JPS62179571A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To improve thermal stability and impact resistance, by adding a hindered phenol compd. to a thermoplastic resin contg. a polymer having an imide group on its side chain. CONSTITUTION:A resin compsn. contains 80-99.95pts.wt. thermoplastic resin contg. a polymer having an imide group on its side chain and 0.05-20pts.wt. hindered phenol compd. Examples of the polymer having an imide group on its side chain are polymers obtd. by imidating a copolymer obtd. by polymerizing an arom. vinyl monomer with an unsaturated dicarboxylic acid anhydride in the presence or absence of a rubber polymer. Examples of the thermoplastic resin are an acrylonitrile/butadiene copolymer, nylon 6, polysulfone, etc. Examples of the hindered phenol compd. are 2,2'-methylene-bis(4-ethyl-6-t- butylphenol); 4,4'-thiobis(3-methyl-6-t-butylphenol), etc.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a thermoplastic resin composition with improved thermal stability and impact resistance, and more specifically, a thermoplastic resin composition comprising a polymer having an imide group in the side chain and a hindered phenol. The composition of the present invention relates to a thermoplastic resin composition containing a type compound as an essential component, and the composition of the present invention can be preferably used for automobile parts, electric/electronic parts, office equipment parts, heating appliances, and the like.

(Prior Art and Problems) The manufacturability of polymers having imide groups in their side chains has been known for some time. (U.S.P. 3,840,499゜U.S.
P 3,998,907) Compositions in which impact resistance is improved by blending rubber grafts or polycarbonate with polymers having imide groups in side chains are also known. (
USP 3,652,726, USP 3.642,
949, Japanese Patent Publication No. 49-12576) Although these polymers having imide groups in their side chains have high heat distortion temperatures,
It has the drawbacks of poor impact resistance and poor color tone due to heat retention. In addition, impact resistance of compositions blended with rubber grafts or polycarbonate has been improved to some extent, but it is still not sufficient. After conducting a study, we were able to successfully obtain a thermoplastic resin composition in which impact resistance was significantly improved by adding a hindered phenol compound, and at the same time, no deterioration in color tone due to heat retention was observed. Deroru.

The present invention provides a thermoplastic resin composition characterized by containing 80 to 99.95 parts by weight of a thermoplastic resin containing a polymer having an imide group in its side chain and 0.05 to 20 parts by weight of a hindered phenol compound. It is a thing.

In the present invention, the polymer having an imide group in the side chain includes 1) a copolymer obtained by polymerizing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride in the presence or absence of a rubbery polymer; Imidized polymer, 11) A copolymer obtained by polymerizing an aromatic vinyl monomer, an unsaturated dicarboxylic acid anhydride, and a vinyl monomer copolymerizable with these in the presence or absence of a rubbery polymer. 111) A polymer obtained by imidizing a copolymer obtained by polymerizing an olefin and an unsaturated carboxylic acid in the presence or absence of a rubbery polymer, 1v) Presence of a rubbery polymer ■) A polymer obtained by imidizing a copolymer obtained by polymerizing a monomer copolymerizable with acrylic acid and/or methacrylic acid in the presence or absence of a rubber-like polymer. aromatic vinyl monomer,
A polymer obtained by polymerizing maleimide and/or N-substituted maleimide, (1) Aromatic vinyl monomer, maleimide and/or N-substituted maleimide, and co-polymerized maleimide and/or N-substituted maleimide in the presence or absence of a rubbery polymer. There are polymers made by polymerizing polymerizable vinyl monomers.

Aromatic vinyl monomers used in the production process of polymers having imide groups in their side chains include nostyrene monomers and their substituted monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene. Among these, styrene is particularly preferred.

As the unsaturated dicarboxylic anhydride, anhydrides such as maleic acid, itaconic acid, citraconic acid, aconitic acid, and maleic anhydride are particularly preferred.

Vinyl monomers that can be copolymerized with these include vinyl cyanide monomers such as acrylonitrile, methacrylatetrile, and α-chloroacrylonitrile; acrylic acid ester monomers such as methyl acrylate and ethyl acrylate; There are methacrylic acid ester monomers such as methyl methacrylic acid ester and ethyl methacrylic acid ester, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide, and methacrylic acid amide. Among these, acrylonitrile and methacrylate Monomers such as acid esters, acrylic acid, and methacrylic acid are preferred.

Examples of N-substituted maleimide include N-methylmaleimide, N
-Butylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-chlorophenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-cyclohexylmaleimide , maleimide derivatives such as N-isopropylmaleimide, itaconic acid imide derivatives such as N-methyl itaconic acid imide, N-phenyl itaconic acid imide, etc. Among these, N-phenyl maleimide is particularly preferred.

In addition, as the thermoplastic resin containing a polymer having an imide group in a side chain in the present invention, acrylonitrile-butadiene-styrene and/or α-methylstyrene copolymer, methyl methacrylate-butadiene-
Styrene copolymer, acrylonitrile-ethylene/propylene-styrene copolymer, acrylonitrile-acrylic rubber-styrene copolymer, acrylonitrile-styrene and/or α-methylstyrene copolymer, rubber-modified styrene polymer, polycarbonate, styrene- butadiene book copolymer, polybutylene terephthalate,
Polyethylene terephthalate, nylon-6, nylon 6.6. Examples include thermoplastic resins containing one or more polymers selected from polyphenylene sulfide, polysulfone, and the like.

Of course, the thermoplastic resin containing a polymer having an imide group in its side chain also includes a polymer alone having an imide group in its side chain.

In the present invention, examples of the hindered phenol compound added to the thermoplastic resin containing a polymer having an imide group in a side chain include the following.

2.2'-methylene-bis-(4-ethyl-6-t-butylphenol).

2.2'-methylene-bis-(4-methyl-6-t-butylphenol), 2-t-butyl-6-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4 -methylphenylacrylate, 4,4'-butylidene-bis-(3-methyl-6-t-
butylphenol), triethylene glycol-bisC3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate].

1.6-hexanethiolupis (3-(3゜5-di-
t-Butyl-4-hydroxyphenyl)propionate, pentaerythrityl-tetrakis(3-(3゜5-di-
t-butyl-4-hydroxyphenyl)propionate], 2.2-thio-diethylenebisC3-(3゜5-di-t
-butyl-4-hydroxyphenyl)propionate]
, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propione).

N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamite)
, 3.5-di-t-butyl-4-hydroxy-penzyl phosphonate diethyl ester.

1.3.5-)limethyl-2,4,6-trisC3,5
-di-t-butyl-4-hydroxybenzyl)benzene, ], 3.51 lis(3,5-di-t-butyl-4-
hydroxybenzyl)-8'-) riazine-2,4,6
-(II(,3I(,5)1)-trion, 1.3.5-) squirrel (3',5'-
di-t-butyl-4-hydroxybenzyl)
Incyanurate, 1.1.3-tris(2-methyl-4-hydroxy-5
-butylphenyl)butane, tetrakis-[methylene-3-(3',5'-t-7'thyl-4'-hydroxyphenyl)propionate]methane, hexamethylene glycol bis[β-(3゜5 -C
t-phthyl-4-hydroxy-phenyl]propionate, tris[β-(3,5-di-t-butyl-4-hydroxyphenyl]propionyl-oxyethylcoin cyanurate, 2,2'-thio-diethyl-bis -(3(3゜5-ji-
t-butyl-4-hydroxyphenyl)propionate], 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bis-octyl-thio-1,3,5-triazine, 4. 4'-thiobis(3-methyl-6-t-butylphenol), 4.4'-methylene-bis(2,6-di-t-butylphenol), 2.6-di-t-butyl-4-methylphenol, Examples include 2.6-di-t-butyl-4-ethylphenol and 2.6-di-t-butyl-4-phenylphenol, and two or more types may be used in combination.

The amount of the hindered phenol compound used in the present invention is 0.05 to 2 parts by weight per 80 to 99.95 parts by weight of the thermoplastic resin containing the polymer having imide groups in the side chain.
A more preferable iF′i0.1 of the hindered phenol compound is 0 parts by weight and the total of both is 100 parts by weight.
If the amount of the hindered phenol compound Noil is less than 0.05 parts by weight, the impact resistance of the composition and the color stability during heat retention are insufficiently improved. On the other hand, if the amount of the hindered phenol compound exceeds 20 parts by weight, the heat deformation resistance of the composition will be significantly reduced and the mechanical strength will also be reduced.

The composition of the present invention is a mixture of a thermoplastic resin containing a polymer having an imide group in its side chain and a hindered phenol compound, but the mixing method is not particularly limited and any known means may be used. can. Examples of the means include a Banbury mixer, a tumbler mixer, a Henschel mixer, a mixing roll, a screw-screw or twin-screw extruder, and the like. Mixing forms include normal melt mixing, multi-stage melt mixing using master pellets, etc., and solution blending.

In addition, the composition of the present invention may further include other phenolic antioxidants, organic sulfur antioxidants, phosphite antioxidants, flame retardants, ultraviolet absorbers, plasticizers, lubricants, glass fibers, carbon fibers, and calcium carbonate. It is also possible to add fillers such as, colorants, metal powders, etc.

The composition of the present invention is used in applications requiring thermal stability and impact resistance, such as automobile parts, electrical/electronic parts,
This applies to household electrical equipment, office equipment, etc.

Experimental Example (1) 60 parts of styrene and 100 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, and after purging the system with nitrogen gas, the temperature was raised to 85°C, and 40 parts of maleic anhydride was charged.
A solution of 0.15 parts of benzoyl peroxide and 0.15 parts of benzoyl peroxide dissolved in 7200 parts of methyl ethyl ketone was added continuously over 8 hours.

The temperature was maintained at 85° C. for an additional 3 hours after the addition. A portion of the viscous reaction solution was sampled and unreacted monomers were determined by gas chromatography. As a result, the polymerization rate was 95% for styrene and 98% for maleic anhydride. To the copolymer solution obtained here, 38.0 parts of aniline and 0.3 parts of triethylamine, which are equivalent to maleic anhydride, were added.
The reaction was carried out at 0°C for 7 hours. 200 parts of methyl ethyl ketone was added to the reaction solution, cooled to room temperature, poured into 1,500 parts of vigorously stirred methanol, precipitated, separated and dried to obtain an imidized polymer.

This is designated as A-1.

Experimental Example (2) Styrene 60 was placed in the same autoclave as Experimental Example (1).
100 parts of methyl ethyl ketone, and 10 parts of polybutadiene cut into small pieces were charged and stirred at room temperature overnight to dissolve the rubber, then the system was replaced with nitrogen gas and the temperature was raised to 85°C.
The temperature rose to .

40 parts of maleic anhydride and 0.0 parts of benzoyl peroxide.
075 parts and azobisisobutyronitrile 0.075 parts
A solution of 200 parts of methyl ethyl ketone was added continuously over 8 hours.

From this point on, exactly the same operations as in Experimental Example (1) were performed.

The polymerization rate is styrene 9696. The amount of maleic anhydride was 98%. This is designated as A-2.

Experimental example (3) 100 parts of styrene in an autoclave equipped with a stirrer,
After charging 50 parts of methyl ethyl ketone and purging the system with nitrogen, the temperature was raised to 83°C, and 100 parts of N-phenylmaleimide,
A copolymer was obtained by carrying out the same operation as in Experimental Example (1), except that a solution of 0.2 parts of benzoyl peroxide dissolved in 400 parts of methyl ethyl ketone was continuously added over a period of 8 hours.

The M unit ratio was 96% for tri-suylene and 95% for N-phenylmaleimide. This will be referred to as Polymer A-3.

Experimental example (4) Styrene 60 was placed in the same autoclave as experimental example (1).
parts, 10 parts of acrylonitrile, 50 parts of methyl ethyl ketone
A solution of 30 parts of maleic anhydride and 0.15 parts of azobisisobutyronitrile dissolved in 250 parts of methyl ethyl ketone was added continuously over 9 hours.
The procedure was exactly the same as in Experimental Example (1) except that 27.0 parts of chlorine was used. The polymerization rate was 99% for styrene, 92% for acrylonitrile, and 96% for maleic anhydride.

This will be referred to as Polymer A-4.

Experimental Example (5) 143 parts of polybutadiene latex (solid content 35 cm, weight average particle size 0.35 μ, gel content 90%), 1 part potassium stearate, 0.1 part sodium formaldehyde sulfoxylate, tetra Sodium ethylenediaminetetraacetic acid 0.03 part, ferrous sulfate 0.00
3 parts and 50 parts of water were heated to 50°C, and to this was added 50 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile, 0.2 part of t-dodecylmercaptaf, and 0.15 parts of cumene hydroperoxide. After the addition, the temperature was raised to 65° C. and polymerization was carried out for 2 hours. The polymerization rate reached 97% according to gas chromatography analysis.

After adding an antioxidant to the obtained latex, it was coagulated with calcium chloride, washed with water, and dried to obtain a graft copolymer as a white powder. This is indicated as ABS.

Example 1 60 parts of imidized copolymer A- obtained in Experimental Example (]), 40 parts of ABS obtained in Experimental Example (5) and 2-t-butyl-6-13'-t-butyl- 5'-methyl-2'-
After mixing 1 part of 1-methylphenylacrylate (hydroxybenzyl) in a Hennel mixer, the mixture was extruded and pelletized in a vented extruder.

The physical properties of the composition thus obtained are shown in Table 1.

Examples 2 to 4 The imidized copolymers obtained in Experimental Examples (2) to (4) and the ABS obtained in Experimental Example (5) were blended, respectively, and Example 1 was prepared.
The physical properties were measured in the same manner as above and are shown in Table 1.

Example 5 The same procedure as in Example 1 was carried out using only the imidized copolymer obtained in Experimental Example (2).

Examples 6 to 8 The same procedures as in Example were carried out except that ABS and acrylonitrile-styrene copolymer (AS) were used in combination, and polycarbonate and nylon-6 were used instead of ABS in Example.

Examples 9 to 12 The same procedure as in Example 1 was carried out except that the hindered phenol compound of Example 1 was replaced with one various hindered phenol compound.

Comparative Examples 1 to 4 Comparative Examples 1 to 4 were carried out in the same manner except that the hindered phenol compound used in Examples 1 to 4 was not used.

Table 1 shows that the compositions of the present invention are significantly improved in impact resistance and retention heat stability compared to compositions containing no hindered phenol compound.

The physical properties were measured by the following method.

(]) Impact resistance... Notched Izot strength, AS
According to TMD-256.

(2) Vicat softening point...Load 5 Kf -AS
According to TMD-1525.

(3) Retention Mature Woman: Changes in color tone of molded products injection molded at 280°C were visually determined.

○: Almost no change in color tone.

X: Yellowing is clearly observed.

Claims (1)

[Scope of Claims] It is characterized by containing 80 to 99.95 parts by weight of a thermoplastic resin containing a polymer having an imide group in its side chain, and 0.05 to 20 parts by weight of a hindered phenol compound. Thermoplastic resin composition.