JPH0441548A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in resistance to heat, impact, and chemicals, rigidity, and flowability by compounding a thermoplastic polyester resin, a specific ABS graft copolymer, and a compatibilizer comprising a specific maleimide copolymer. CONSTITUTION:The title compsn. comprises 30-70wt.% thermoplastic polyester resin, 30-70wt.% ABS graft copolymer, and 0.1-10wt.% maleimide copolymer. The ABS graft copolymer is prepd. by graft copolymerizing, onto a rubberlike polymer, a monomer component comprising an arom. vinyl monomer and a vinyl cyanide monomer or comprising these two monomers and another vinyl monomer copolymerizable with these monomers. The maleimide copolymer is prepd. by copolymerizing 0-30 pts.wt. rubberlike polymer with 70-100 pts.wt. monomer component comprising 30-65mol% arom. vinyl monomer, 25-50mol% unsatd. dicarboximide monomer, 1-15 mol% unsad. dicarboxylic anhydride monomer, and 0-20mol% other vinyl monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a thermoplastic resin composition having excellent heat resistance, impact resistance, chemical resistance, rigidity, and fluidity.

More specifically, the present invention relates to a polymer alloy of a thermoplastic polyester resin and an ABS-based graft copolymer containing a maleimide-based copolymer having a specific composition as a compatibilizer.

[Conventional technology]

Resin compositions in which ABS resin is mixed in order to improve the impact resistance of thermoplastic polyester resins have been known (Japanese Patent Laid-Open Nos. 50-3450, 56-14546, 57-137350, 1983). 61-297456) However, although the impact resistance of these resin compositions is improved, the degree of improvement is not necessarily sufficient, and they also have disadvantages of poor heat resistance and rigidity.

[Problems to be Solved by the Invention] Also known is a resin composition in which a maleimide copolymer is mixed for the purpose of improving the heat resistance of thermoplastic polyester resin under high loads (Japanese Unexamined Patent Publication No. 59-53547). Publication No.)
However, this resin composition has a drawback of poor impact resistance.

An object of the present invention is to provide a thermoplastic resin composition that eliminates the above-mentioned drawbacks and has excellent properties.

[Problem to be solved by the invention]

To summarize the present invention, the present invention relates to a thermoplastic resin composition, comprising: (a) thermoplastic polyester resin 3;
0 to 70% by weight, (b) 30 to 70% by weight of ABS-based graph graft copolymer, and (c) 0% of maleimide-based copolymer.
．． In a thermoplastic resin composition consisting of 1% by weight or more and less than 10% by weight, an aromatic vinyl monomer and a vinyl cyanide monomer, or an aromatic vinyl monomer and a vinyl cyanide monomer, or A copolymer obtained by copolymerizing a monomer and another vinyl monomer that can be copolymerized with the monomer,
The maleimide copolymer (c) contains 30 to 65 mol% of aromatic vinyl monomer residues, 25 to 50 mol% of unsaturated dicarboxylic acid imide monomer residues, and unsaturated dicarboxylic anhydride monomers. A copolymer consisting of 70 to 100 parts by weight of a monomer component consisting of 1 to 15 mol% of vinyl monomer residues and 0 to 20 mol% of other vinyl monomer residues and 0 to 30 parts by weight of a rubbery polymer. It is characterized by

As a result of intensive studies to solve the above problems, the present inventors have discovered that a maleimide copolymer contains aromatic vinyl monomer residues and unsaturated dicarboxylic acid imide monomer residues in a specific proportion. The compatibility of the ABS-based graph graft copolymer with the thermoplastic polyester resin is dramatically improved only when it contains a group, an unsaturated dicarboxylic acid anhydride monomer residue, and other vinyl monomer residues as necessary. By mixing a thermoplastic polyester resin, an ABS-based graph graft copolymer, and a maleimide-based copolymer in a specific ratio, a thermoplastic resin with excellent heat resistance, impact resistance, chemical resistance, rigidity, and fluidity can be obtained. The present invention was achieved by successfully obtaining a plastic resin composition.

The present invention will be explained in detail below.

First, (c) the maleimide copolymer and its manufacturing method will be explained.

In the present invention, the proportion of unsaturated dicarboxylic acid anhydride monomer residues in the maleimide copolymer is 1 to 15 mol% of the so-called ma) IJ hooks excluding the rubbery polymer.
It has two characteristics in that it is within the range of .

The first method for producing a maleimide copolymer is to use an aromatic vinyl monomer, an unsaturated dicarboxylic acid imide monomer, an unsaturated dicarboxylic anhydride monomer, in the presence of a rubbery polymer if necessary. A second method for copolymerizing a mixture of vinyl monomers and, if necessary, vinyl monomers copolymerizable with these monomers.
As a method for producing , a mixture of an aromatic vinyl monomer, an unsaturated dicarboxylic anhydride monomer, and, if necessary, a vinyl monomer copolymerizable with these, is used in the presence of a rubbery polymer if necessary. Examples include a method in which a polymerized polymer is reacted with ammonia and/or a primary amine (imidization reaction) to convert acid anhydride groups into imide groups.

Examples of the aromatic vinyl monomer include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene, and substituted monomers thereof, and among these, styrene is particularly preferred. .

Examples of unsaturated dicarboxylic acid imide monomers include maleimide, N-methylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-arylmaleimide (Aryl groups include, for example, phenyl, 4-diphenyl, 1- Maleimide derivatives such as naphthyl, 2-chlorophenyl, 4-bromophenyl and other halophenyl and dihalophenyl g-isomers, 2,4,6-) IJ dibromhenyl, methoxyphenyl, etc.), N-methylitaconimide and itaconic acid imide derivatives such as N-phenyl itaconic acid imide.
-Phenylmaleimide is preferred.

Examples of the unsaturated dicarboxylic anhydride monomer include anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, with maleic anhydride (maleic anhydride) being particularly preferred.

Vinyl monomers copolymerizable with these include vinyl monomers other than aromatic vinyl monomer residues, unsaturated dicarboxylic acid imide monomer residues, and unsaturated dicarboxylic acid anhydride monomer residues. Constitutes polymer residues, such as vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, acrylic acid ester monomers such as methyl acrylate and ethyl acrylate, and methyl methacrylate. Examples include acid esters, methacrylic acid ester monomers such as ethyl methacrylic ester, acryl amide, methacrylic acid amide, etc. Among these, monomers such as acrylonitrile and methacrylic ester are preferred.

Examples of rubbery polymers include butadiene polymers, copolymers of butadiene and copolymerizable vinyl monomers, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, and butadiene and aromatic vinyl monomers. Block copolymers of acrylic esters, acrylic ester polymers, and copolymers of acrylic esters and vinyl monomers copolymerizable therewith are used.

Furthermore, in the second production method, ammonia and primary amine used in the imidization reaction may be in either an anhydrous state or an aqueous solution state. Examples of primary amines include alkylamines such as methylamine, ethylamine, butylamine, and cyclohexylamine; aromatic amines such as chloro- or bromine-substituted alkylamines; aniline, tolylamine, and naphthylamine; Examples include substituted aromatic amines such as substituted aniline, and among these, aniline is particularly preferred.

Furthermore, when the imidization reaction is carried out in a solution or suspension state, it is preferable to use a normal reaction vessel such as an autoclave, and when it is carried out in a bulk molten state, an extruder equipped with a devolatilization device is used. Good too. Further, a catalyst may be present during imidization, and for example, a tertiary amine or the like is preferably used.

The temperature of the imidization reaction is usually about 80 to 350°C, preferably 100 to 300°C.

If the temperature is less than 80°C, the reaction rate will be slow and the reaction will take a long time, making it impractical, while if it exceeds 350°C, the physical properties will deteriorate due to thermal decomposition of the polymer.

The maleimide copolymer contains 0 to 30 parts by weight, preferably 0 to 20 parts by weight, of a rubbery polymer, 30 to 65 mol%, preferably 40 to 65 mol%, of aromatic vinyl monomer residues, and unsaturated Dicarboxylic acid imide monomer residue 25-50 mol%
, preferably from 25 to 40 mol%, from 1 to 15 mol%, preferably from 5 to 15 mol%, of unsaturated dicarboxylic anhydride monomer residues, and from 0 to 20 mol% of other vinyl monomer residues. It is a copolymer consisting of 70 to 100 parts by weight of the constituent monomer components.

If the amount of the comb-like polymer exceeds 30 parts by weight, thermal properties, moldability and dimensional stability will be impaired.

If the amount of aromatic vinyl monomer residue is less than 30 mol %, moldability and dimensional stability will be impaired, and if it exceeds 0.5 mol %, heat resistance will decrease.

If the amount of unsaturated dicarboxylic acid imide monomer residue is less than 25 mol %, heat resistance will be impaired, and if it exceeds 50 mol %, moldability and dimensional stability will decrease.

Furthermore, if the amounts of the aromatic vinyl monomer residue and the unsaturated dicarboxylic acid imide monomer residue are outside the composition range described in 1., the function of the maleimide copolymer as a compatibilizer will be reduced.

The amount of unsaturated dicarboxylic anhydride monomer residues is important;
If it is less than mol%, the solubility between the thermoplastic polyester resin and the ABS-based graphograft copolymer will be insufficient, and the impact strength of the final composition will be reduced. If it exceeds 15 mol%, the reaction with the terminal hydroxyl groups in the thermoplastic polyester resin will be excessive, resulting in a decrease in fluidity. When the thermoplastic resin composition of the present invention was observed under an electron microscope, it was confirmed that ABS-based graph graft copolymer plastic polyester resin (IJ Fuchs) was present in finely dispersed form as particles with a particle diameter of 0.1 to 1 μm. can.

It is presumed that because of this morphology, the thermoplastic resin composition of the present invention has excellent heat resistance, impact resistance, chemical resistance, rigidity, and fluidity. In order to form such a morphology, the amount of unsaturated dicarboxylic anhydride monomer residues needs to be in the range of 1 to 15 mol%.

In addition, the amount of vinyl monomer residues other than aromatic vinyl monomer residues, unsaturated dicarboxylic acid imide monomer residues, and unsaturated dicarboxylic acid anhydride monomer residues exceeds 20 mol%. dimensional stability and heat resistance are impaired.

Next, (b) the ABS-based graft copolymer is prepared by adding an aromatic vinyl monomer and a vinyl cyanide monomer, or those monomers, to the comb-like polymer. It is formed by copolymerizing other copolymerizable vinyl monomers, and examples of the rubbery polymer include the same rubbery polymers exemplified as maleimide copolymers.

Examples of aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene,
Examples include styrene monomers such as chlorostyrene and substituted monomers thereof.

Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile.

Vinyl monomers that can be copolymerized with these are vinyl monomers other than aromatic vinyl monomers and vinyl cyanide monomers,
For example, acrylic ester monomers such as methyl acrylic ester and ethyl acrylic ester, methacrylic ester monomers such as methyl methacrylic ester and ethyl methacrylic ester, acrylic acid amide, methacryl seikomide, and maleimide copolymers. Examples include the unsaturated dicarboxylic acid imide monomers exemplified by the combination.

A preferable composition of the ABS-based graph graft copolymer is 30 to 70 parts by weight, preferably 40 to 60 parts by weight of a rubbery polymer, and 35 to 65 mol%, preferably 4 parts by weight, of an aromatic vinyl monomer.
5 to 65 mol%, vinyl cyanide monomers 35 to 55 mol%, preferably 40 to 50 mol%, and other vinyl monomers copolymerizable with these monomers 0 to 20 mol%. , preferably composed of 0 to 10 mol% monomer component 30
~70 parts by weight.

Next, examples of the thermoplastic polyester resin (a) include polybutylene terephthalate resin, polyethylene terephthalate resin, and mixtures thereof.

The proportion of the thermoplastic polyester resin, ABS-based graph graft copolymer, and maleimide-based copolymer contained in the thermoplastic resin composition of the present invention is 30% of the thermoplastic polyester resin.
-70% by weight, preferably 35-65% by weight, 30-70% by weight of ABS-based graft copolymer or 35-70% by weight
65% by weight, maleimide copolymer 0.1% by weight or more 1
It is less than 0% by weight, preferably 0.5% by weight or more and less than 5% by weight. If the thermoplastic polyester resin is less than 30% by weight, chemical resistance, rigidity and fluidity will be reduced, and if it exceeds 70% by weight, impact resistance will be reduced. If the ABS-based graphograft copolymer is less than 0% by weight, the impact strength will decrease, and if it exceeds 70% by weight, the chemical resistance, rigidity and fluidity will decrease.

If the maleimide copolymer content is less than 0.1% by weight, the impact strength, heat resistance and rigidity will be reduced, and if it is more than 10% by weight, the fluidity will be reduced and the impact strength will also be reduced. The proportion of maleimide copolymer contained in the composition of the present invention is important;
．． If it is less than 1% by weight, it is considered to be an insufficient amount to exhibit the effect as a compatibilizer and form a useful morphology. At 10% by weight or more, heat resistance and rigidity improve as the content of the maleimide copolymer increases, but the amount acting as a compatibilizer on the surface of the thermoplastic polyester resin and ABS graph graft copolymer becomes excessive, and on the contrary, This results in a decrease in impact strength.

In order to obtain the thermoplastic resin composition of the present invention, the above (a)
There is no particular restriction on the method of mixing the components (i) and (e), and any known means can be used. Examples of the means include a Banbury mixer-tumbler mixer, a mixing roll, a single-screw or twin-screw press ratio machine, and the like. Mixing forms include normal melt mixing, multi-stage melt mixing using master pellets, etc., and solution blending.

The thermoplastic resin composition of the present invention further includes antioxidants, flame retardants, antistatic agents, ultraviolet absorbers, plasticizers, lubricants, fillers such as glass fibers, carbon fibers, and calcium carbonate, colorants, It is also possible to add metal powder or the like.

Further, other resins and elastomers may be added depending on the purpose. Specifically, AS resin, polyamide,
Examples include resins such as polycarbonate and polyphenylene ether, and elastomers such as acrylic rubber, ethylene propylene rubber, and styrene-butadiene rubber. especially,
AS resin is preferably used because it has good compatibility with the thermoplastic resin composition of the present invention. The amount of these other resins and elastomers added is preferably 50 parts by weight or less, preferably 0 to 25 parts by weight, based on 100 parts by weight of the thermoplastic resin composition.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.
The invention is not limited to these examples.

Note that all parts and percentages in the examples are expressed on a weight basis.

Examples 1 to 7 and Comparative Examples 1 to 6 (1) Maleimide copolymer Styrene 100 was placed in an autoclave equipped with a stirrer.
After preparing the mixture and replacing the inside of the agitated bobbin thread with nitrogen gas,
It was heated to a temperature of 80°C. To this, 67 parts of maleic anhydride,
02 parts of benzoyl peroxide to 3 parts of methyl ethyl ketone
00 parts of the solution was added over a period of 8 hours. After the addition, the temperature was maintained at 80°C for an additional 4 hours to complete the polymerization reaction.

Next, 1.2B of triethylamine and 45 parts of triethylamine were added, and an imidization reaction was carried out at 150°C for 10 hours. The reaction solution was cooled to 100° C. and purged into a stainless steel vat.

Next, vacuum drying was performed at 180° C. for 3 hours, and after removing the solvent, a pulverization treatment was performed to obtain a powdery copolymer.

According to C-C-13N analysis, the conversion rate of maleic anhydride groups to imide groups was 70.8 mol%, and the content of imide derivative residues in the copolymer was 28.3 mol%. This copolymer was designated as A-1.

Other unsaturated dicarboxylic acid imide copolymers (A2-8-4
) is also A except that the conversion rate of maleic anhydride groups to imide groups was adjusted by adjusting the amount of aniline added.
It was created in the same way as -1.

Next, a method for producing an unsaturated dicarboxylic acid imide copolymer containing a rubbery polymer will be described.

Styrene 100 in an autoclave equipped with a stirrer
1 part, 50 parts of methyl ethyl ketone, and 24 parts of polybutadiene rubber cut into small pieces (Asahi Kasei Co., Ltd., NF35AS) were added, and after IPY was exchanged in the system with nitrogen gas, the rubber was dissolved by stirring at room temperature overnight. After setting the temperature to 80℃,
6'7 parts of maleic anhydride and 0.0 parts of benzoyl peroxide.
A solution of 3 parts dissolved in 400 parts of methyl ethyl ketone is
It was added continuously over time. After addition, further 4 hours at 80°C
The polymerization reaction was completed by maintaining the temperature at After the imidization reaction, A-
It was created in the same manner as 1.

The unsaturated dicarboxylic acid imide copolymer containing this rubbery polymer is designated as A and -5, and the compositions of A-1 to A-5 are shown in Table 1.

Table 1 (2) 80 parts of ABS-based graph graft copolymer butadiene latex (solid content 50%, average particle size 0.35μ, gel content 90%) 1 part sodium stearate, 0.1 part sodium formaldehyde sulfoxylate , 0.03 parts of EDTA tetrasodium salt, 0.003 parts of ferrous sulfate, and 200 parts of water were charged into an autoclave purged with nitrogen gas. After heating the temperature to 65°C, 50 parts of a monomer mixture consisting of 30% acrylonitrile and 70% styrene, 0.3 part of t-dodecyl mercaptan, and 0.2 part of cumene hydroperoxide were added to 4 parts of cumene hydroperoxide.
The mixture was added continuously over a period of time, and after the addition was completed, polymerization was further carried out at 65° C. for 2 hours. The grafting rate was 80% and the polymerization rate was 98%.

After adding an antioxidant to the obtained latex, it was salted out with calcium chloride, washed with water, and dried to obtain a white powdery copolymer. This graft copolymer was designated as B-1.

Also, instead of 50 parts of a monomer mixture consisting of 30% acrylonitrile and 70% styrene, 2 parts of acrylonitrile
B-2 was a graft copolymer obtained in the same manner as B-1 except that 50 parts of a monomer mixture consisting of 5% styrene, 65% styrene, and 10% methyl methacrylate was used. The grafting rate of B-2 was 78%, and the polymerization rate was 97%.

(3) Thermoplastic polyester resin Commercially available polybutylene terephthalate resin [Tubadol 5
010J [manufactured by Mitsubishi Kasei ■] was used. It is set as C-1.

Maleimide copolymers A-1 to A-5) ABS graph graft copolymers-1, B-2) and polybutylene terephthalate resin (c-1) are blended at your company as shown in Table 2, and this blend is The material was extruded at 250° C. using a 35 m/m twin-screw directional rotary extruder equipped with a devolatilizer to pelletize it.

The blend also contains octadecyl as an antioxidant.
0.25 part of 3-(3',5'-di-t-butyl-4'hydroxyphenyl)propionate was contained. Using this pellet, a test piece for measuring physical properties was prepared at 240° C. using an injection molding machine, and various physical properties were measured. The results are shown in Table 2.

The measurement methods for various physical properties in Table 2 are as follows.

Heat resistance: The heat distortion temperature (HDT) was measured according to ASTM D-648 using an injection molded product with a thickness of 174' under a load of 4.6 kg/cm2.

Impact strength: Notched isot measurements were made on injection molded articles having a thickness of 178' in accordance with ASTM D-256. The ambient temperature was 23℃.

Fluidity: Melt flow rate (VFR) was measured at a temperature of 265° C. and a load of 10 kg in accordance with 8STM D-1238.

Stiffness In accordance with ASTM D-790, a 178' thick injection molded article was subjected to a bending test and the bending modulus (BM) was measured.

Chemical resistance: As shown in FIG. 1, an ASTM D-6381 dumbbell was bent, kerosene was applied to the dumbbell, and it was observed after being left at room temperature for 24 hours. Dumbbells with no cracks or crazes were rated ○, and those with these were rated x.

In addition, FIG. 1 is an explanatory diagram showing a test method for chemical resistance of a resin obtained from a resin composition, and the reference numeral 1 means a jig and 2 means an ASTM D-6381 dumbbell.

〔Effect of the invention〕

As explained above, the resin obtained from the thermoplastic resin composition of the present invention has excellent heat resistance, impact resistance, fluidity, rigidity, and chemical resistance. In particular, the resin obtained from the thermoplastic resin composition of the present invention has extremely high impact strength and has high practical value as a material for various industrial parts and vehicle exterior parts.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram showing a method for testing the chemical resistance of a resin obtained from a resin composition. 1.Jig 2...^STM D-6381 Dumbbell Patent applicant: Denki Kagaku Kogyo Co., Ltd. Agent: Sadako Nakamoto
Akito Inoue
Yoshimine Katsura ASTM ＼ No. 7 Ribenbell

Claims (1)

[Claims] 1. (a) Thermoplastic polyester resin 30-70% by weight
, (b) 30 to 70% by weight of ABS-based graft copolymer,
and (c) maleimide copolymer 0.1% by weight or more 10
In a thermoplastic resin composition consisting of less than % by weight, the (
b) The ABS-based graft copolymer is a rubbery polymer containing an aromatic vinyl monomer and a cyanated vinyl monomer, or these monomers and other copolymerizable monomers. It is a copolymer obtained by copolymerizing vinyl monomers, and the maleimide copolymer (c) contains 30 to 65 mol% of aromatic vinyl monomer residues and unsaturated dicarboxylic acid imide monomer residues. Group 25-5
0 mol%, unsaturated dicarboxylic anhydride monomer residue 1-1
It is characterized by being a copolymer consisting of 70 to 100 parts by weight of a monomer component consisting of 5 mol% and 0 to 20 mol% of other vinyl monomer residues and 0 to 30 parts by weight of a rubbery polymer. A thermoplastic resin composition.