JPS61101547A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having excellent processability and resistance to low-temperature impact and heat, consisting of a graft polymer and a maleimide copolymer. CONSTITUTION:10-80pts.wt. graft polymer (A) composed of 10-90pts.wt. at least one member selected from among an arom. vinyl monomer, an unsaturated monomer, a (meth)acrylate monomer and a maleimide monomer and 90-10pts. wt. rubbery polymer, wherein graft rubber has a weight-average particle size of 0.03-0.29mum and a graft ratio of 20-90% and ungrafted polymer in the graft polymer has an intrinsic viscosity of 0.3-1.0, is blended with 90-20pts.wt. copolymer (B) having an intrinsic viscosity of 0.4-1.3 and a Q value (a ratio of weight-average MW to number-average MW) of 4 or above, composed of 1-60pts.wt. maleimide monomer, 99-40pts.wt. at least one monomer selected from among an arom. vinyl monomer, an unsaturated nitrile monomer and a (meth)acrylate and 0-30pts.wt. copolymerizable monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Object of the Invention The present invention relates to a resin composition that has an excellent balance of impact resistance, processability, and heat resistance, and also has excellent impact resistance at low temperatures.

α-
The heat-resistant ABS resin, which is made by blending methylstyrene-based polymer and furyic anhydride-based copolymer, has been known for a long time.
) (For example, "ABS resin" published by the Society of Polymer Science and Technology in 1972)
However, such heat-resistant ABS resins have the disadvantage of being susceptible to thermal decomposition during molding. Furthermore, as the field of use expands, compositions with even better heat resistance are required.

In recent years, maleimide copolymers with excellent heat resistance and thermal decomposition resistance have attracted attention, but maleimide copolymers are significantly inferior in impact resistance and processability. For this reason,
One method is to polymerize maleimide with another vinyl compound in the presence of a rubbery polymer. One method is to improve impact resistance by mixing a maleimide-based copolymer with a graft polymer of rubber and a vinyl compound. has been proposed, but it still has problems such as poor workability. (Unexamined Japanese Patent Publication No. 57
On the other hand, compositions with improved processability by mixing a maleimide copolymer with a styrene-acrylonitrile copolymer have been proposed, but they still have poor impact resistance. There are problems. (Unexamined Japanese Patent Publication No. 58-217535
, JP-A-58-217537) As a result of research in view of the above-mentioned problems, the present inventors have found that a composition comprising a limide copolymer and a graft polymer having a specific intrinsic viscosity and Q value is excellent. We discovered that this material has excellent impact resistance, processability, and heat resistance, and filed a patent application earlier. As a result of extensive research into not only the structure of maleimide copolymers, but also the composition and structure of graft polymers, the present inventors first found a specific graft polymer and mixed it with a specific copolymer. The composition has superior impact resistance compared to the base composition.

The present invention was achieved by discovering that it has processability and heat resistance as well as excellent impact resistance at low temperatures.

The present invention will be explained in detail below.

■ Structure of the invention Graft polymer (N) The graft polymer (A) used in the present invention is an aromatic vinyl monomer, an unsaturated nitrile monomer, (meth)
A graft polymer consisting of one or more monomer components selected from acrylic acid ester monomers and 7-reimide monomers and a rubber-like polymer, the graft rubber weight average particle diameter of 0.03 to 0.29 μm
1 craft ratio is 20 to 70%, and the intrinsic viscosity of the ungrafted polymer contained in the graft polymer is 0.3 to 70%.
It is a graft polymer with a molecular weight of 1.0.

In the present invention, a graft polymer having a specific value as described above is used, and in graft polymerization, the entire amount of the above monomer components is bonded (grafted) to a rubbery polymer.
It is difficult to achieve this, and it generally contains ungrafted polymers that are produced as by-products during graft polymerization.

Examples of aromatic vinyl monomers used as one of the monomer components include styrene, α-methylstyrene, α-chlorostyrene, p-butylstyrene, p-methylstyrene, and 0-chlorostyrene. , p-chlorostyrene, 2.
Examples include 5-dichlorostyrene and 3,4-dichlorostyrene.

Examples of unsaturated IJ monomers include acrylonitrile, methacrylonitrile, maleonitrile, and fumaronitrile.

Examples of (meth)acrylic acid ester monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate,
Benzyl (meth)acrylate, hexyl (meth)acrylate, lauryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, etc. nru.

Examples of maleimide monomers include maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-2,3
or 4-methylphenyl 7reimide, N-2,3 maf
c is 4-ethyl/l/maL/imide, N-2,3'i
j 4-7" tylphenylmaleimide, N-2,6-simethyllimide, N-2,327'CH4-chlorophenyl7reimide, 3'1ftlri4-qL-romophenylmaleimide, N-2,5-dichloromaleimide , N-3,4
-dichloromaleimide, N-2,5-dibromomaleimide, N-3,4-dibromomaleimide, N-2,4,6
-) Lichlorobroimide, N-2,4,6-dripromomaleimide, N
-2,3 or 4-hydroxyphenylmaleimide, N
-2, 3i friend is 4-methoxyphenylmaleimide, N-
2, 3fi friend is 4-carpoxyphenylimide, N-
4-nitrophenylmaleimide), N-4-diphenylimide, N-1-naphthylphenyl 7-reimide, N
-4-cyanophenyl 7-reimide, N-4-phenoxyphenyl male (mi)'', N-4-benzylphenyl reimide, N-2-methyl-5 chlorophenyl male)
”, N-2-methoxy-5-chlorophenylmaleimide, etc., and one or more types thereof are used. Preferably, N
-substituted limide=i), 4'! Examples of the rubbery polymer which is KN-phenylmaleimide include diene rubbers such as polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer, and ethylene-propylene-nonconjugated diene. Examples include ethylene-propylene rubber such as a copolymer, chlorinated polyethylene, acrylic rubber, ethylene-vinyl acetate copolymer, and ethylene-methyl acrylate copolymer.

Graft polymers (methods for obtaining N include known emulsion polymerization methods, suspension polymerization methods, bulk polymerization methods, solution polymerization methods, emulsion-suspension polymerization methods, bulk-suspension polymerization methods, emulsion-bulk polymerization methods, etc.) are mentioned.

Regarding the structure of the graft polymer, the weight average particle diameter of the graft rubber is 0.03 to 0.29 μm, and the graft ratio is 20.
~70%, and the intrinsic viscosity of the ungrafted polymer (dimethylformamide solution, 30°C) is 0.3~1. Limited to O.

Here, the weight average particle diameter of the graft rubber is 0.03 μm.
If it is less than that, not only will it not be possible to obtain a product with high impact strength, but also the melt flowability will be markedly reduced, resulting in poor processing properties. On the other hand, even if the weight average particle diameter exceeds 0.29 μm, it is difficult to obtain a material with high impact strength.

Furthermore, if the intrinsic viscosity of the ungrafted polymer is less than 0.3, it will not be possible to obtain a product with high impact strength, while if it is greater than 1.0, processability will be poor. Note that the gel content of the graft rubber is preferably 80% or more. In addition, the ratio of monomer component/rubber-like polymer of the graft polymer is 10 to 90/
The range is preferably from 90 to 10 (parts by weight).

0 copolymer (uniform) The copolymer (B) used in the present invention is the above-mentioned 7
1 to 60 parts by weight of a leimide monomer, an aromatic vinyl monomer, an unsaturated monomer, an IJ monomer, and a (meth)
It consists of 99 to 40 M parts of one or more monomer components selected from acrylic acid ester monomers.

If the composition ratio is outside this range, the object of the present invention will not be achieved, but the impact strength will decrease.

The maleimide copolymer can be produced by direct copolymerization of a limide monomer and the above various monomers, or by imidization of a copolymer of maleic anhydride and the above various monomers. can. Examples of polymerization methods include bulk polymerization, solution polymerization, bulk-suspension polymerization, suspension polymerization, and emulsion polymerization. Additionally, during the polymerization, if necessary, 30 parts by weight or less of a monomer copolymerizable with the above monomers may be added.

Furthermore, C (what is important in the present invention is the copolymer (B)
The intrinsic viscosity (measured at 30° C. in a dimethylformamide solution) is 0.4 to 13, and the Q value (M weight average molecular weight/number average molecular weight) is 4.0 or less.

If the intrinsic viscosity is less than 0.4, the mechanical strength will decrease, and if it exceeds 1 or 3, the processability will be markedly poor, which is not preferable. ″
Moreover, when the Q value exceeds 4.0, mechanical strength decreases.

From the mechanical strength, processability, and ease of polymerization of the copolymer, it is particularly important that the intrinsic viscosity is 0.5 to 0.9 and the Q
Preferably, the value is between 1.5 and 3.5.

A method for obtaining a copolymer whose intrinsic viscosity and Q value fall within these ranges is to change the type and amount of the polymerization catalyst and molecular weight modifier used during copolymerization, the method of their addition, the polymerization temperature, etc. can be mentioned.

Note that the Q value can be determined by gel permeation chromatography.

θ composition ratio The composition of the present invention is composed of the above-mentioned graft polymer (A) and copolymer (B), and there is no particular restriction on the composition ratio, but the composition ratio is not particularly limited. In terms of balance, kraft polymer (~lO~80 parts by weight, copolymer (B)
), preferably 90 to 20 parts by weight.

The 0-mix graft polymer (8) and the copolymer (B) can be mixed using a known mixer such as a Banbury mixer, 1-screw extruder, or a twin-screw extruder.

Alternatively, they can be mixed in latex form and recovered as a composition.

In addition, known stabilizers, antistatic agents, lubricants,
Additives such as dyes and pigments may be added as appropriate.

In addition, other thermoplastic resins such as polycarbonate, polyester, polyamide, polyphenylene oxide, polyetherney f k'! may be added to the composition of the present invention as appropriate depending on the purpose of use. ), polyethersulfone, polysulfone, polyoxymethylene, etc. can be blended.

Examples will be described below, but the present invention is not limited to these in any way.

It should be noted that all numbers of parts and weights shown in Examples and Comparative Examples are based on weight unless otherwise specified.

Examples and Comparative Examples Graft polymer particles and copolymers (B) shown in Tables 1 to 2 were synthesized by a known emulsion polymerization method, and
After melt-kneading in Banbury mixer, 25 in injection molding machine.
Test pieces were prepared at 0 to 300°C and their physical properties were measured. The results are shown in Tables 1 and 2.

Effects of the Invention The graft polymer (A) of the present invention having a specific particle size, graft ratio, and intrinsic viscosity, a specific amount of a 7-reimide monomer, and a copolymer (B) having a specific intrinsic viscosity and Q value. The resin composition has excellent impact resistance, processability and heat resistance.

Claims (1)

[Claims] One or more monomer components selected from aromatic vinyl monomers, unsaturated nitrile monomers, (meth)acrylic acid ester monomers, and maleimide monomers; A graft polymer consisting of a rubber-like polymer, wherein the weight average particle diameter of the graft rubber is 0.03 to 0.29.
μm, the grafting ratio is 20 to 70%, and the intrinsic viscosity of the ungrafted polymer contained in the grafted polymer is 0.
3 to 1.0, 1 to 60 parts by weight of a maleimide monomer and an aromatic vinyl monomer,
99 to 40 parts by weight of one or more monomer components selected from unsaturated nitrile monomers and (meth)acrylic acid ester monomers, and copolymerizable with these monomers A copolymer ( B)
A resin composition consisting of.