymer composition and abbreviation of Polymer A used in Examples are as follows.

[Table] Polymer B The copolymer composition and abbreviation of Polymer B used in Examples are as follows.

[Table] Original copolymer rubber reference example Production of polymer C Polymerization of polymer (C-1) ω-aminododecanoic acid 81.9 parts, dodecanedioic acid
6.8 parts of poly(tetramethylene oxide) glycol and 19.3 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of 650 were charged together with 0.5 parts of "Irganox" 1098 (antioxidant) into a reaction vessel equipped with a helical ribbon stirring blade, and the mixture was purged with nitrogen and heated at 260°C. After heating and stirring for 1 hour to obtain a homogeneous transparent solution, 0.015 parts of antimony trioxide catalyst, 0.015 parts of monobutyl monohydroxytin oxide catalyst,
0.005 parts of phosphoric acid (anti-coloring agent) was added and the polymerization conditions were brought to below 1 mmHg in 1 hour according to a vacuum program. When reacted under these conditions for 2.5 hours, a viscous colorless and transparent molten polymer was obtained.
When this polymer was discharged into water as a gut, it crystallized and turned white. The obtained polyether ester amide (C-1) had a relative viscosity (ηr) measured in orthochlorophenol at 25°C at a concentration of 0.5%.
1.81, and the crystal melting point by DSC was 167°C. Polymerization of polymer (C-2) 49.1 parts of ω-aminododecanoic acid, terephthalic acid
7.9 parts, 48.8 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 1020, 0.5 parts of "Irganox" 1098, 0.015 parts of antimony trioxide,
0.015 parts of monobutyl monohydroxytin oxide,
and 0.005 part of phosphoric acid under the same conditions as Polymer (C-1) to obtain polyetheresteramide (C-2) having a relative viscosity of 1.93 and a melting point of 154°C. Polymerization of polymer (C-3) ω-aminododecanoic acid 27.3 parts, terephthalic acid
5.7 parts, 70.5 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 2060, 0.5 parts of "Irganox" 1098, 0.015 parts of antimony trioxide,
0.015 parts of monobutyl monohydroxytin oxide,
and 0.005 part of phosphoric acid under the same conditions as Polymer (C-1) to obtain polyetheresteramide (C-3) having a relative viscosity of 1.92 and a melting point of 145°C. Polymerization of polymer (C-4) Undecamethylenediamine-adipate 44.9
12.8 parts of terephthalic acid, 50.0 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 650.
1 part, "Irganox" 1098 0.5 part, antimony trioxide 0.015 part, monobutyl monohydroxytin oxide 0.015 part, and phosphoric acid 0.005 part under the same conditions as Polymer (C-1), and the relative viscosity was 1.80.
Polyether ester amide (C-
4) was obtained. Examples 1 to 10, Comparative Examples 1 to 5 (Comparative Examples 6 to 10 will be described later) When using polymer A and polymer B together, mix polymer A and polymer B in advance,
The mixture was melt-kneaded in a 30 mmφ extruder heated to ℃ and then pelletized. As shown in the table, polymers (A-1), (A-2),
Mix (A-3) or (A-4) and heat to 220℃.
When the polymer (A-4) was used, it was melt-kneaded in a 30 mm diameter extruder heated to 240 DEG C. and then pelletized. The obtained pellets were molded into polymers (A-1) and (A-1) using an injection molding machine with an injection capacity of 5 oz.
2) and (A-3) at 220℃,
When (A-4) was used, JIS No. 2 tensile test pieces and Izot impact test pieces were molded at 240°C and the mold temperature was 40°C. The tensile properties were measured according to ASTM D-638, and the Izod impact energy was measured according to ASTM D-256. The results are shown in the table. Comparative Examples 6 to 10 When Polymer A and Polymer B were used together, Polymer A and Polymer B were mixed, melted and kneaded, and then pelletized. And Examples 1 to 10, Comparative Examples 1 to
Tensile properties and Izot impact energy were measured in the same manner as in Example 5. The results are shown in the table. As seen in Examples 1 to 10, the resin composition of the present invention has rigidity and excellent mechanical properties, and is also imparted with a high degree of impact resistance. As seen in Comparative Examples 1 to 5, when the blending ratio of Polymer C is 40 parts by weight or more to 100 parts by weight of the resin composition, the inherent rigidity of ABS and MBS resins is lost.

【table】

[Table] *1 The blending ratio represents parts by weight.
*2 Izotsu impact value is the value with 1〓2″ V notch.
*3 NB indicates non-destructive.
<Effects of the Invention> According to the present invention, a resin composition having high impact resistance while retaining the rigidity and excellent mechanical properties of ABS and MBS resins can be obtained.

Claims (1)

[Claims] 1 Random copolymer derived from vinyl cyanide (d) and at least one selected from aromatic vinyl (a), acrylic ester (b) and methacrylic ester (c) ), and at least one selected from aromatic vinyl (a), acrylic ester (b) and methacrylic ester (c) and vinyl cyanide (d) are graft polymerized to the rubbery polymer (e). An aminocarboxylic acid having 6 or more carbon atoms or Lactam or a salt of diamine and dicarboxylic acid having 6 or more carbon atoms (f), poly(alkylene oxide) glycol (g) having a number average molecular weight of 300 to 6000, and 4 carbon atoms
A resin composition comprising a polyether ester amide (polymer C) derived from a dicarboxylic acid (h) of ~20 in an amount exceeding 1 part by weight and less than 40 parts by weight.