JPS6173753A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having high rigidity, excellent mechanical properties and moldability and improved impact resistance, by blending a polyether ester amide with an ABS resin or on MBS resin. CONSTITUTION:A polyether ester amide is prepared from a 6C or higher aminocarboxylic acid or lactam or a salt of a dicarboxylic acid with a 6C or higher amine (i), a poly(alkylene oxide) glycol (ii) having a number-average MW of 300-6000 and a 4-20C dicarboxylic acid (iii). 40-1pt.wt. said polyether ester amide is blended with 60-99pts.wt. ABS or MBS resin.

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 styrenic resins, especially A, which consists of a resin phase and a rubber phase.
BS or 1VBs resin is tough, has excellent impact resistance and mechanical properties, has high rigidity, and has excellent chemical resistance.

Moreover, it has good finishing workability and metal plating is also possible. For this reason, demand for automotive and electrical equipment applications is increasing, but since there is a limit to impact resistance, the purpose is to impart a high degree of impact resistance to ABS and MBS resins that have excellent mechanical properties and moldability. shall be.

Means for Solving the Problems> The above-mentioned object of the present invention is to provide at least one selected from aromatic vinyl (a), acrylic ester (b), and methacrylic ester (c) and cyanide. Aromatic vinyl (a), acrylic ester (1) and methacrylic ester (c) are added to a random copolymer (polymer A) derived from vinyl (d) and a rubbery polymer (e). An aminocarboxylic acid or lactam having 6 or more carbon atoms,
Or a salt of diamine and dicarboxylic acid having 6 or more carbon atoms (
f), a poly(alkylene oxide) glycol (g) having a number average molecular weight of 300 to 6,000, and a polyether ester amide (polymer C) derived from a dicarboxylic acid having 4 to 20 carbon atoms (th). This can be achieved by blending the resin composition in an amount of more than 1 part and less than 40 parts.

The configuration, embodiments, and effects of the present invention will be described in detail below.

The aromatic vinyl (a) of polymer A in the present invention includes styrene, α-methylstyrene, vinyltoluene, p-
Examples include methylstyrene and pt-butylstyrene, and styrene and α-methylstyrene are particularly preferred, and these can also be used in combination.

In addition, acrylic ester Q]), methacrylic ester (c) includes methyl acrylate, ethyl acrylate,
Examples include methyl methacrylate and ethyl methacrylate, with methyl methacrylate being preferably used. Examples of vinyl cyanide (d) include acrylonitrile and methacrylonitrile.

3 as the copolymerized amount of vinyl cyanide (d) in polymer A
~50% is suitable.

The polymerization method for polymer A is not particularly limited, and known methods such as bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, and bulk-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), Examples include acrylic rubbers such as butyl acrylate and polyolefin rubbers such as ethylene-propylene-nonconjugated diene terpolymer rubber (EPDM). A preferred rubbery polymer is polybutadiene.

Aromatic vinyl (a), acrylic ester (b), methacrylic ester (c) and vinyl cyanide (d)
Examples include those explained in connection with the polymer A above. The copolymerization amount of the rubbery polymer (e) in the polymer B is preferably 5 to 80%.

In the graft component, the total amount of one or more selected from aromatic vinyl (a), acrylic ester (1)) and methacrylic ester (c) is 50 to 97% by weight, and vinyl cyanide is used. (d) is preferably 3 to 50% by weight.

The polymerization method for polymer B is not particularly limited, and known methods such as bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, and bulk-suspension polymerization can be used.

Salts of aminocarboxylic acids or lactams having 6 or more carbon atoms or diamines and dicarboxylic acids having 6 or more carbon atoms in the polyetheresteramide (polymer C) of the present invention (
f) is an amine carboxylic acid such as ω-aminocaproic acid, ω-amine enanthate, ω-amitsukaglylic acid, ω-aminopelargonic acid, ω-aminecapric acid, +1-aminoundecanoic acid, 12-aminododecanoic acid, or Lactams such as cabronlactam, enantlactam, capryllactam, laurolactam, and hexamethylenediamine-adipate, hexamethylenediamine-sepacate, hexamethylenediamine-isophthalate, undecamethylenediamine-adipate, 4 .4'
There are salts of diamine dicarboxylic acids such as -diaminodicyclohexylmethane dodecanedate, especially 11-
Aminoundecanoic acid and 12-aminododecanoic acid are preferred, and these may 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 polyneedle ester amide or increasing adhesiveness.

Examples of the poly(alkylene oxide) glycol (2)) having a number average molecular weight of 300 to 6,000 in the polyether ester amide (polymer C) of the present invention include polyethylene glycol, poly(1°2- and 1.3- Examples include propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, etc. Poly(tetramethylene oxide) glycol is preferably used because of the excellent physical properties of polyether ester amide, such as heat resistance, water resistance, mechanical strength, and elastic recovery.

The number average molecular weight of poly(alkylene oxide) glycol can be used in the range of 300 to 6,000, 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. The molecular weight range varies depending on the type of poly(alkylene oxide) glycol. For example, in the case of polyethylene glycol, 300-6,
000, particularly preferred); i 1,000-4,00
3 if 0 is poly(propylene oxide) glycol
00-5,000. Particularly preferably 500 to 3,000
However, in the case of poly(tetramethylene oxide) glycol, it is 500 to 3.0001, particularly preferably 500 to 2.
, 500 are preferably used.

Examples of dicarboxylic acids (th) having 4 to 20 carbon atoms in the polyether ester amide (polymer C) of the present invention include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl Aromatic dicarboxylic acids such as -4,4'-dicarboxylic acid, diphenoxyethane dicarboxylic acid, sodium 3-sulfoisophthalate, 1,4-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, synchromequinol 4. Mention may be made of alicyclic dicarboxylic acids such as 4'-dicarboxylic acid, and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedioic acid (decanedicarboxylic acid). In particular, dicarboxylic acids such as terephthalic acid, isophthalic acid, lI4-cyclohexanedicarboxylic acid, sebacic acid, and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone, and physical properties of the polymer = 8-.

In order for the effect of the present invention to be particularly noticeable in the middle stage, the copolymerization amount of poly(alkylene oxide) glycol (2) in the polyether ester amide (polymer C) must be 5 to 5.
90% by weight is preferred. If the copolymerization amount is 5% by weight, flexibility and elastic recovery properties are lost, and if it exceeds 90% by weight, the high temperature properties and mechanical properties are 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 (th) to create a polyamide prepolymer with carboxylic acid groups at both ends, and then poly(alkylene oxide) glycol (2)) is reacted with this under vacuum. Alternatively, the compounds of (f), (g), and th) above are charged into a reaction tank and heated to react at high temperature in the presence or absence of water to produce a carboxylic acid-terminated polyamide prepolymer, A method is known in which the polymerization is then proceeded under normal pressure or reduced pressure. In addition, the above (f), (g
There is also a method in which the compounds () and (h) are simultaneously charged into a reaction tank, melt-polymerized, and then polymerized 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 needs to exceed that of the 5-layer division. If the amount of polymer C is 40 parts by weight or more, the rigidity of the ABS1MBS resin will be impaired, and if it is less than 1 part by weight, the brightness and impact resistance of the present invention will not be sufficiently imparted.

The resin composition of the present invention is preferably melt-kneaded, and a known method can be used for the melt-kneading method. For example, a resin composition can be prepared by melt-kneading the resin composition using a Pant-Lee mixer, a rubber roll machine, a -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 A1
Polymer B and polymer C can be blended together, or polymer A and polymer B can be blended and then polymer C can be blended therewith.

The resin composition of the present invention also contains known antioxidants, thermal decomposition inhibitors, ultraviolet absorbers, hydrolysis resistance improvers, colorants (
pigments, dyes), antistatic agents, conductive agents, flame retardants, reinforcing agents,
Fillers, lubricants, nucleating agents, preforming agents, plasticizers, adhesion aids, adhesives, and the like can be optionally contained.

The present invention will be explained below with reference to Examples. In the examples, unless otherwise specified, the number of parts means the number of parts.

<Example> Polymer A The copolymer composition and abbreviation of Polymer A used in Examples are as follows.

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

PBD: Polybutadiene rubber = 12- 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 into a reaction vessel equipped with a helical ribbon stirring blade together with 0.5 parts of ``Irganox'' 1098 (antioxidant). After cumulative purging and heating and stirring at 260°C for 1 hour to obtain a homogeneous transparent solution, 0.015 parts of antimony dioxide catalyst, 0.015 parts of motuputyl monohydroxytin oxide catalyst, and 0.0 part of phosphoric acid were added.
0.05 parts (anti-coloring agent) were added and the vacuum program was followed to bring the polymerization conditions below 1 wwHy in 1 hour.

When the reaction was carried out under these conditions for 2.5 hours, a viscous colorless and transparent molten polymer was obtained, and when this polymer was discharged into water as a gut, it crystallized and turned white. The obtained polyether ester amide (c-1) has a relative viscosity (η
r) is 1.81, and the crystal melting point by DSC is 167.
It was ℃.

Polymerization of polymer (c-2) 49.1 parts of ω-aminododecanoic acid, 7.9 parts of terephthalic acid
48.8 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 1020, "Irganox°
'10980.5 parts, antimony trioxide 0.015 parts,
Polyether ester amide with a relative viscosity of 1.9-3 and a melting point of 154°C ( c-2) was obtained.

Polymerization of polymer (c-3) 27.3 parts of ω-aminododecanoic acid, 5.7 parts of terephthalic acid
5 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 2060, 10980.5 parts of Irganox, 0.015 parts of antimony dioxide
Polyether ester amide (1.92% relative viscosity, 145°C melting point) was polymerized under the same conditions as polymer (c-1) from 0.015 parts of motuputyl monohydroxytin oxide and 0.005 parts of phosphoric acid. c-3) was obtained.

44.9 parts of polymerized undecamethylenediamine-adipate of polymer (c-4),
12.8 parts of terephthalic acid, 50.0 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 650,
Irganox n10980.5 parts, trioxide 7y thymoy
0.015 parts, motuputyl monohydroxytin oxide 0
．． 015 parts of phosphoric acid and 0.005 parts of phosphoric acid to polymer (c
Polymerization was carried out under the same conditions as -1), and the relative viscosity was 1.80. A polyether ester amide (c-4) having a melting point of 209°C was obtained.

Examples 1-10. Comparative Examples 1 to 5 (Comparative Examples 6 to IO will be described later) When using Polymer A and Polymer B together, Polymer A and Polymer B were mixed in advance and extruded with 3 3 zzφ heated to 220°C. The mixture was melted and kneaded in a machine and then pelletized.

As shown in the table, Polymer A and/or Polymer B (A
When using A and B in combination, mix the polymer (A-1), (A-2), (A-3) or (A-4) with a mixture of A and B in advance, and heat at 220°C. In, polymer (A-4)
When using a 30mm extruder heated to 240°C, the mixture was melt-kneaded and then pelletized. When using polymers (A-1), (A-2) and (A-3), the obtained pellets were molded using an injection molding machine having an injection capacity of 5 oz. ) at 240℃,
Further, the JI No. 52 tensile test piece and the Izot impact test piece were molded at a mold temperature of 40°C. ASTM D-63
Tensile properties were measured according to 8 and Izod impact energy 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 mixed, and then pelletized.

The tensile properties and Izot impact energy were measured in the same manner as in Examples 1-10 and Comparative Examples 1-5. The results are shown in the table.

As seen in Examples 1 to IO, 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 I to 5, when the blending ratio of Polymer C is 40 parts by weight or more with respect to 100 parts by weight of the resin composition,
The inherent rigidity of AB31MBS resin is lost.

<Effects of the Invention> According to the present invention, a resin composition having high impact resistance while retaining the cocoon-like properties and excellent mechanical properties of AB51MBS resin can be obtained.

Patent application Daitoshi Co., Ltd. QQ-

Claims (1)

[Claims] Random copolymer (polymer A) derived from at least one selected from aromatic vinyl (a), acrylic ester (b) and methacrylic ester (c) and vinyl cyanide (d) 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). Aminocarboxylic acid or lactam having 6 or more carbon atoms for an amount exceeding 60 parts by weight and less than 99 parts by weight of at least one kind of polymer selected from the graft copolymers (polymer B) , or a salt of diamine and dicarboxylic acid having 6 or more carbon atoms (f), number average molecular weight 300 to 6,0
00 poly(alkylene oxide) glycol (g),
and a polyether ester amide (polymer C) derived from a dicarboxylic acid (h) having 4 to 20 carbon atoms.
A resin composition containing more than 40 parts by weight but less than 40 parts by weight.