JPS62100551A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:A composition, consisting of polyphenylene ether, maleimide based copolymer, aromatic vinyl compound/conjugated diene block copolymer and styrene based resin and having well-balanced heat and impact resistance and moldability. CONSTITUTION:A thermoplastic resin composition obtained by incorporating (A) 10-80wt% polyphenylene ether, preferably having 0.3-0.7dl/g intrinsic viscosity [eta] measured in chloroform at 30 deg.C with (B) 5-80wt% maleimide based copolymer, prepared by polymerizing 15-70wt% N-substituted maleimide and 30-85wt% aromatic vinyl compound in the presence or absence of a rubber and having preferably 0.05-0.5dl/g intrinsic viscosity [eta] measured in methyl ethyl ketone at 30 deg.C, (C) 1-60wt% aromatic vinyl compound-conjugated diene block copolymer having preferably 50,000-500,000 weight-average molecular weight and (D) 0-75wt% styrene based resin. The preferred compounding ratios of the respective components are as follows; 56-70wt% component (A), 10-50wt% component (B), 3-30wt% component (C) and 0-60wt% component (D).

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a thermoplastic resin composition having excellent heat resistance, moldability, and impact resistance. The present invention relates to a thermoplastic resin composition comprising a group vinyl compound-conjugated diene block copolymer and a styrene resin.

b. Conventional technology Polyphenylene ether is widely known as a resin with excellent heat resistance, mechanical properties, and electrical properties, but it has low impact resistance, poor processability and chemical resistance, and is difficult to heat at high temperatures. It has defects such as discoloration and gelation. Therefore, it is rarely used alone, and is usually used as a modified polyphenylene ether resin consisting of a composition with polystyrene or rubber-modified polystyrene.

This modified polyphenylene ether resin has excellent mechanical properties, electrical properties, and pressurizing properties, and is therefore widely used in automobile parts, office equipment, electrical appliance parts, and the like.

However, although the impact resistance and moldability have been improved to some extent, they have not yet reached a sufficient level. Furthermore, the excellent heat resistance of polyphenylene ether resins is sacrificed. These drawbacks are a major obstacle when using the above-mentioned modified polyphenylene ether resin in applications that take advantage of the characteristics of the polyphenylene ether resin.

As a method to improve the impact resistance mentioned above, mixing a rubber-like elastic material has been carried out, but the strength and impact resistance of the weld part are still insufficient, and it also tends to discolor due to heat, making it difficult to form. has the disadvantage of being inferior.

On the other hand, in order to improve heat resistance, a method of increasing the content of polyphenylene ether has been carried out.

However, although heat resistance is improved, moldability and impact resistance are poor.

As described above, conventional modified polyphenylene ether resins have had the drawback of not having a sufficient balance of physical properties among impact resistance, heat resistance, and moldability.

C8 Problems to be Solved by the Invention The present inventors have conducted extensive studies on polyphenylene ether compositions with an excellent balance of physical properties such as impact resistance, heat resistance, and moldability, and have surprisingly found that polyphenylene ether contains maleimide. A thermoplastic resin composition having an excellent physical property balance of impact resistance, heat resistance, and moldability can be obtained by blending a specific amount of a resin, an aromatic vinyl compound-conjugated diene block copolymer, and a styrene resin. The present invention was developed based on the findings.

Means for solving the d0 problem, that is, the thermoplastic resin composition of the present invention is (a)
Polyphenylene ether 10-80ffiit%, (b
) 15% to 0% of N-1F-converted mamaleimide and 30% to 0% of an aromatic vinyl compound in the presence or absence of Goto.
5-80% copolymer obtained by polymerizing 85% by weight, f
c) A thermoplastic resin composition comprising 1 to 60% by weight of an aromatic vinyl compound-conjugated diene block copolymer and 0 to 75% by weight of a dl styrene resin.

The polyphenylene ether (a) used in the present invention is obtained by oxidative coupling polymerization of one type of phenol compound represented by the general formula % in the presence of a known catalyst.

Particularly preferred among the phenol compounds are those represented by the general formula, and specific examples (X) of the most preferred phenol compounds include 2.6-dimethylphenol, 2.6-dinitylphenol, 2. -Methyl-6-nitylphenol, 2-methyl-6-allylphenol, 2-methyl-6-phenylphenol, 2
, 6-diphenylphenol, 2゜6-sibutylphenol, 2-methyl-6-propylphenol, 2,3.
Examples include 6-dolimethylphenol and 2,3-dimethyl-6-nitylphenol.

On the other hand, specific examples (Y) of other preferred phenol compounds include 2,3.6-)limethylphenol, 2゜3-
Dimethyl-6-nitylphenol, 2.3.6-driethylphenol, 2,3.6-)liprovirphenol, 2.6-dimethyl-3-ethylphenol, 2.6-
It is dimethyl-3-propylphenol. these(
χ) and (Y) may be polymerized alone, or may be a copolymerization of (X) and (Y).

In the case of copolymerization of (X) and (Y), there are no particular restrictions on the ratio of each component, but the preferred content of (Y) is 1 to 20 mol%, more preferably 3 to 15 mol%. The intrinsic viscosity [η] (30°C in chloroform) of polyphenylene ether (a) is not particularly limited, but is preferably 0.2 to 1417 g, more preferably 0.3 to 0.
It is 7 dl/g.

The amount of polyphenylene ether blended in the thermoplastic resin composition of the present invention is 10 to 80% by weight, preferably 10 to 60% by weight, and more preferably 20 to 60% by weight.
It is. When the amount of polyphenylene ether is less than 10% by weight, no remarkable effect is seen in improving heat resistance;
If it exceeds 50%, no effect of improving impact resistance or processability will be observed.

The amount of N-substituted maleimide used in the copolymerization components (excluding the rubbery polymer component) of the maleimide copolymer (hereinafter also referred to as copolymer (b)) used in the present invention is 1
Quintuplets 9 to 70% by weight, good, toshi < 30 to 70% by weight
More preferably, it is used in an amount of 56 to 70% by weight.

If it is less than 15% by weight, the heat resistance, which is the objective of the present invention, will be deteriorated, which is not preferable. Moreover, if it exceeds 70% by weight, the moldability, which is the object of the present invention, will deteriorate, which is undesirable. If it is in the range of 56 to 70% by weight, a product with excellent heat resistance and impact resistance can be obtained.

On the other hand, the aromatic vinyl compound is 30 to 85% in the copolymer component.
% by weight, preferably 30-70% by weight, more preferably 30-44% by weight. Aromatic vinyl compounds are
If it is less than 30% by weight, the molding and pressurizing properties, which is the objective of the present invention, will deteriorate, and if it exceeds 85% by weight, the heat resistance, which is the objective of the present invention, will be reduced, which is not preferred.

Copolymer (b) contains -F in addition to the above-mentioned monomer components.

It may also be a product obtained by co-merging monomers that copolymerize with the monomer. The copolymerizable monomer is used in an amount of 55% by weight or less, preferably 40% by weight or less, and more preferably 14% by weight or less. The copolymerizable monomers include:
Examples include vinyl cyanide compounds, acrylic esters, and methacrylic esters.

The N-substituted maleimide used in the present invention includes N-
These include phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, Nt-butylmaleimide, N-cyclohexylmaleimide, Np-chlorophenylmaleimide, N-naphthylmaleimide, and the like. Especially N-
Phenylmaleimide, N-cyclohexylmaleimide,
N-0-methylphenylmaleimide and the like are preferably used.

Aromatic vinyl compounds used in the present invention include styrene, 0-methylstyrene, m-methylstyrene, p-
Methylstyrene, chlorstyrene, dichlorostyrene,
Examples include bromustyrene, dibromustyrene, α-methylstyrene, α-ethylstyrene, methyl-α-methylstyrene, dimethylstyrene, vinylnaphthalene, and the like. Among these, styrene, p-methylstyrene, and α-methylstyrene are preferred, and styrene and α-methylstyrene are more preferred.
- methylstyrene or mixtures thereof.

Rubbers include diene rubbers such as polybutadiene, polyisoprene, styrene-butadiene copolymers, and nitrile rubbers, and non-diene rubbers such as ethylene-propylene copolymers, ethylene-propylene-diene copolymers, and acrylic rubbers. Can be used. The amount of rubber used is the copolymer (
θ to 60% by weight in bl is preferable, more preferably 0 to 60% by weight.
45% by weight, particularly preferably 0 to 40% by weight.

The amount of copolymer (b) used is 5 to 80% by weight, preferably 10 to 70% by weight, more preferably 10 to 50% by weight.
It is. If it is less than 5% by weight, the desired heat resistance will not be obtained, while if it exceeds 80% by weight, molding pressure properties and impact resistance will be poor, which is not preferable.

The copolymer (b) may generally be produced by any method such as solution polymerization, suspension polymerization, or emulsion polymerization.

Further, the intrinsic viscosity [η] of the copolymer (b) is 0.05 to 0.
5 (30°C in methyl ethyl ketone) di/g.

The aromatic vinyl compound-conjugated diene block copolymer (referred to as block copolymer (c)) used in the present invention is
It is a polymeric copolymer of an aromatic vinyl compound and a conjugated diene, and the amount used is 1 to 60% by weight, preferably 2 to 40% by weight, and more preferably 3 to 30% by weight based on the total composition. If it is less than 1% by weight, it is not possible to improve the impact resistance as the objective of the present invention, while if it exceeds 60% by weight, the moldability and surface appearance of the molded product, which are the objectives of the present invention, deteriorate, which is not preferred.

As the aromatic vinyl compound constituting the block copolymer (e), those shown above for the copolymer (b) can be used. Among these, styrene is particularly preferred.

On the other hand, examples of the conjugated diene compound include butadiene, isoprene, piperylene, and the like. Among these, preferred are butadiene and isoprene.

Preferable block copolymers (c) used in the present invention include (A-B), and/or ABA and/or (A-B), wholly aromatic vinyl compounds represented by X. It is a block copolymer with a content of 25 to 95% by weight, preferably 28 to 90% by weight.

A particularly preferred block copolymer (e) has the following structure, and the use of this block copolymer can be expected to further improve weld strength.

In other words, it is a block copolymer having an aromatic vinyl compound content of 25 to 95% by weight, and the copolymer is represented by the general formula A-B-A or/and (A-B), IX. and the content of the aromatic vinyl compound constituting a chain of 1 or 4 or less aromatic vinyl compounds in units of 1,000 is 1 to 25% by weight of the entire aromatic vinyl compound, Preferably it is 2 to 20% by weight, more preferably 5 to 20% by weight.

On the other hand, the preferred number of tapered blocks is 2 to 7.

The block copolymer (c) used in the present invention can be produced, for example, by the following method.

That is, an ether or a tertiary amine is added to a hydrocarbon solvent, and an organic lithiated N compound is used as an initiator.
First, an aromatic vinyl compound is polymerized 2, and after the polymerization reaction is substantially completed, a conjugated diene compound or a mixture of an aromatic vinyl compound and a conjugated diene compound is added, preferably in 2 to 10 times. If necessary, then an amount of conjugated diene equivalent to the one-time addition is added and polymerized.

Furthermore, the block copolymer of the general formula ABA is obtained by subsequently polymerizing an aromatic vinyl compound.

Further, the block copolymer of the general formula (A-B), , X can be obtained by performing a coupling N reaction using a conventionally known coupling agent such as tetrachlorosilane.

The mixture of the above aromatic vinyl compound and conjugated diene is
In the two stages of polymerization divided into 10 times, it is preferable that the amount of monomer used in each stage is about the same. How to add 1000 tsummer mixture,
Alternatively, the conjugated diene and the aromatic vinyl compound may be added separately and simultaneously.

The preferred amount of aromatic vinyl compound chain distribution in block copolymer (e) is 0.000% -I-thyl or tertiary amine per 100 parts by weight of monomer in a hydrocarbon solvent.
It can be obtained by adding 5 to 5 parts by weight, preferably 5 to 0.5 parts by weight.

The aromatic vinyl compound of the block copolymer (c) used in the present invention includes styrene, α-methylstyrene,
p-methylstyrene, m-methylstyrene, O-methylstyrene, p-tert-butylstyrene, dimethylstyrene, vinylnaphthalene, etc. can be used, and among these, styrene is preferred.

Further, as the conjugated diene, butadiene, isoprene, piperylene, etc. can be used, but among these, butadiene is preferred.

The weight average molecular weight of the block copolymer (c) used in the present invention is io, ooo to 800,000, preferably so, oo.

~500.000, and if it is smaller than this range, no improvement in impact resistance can be expected, and if it is larger than this range, (a)
, (b), (c), and (d), which is undesirable.

Hydrocarbon solvents used in the production of the block copolymer (c) used in the present invention include cyclopentadiene,
Cyclo, xene, xylene, and mixtures of these with pentahexane, hebutane, phytane, etc. are used.

In addition, as an organic lithium compound, n-butyllithium, sec -butyllithium, tert-butyllithium, n-.\xyllithium, iso -hekiu/
Luli (...7), phenyllithium, naphthyllithium 14, etc. are used.

The styrenic resin (d) of the present invention is a rubber obtained by copolymerizing a monomer containing an aromatic vinyl compound as a main component in the presence of a polymer containing an aromatic vinyl compound as a main component and/or Go 1. It is a modified styrene resin.

The amount of styrene resin used is O.~75% by weight, preferably 0~60% by weight, more preferably 0~5% by weight.
If the weight ratio exceeds 675 weight percent, the heat resistance, which is the LJ characteristic of the present invention, will be lowered, which is not preferable.

The aromatic vinyl compounds listed above (7 and copolymers (]]) can be used.

Monomers copolymerizable with aromatic vinyl compounds include vinyl cyanide compounds, such as acrylonitrile, (meth)
Examples include acrylic acid esters. These copolymerizable monomers can be used depending on the purpose. It is preferable to use a vinyl cyanide compound because a composition with excellent chemical resistance and paintability can be obtained.

Among copolymers containing an aromatic vinyl compound and cyanide, the composition of the copolymer is a mixture of copolymers having different amounts of vinyl cyanide bond.

The compositional distribution of the vinyl cyanide tetracompound in such a copolymer (mixture) is such that (a) the amount of bound metal of the vinyl cyanide compound is 1% by weight or more, and 10% by weight with respect to the copolymer; The copolymer component with a composition of less than
The copolymer component with a composition of less than 40% by weight is 1 to 70% (9c) The amount of bonded metal of the vinyl cyanide compound is 20% or more by weight, and the copolymer component with a composition of less than 40% by weight is 5 to 70% 90% by weight, and 0 to 70% by weight of a copolymer component having a composition in which the amount of bonded metal of (d) vinyl cyanide compound is 40% by weight or more, and vinyl cyanide in the copolymer, The average bond amount of the compound is 10-40% by weight.

The rubber used in the rubber-modified styrenic resin contains a polymer of conjugated diene φ-mer and/or conjugated diene as an essential component, and a cyanide vinyl compound, an aromatic vinyl compound, and (meth)acrylic. It is a rubber obtained by copolymerizing with at least one of acid ester and (meth)acrylic acid. Examples include polybutadiene rubber, styrene butadiene rubber, polyisoprene rubber, butadiene acrylonitrile rubber, chloroprene rubber, and the like. Examples of the non-diene rubber include 1.1,000-thousand propylene rubber, ethylene propylene conjugated diene rubber, butyl rubber, acrylic rubber, chlorinated polyethylene, butadiene copolymerized acrylic rubber, and the like.

The monomer components that polymerize in the presence of rubber are 1, 10, i, 4.
The monomer component c can be used, and the same effect as described in L can be obtained when a cyanide vinyl compound is co-present. It is preferable that the monomorphic distribution of the vinyl cyanide compound in the total free polymer (methyl ethyl ketone soluble portion) in the rubber-modified styrenic resin is within the above-mentioned range.

Methods for preparing the thermoplastic resin composition of the present invention include: (1) A method in which each component is dissolved in an organic solvent, swollen, and mixed.

■ A method in which each component is mixed using a mixer, etc., then melted and mixed using an extruder, and then pelletized.

(2) A method in which the powder mixture recovered using a non-solvent in (2) is melt-mixed using an extruder and then pelletized.

■ A method in which thermoplastic resin, styrene resin, polyphenylene ether, etc. are further added to the pellets of ■, mixed in a mixer, etc., and then melted and mixed using an extruder and then pelletized.

There is a method in which the pellets or powders of (1) and (2) to (3) are used alone or in a mixture, or each component is further added and mixed, and then a molded article is obtained using an injection molding machine.

Further, it is also possible to use known mixing equipment such as a Banbury or a kneader in each of the above methods.

In addition, other thermoplastic resins may be added to the composition of the present invention.
A styrene resin, boroph, -rene ether, polyamide, polyester, acrylic resin or other polymer may be added and mixed and melt-mixed in an extruder to obtain a 1-piece product.

The thermoplastic resin composition of the present invention can be used as various molded products by injection molding, sheet extrusion, vacuum molding, irregular molding, foam molding, and the like.

When using the thermoplastic resin composition of the present invention, commonly used antioxidants, ultraviolet absorbers, lubricants, flame retardants, antistatic agents, blowing agents, glass fibers, etc. can be added.

The thermo-oJ plastic resin of the present invention can be suitably used for automobile parts, electrical products, household goods, various industrial goods, and the like.

e. Examples Next, the present invention will be explained in more detail with reference to Production Examples and Examples, but these are merely illustrative.
This is not intended to limit the content of the present invention. In addition, parts and % on each side below are parts and weight %, respectively.
shows.

Production Examples Polyphenylene ether used in Examples and Comparative Examples was obtained by the following method.

(1) Production of polyphenylene ether - Polymer - A-1 After sufficiently purging the inside of a stainless steel reaction vessel equipped with an oxygen suction device, a cooling coil, and a stirrer at the bottom of the reactor with nitrogen, the cupric bromide 53. 6g of di-n-butylamine, and 8.75kg of 2,6-xylenol dissolved in 406g of toluene were added. After stirring to make a homogeneous solution, polymerization was carried out for 120 minutes while rapidly blowing oxygen into the reaction vessel. During the polymerization, water was circulated through a cooling coil to maintain the internal temperature at 30°C. After polymerization, toluene 307! and 430 g of disodium ethylenediaminetetraacetate was dissolved in water.
% aqueous solution was added to stop the reaction.

Next, the polymer solution phase was taken out by centrifugation.

While vigorously stirring this polymer solution phase, methanol was gradually added to form a slurry. After being furnace-separated, the polymer was thoroughly washed with methanol, further furnace-separated, and then dried to obtain Polymer A-1.

Polymerization (A--form = 2,6-xylenol/2,3.6-dolimethylphenol 90/10 (molar ratio) was used instead of the 2,6-xylenol used in the production of polymer A-1. Polymer A-2 was obtained.

(2) Method for producing block copolymer 4500 g of cyclohexane and 1 g of tetrahydrofuran were charged into a washed and dried autoclave equipped with a stirrer and a jacket under a nitrogen atmosphere, and the internal temperature was then raised to 70°C.

Next, after adding a hexane solution containing 0.5 g of n-butyllithium, 130 g of styrene was added and polymerized for 60 minutes.

The polymerization conversion rate of styrene was 100%. Next, a mixture of 15 g of styrene and 115 g of butadiene was added to
Polymerization took place for 0 minutes. The polymerization conversion rate of styrene and butadiene is 1
It was 00%. This operation was further repeated twice.

Next, 115g of butadiene was added to increase the polymerization conversion rate to 100.
The % gel content is determined by coagulating and drying the latex, then dissolving it in toluene at room temperature (20°C) for 20 hours.
It means the weight percent of undissolved matter separated in a furnace using a 00 mesh wire mesh. ] D-3 was manufactured by emulsion polymerization using the rubbery polymer latex shown in Table 3, styrene, and acrylonitrile.

Polymerization was carried out in three stages, and the amount of monomers used in each stage was appropriately adjusted so that the composition distribution of acrylonitrile in all educts in the obtained thermoplastic resin was as shown in Table 3. Hatch polymerization was performed, and in the second and third stages, polymerization was carried out while continuously adding monomers, and the polymerization was finally carried out to a polymerization conversion rate of nearly 100%.

Examples 1 to 10, Comparative Examples 1 to 5 Various polymers were mixed according to the composition ratios in Table 4,
After extruding into pellets at a temperature of 260 to 300"C using a twin-screw kneading extruder, it was thoroughly dried and subjected to tests for measuring impact resistance, heat resistance, and weld strength at a temperature of 240 to 280"C using an injection molding machine. A piece was molded and measured according to the test method below. The results are shown in Table 4.

Evaluation method: Heat-resistant molded product is annealed at 110°C for 2 hours, then 8S
TM D648 thickness%', 264p
The heat distortion temperature was measured using SI.

■Impact resistance Measured with thickness V4# notched according to ASTM D256.

■Weld strength retention rate ASTM A test piece molded using a mold with a weld line in the center of a No. 1 dumbbell, with tensile strength T-
Measure.

Next, the tensile strength To is measured using a test piece molded with a mold without weld lines.

The well 1 intensity retention rate was determined at (Tw/To) x 100%.

■Molding processability JIS K72 using Mel 1-Indexa manufactured by Ukogyo
According to 10C, cylinder temperature 280'e, load 0k
Melt flow index (MFR) in g (g/10
m1n) was measured.

The purpose of comparing Examples 1 to 10 and Comparative Examples 1 to 5 is as follows.

Comparative Example 1 is a system that does not contain the block copolymer (c), so the Izodgai g strength and the Izodgai g strength retention rate (
χ) is inferior.

Since Comparative Example 2 is a system that does not contain the maleimide copolymer (1)), it is inferior in heat distortion temperature (° C.) and weld strength retention (χ).

In Comparative Example 3, the content of polyphenylene ether (a) was 5%, and the content of polyphenylene ether a) was 1%.
It deviates from 0 to 80%. Therefore, since there is less borif-1 nylene ether, the heat distortion temperature is inferior.

In Comparative Example 4, the content of polyphenylene ether (a) is too high, so the Izot impact strength is poor.

Comparative Example 5 uses 30% maleimide copolymer b-4, but b-4 is a copolymer of 10% N-phenylmaleimide and 90% α-methylstyrene. This is because the maleimide copolymer contains 15 to 70% N-phenylmaleimide.
It deviates from the claimed range that it consists of 30-85% of aromatic vinyl compounds. Therefore, moldability and Izot impact strength are inferior.

e. Effects of the invention Currently, in the molding industry that uses thermoplastic resins, molded products tend to become more complex and larger due to the diversification of molded product applications. In order to obtain such a molded article, it is required to have better heat resistance, moldability, and impact resistance than conventional molded articles. However, conventional modified polyphenylene ether resin compositions have not been sufficient to meet these requirements. The composition of the present invention has a highly balanced heat resistance, moldability, and impact strength.

In addition, in order to mold complex and large-sized molded products, in order to fill the mold with enough molten thermoplastic resin, we currently have many injection ports for the molten thermoplastic resin into the mold. Therefore, the molded product has many welded parts, and the strength and appearance of the welded parts have become important.However, compared to conventional compositions, the composition of the present invention It is excellent in terms of quality and also has a good appearance.

As described above, the composition of the present invention is a molding material that improves the drawbacks of conventional polyphenylene ether resin compositions and satisfies the demands of the molding industry, and has great industrial value.

Patent issued by I*n person r1 Honsei Rubber Co., Ltd.
(Ryo-111-cho) (2 others)

Claims (1)

[Scope of Claims] (a) 10 to 80% by weight of polyphenylene ether, (b
) 15-70% by weight of N-substituted maleimide and 30-85% by weight of an aromatic vinyl compound in the presence or absence of rubber.
(c) 1-60% by weight of an aromatic vinyl compound-conjugated diene block copolymer, (d) 0-75% by weight of a styrene resin, and A thermoplastic resin composition comprising: