JPH02225552A - Thermoplastic polymer composition - Google Patents

Abstract

PURPOSE:To provide the title composition excellent in transparency, impact resistance, hardness, heat resistance, etc., by mixing a block copolymer of a specified composition with a polyphenylene ether in a specified mixing ratio. CONSTITUTION:A block copolymer comprising a plurality of polymer segments based on a vinylaromatic hydrocarbon and at least one polymer segment based on a conjugated diene is produced. It is necessary that the vinylaromatic hydrocarbon content should be 60-95wt.%, and that the content of the vinylaromatic hydrocarbon present as the vinylaromatic hydrocarbon polymer in the copolymer should be 75-98wt.% based on the total vinylaromatic hydrocarbon. It is further necessary that the ratio of the weight-average MW of the vinylaromatic hydrocarbon polymer block in the copolymer to its number-average MW should be 1.2-2 on the average. 10-95 pts.wt. this block copolymer is mixed with 90-5 pts.wt. polyphenylene ether to produce a thermoplastic polymer composition.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermoplastic polymer composition that has excellent transparency, impact resistance, surface hardness, heat resistance, and gloss, and is less warped.

[Conventional technology]

A block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon has excellent transparency when the vinyl aromatic hydrocarbon content is relatively high, and a thermoplastic resin with better impact resistance than polystyrene can be obtained. Its usage has been increasing in recent years, mainly in fields such as food packaging containers, daily necessities, toys, and light electrical parts. However, such block copolymers have the disadvantage that their surface hardness and heat resistance are lower than those of other plastics.

On the other hand, polyphenylene ether resin is a resin with excellent dimensional stability, electrical properties, heat deformation resistance under high loads, water resistance, etc., and is widely used industrially. It has the disadvantage of poor properties and molding fluidity.

For this reason, various attempts have been made to blend block copolymers consisting of conjugated dienes and vinyl aromatic hydrocarbons and polyphenylene ether resins, with the aim of taking advantage of their respective strengths and compensating for their shortcomings. .

For example, JP-A-48-62851 and JP-A-51
Publication No. 129450 describes (a) a polyphenylene ether resin, (b) an A-B-A' type elastomer block copolymer (wherein, the central block B has a molecular weight larger than the combined molecular weight of the terminal blocks A and A'). and (c) a styrene homopolymer or random copolymer resin are described. Furthermore, JP-A-52-125560 describes a thermoplastic molding composition comprising a homogeneous mixture of (i) a polyphenylene ether resin, a phantom styrene resin, and an oil radial teleblock copolymer. Furthermore, JP-A-58-176240 discloses that 10 to 60 parts by weight of a vinyl aromatic compound and 40 to 40 parts by weight of a conjugated diene are added to 100 parts by weight of a modified polyphenylene oxide resin.
A thermoplastic resin composition is described which comprises as a main component 90 parts by weight of a pro-polymer copolymer and 1 to 20 parts by weight.

However, the block copolymers used in these compositions have a vinyl aromatic compound content of 60% by weight or less, and these compositions have poor transparency, surface hardness, and heat resistance. Poor quality and gloss.

On the other hand, Japanese Patent Publication No. 54-27025 discloses (A) 1 to 45% by weight of polyarylene oxide and (B) 10 to 90% by weight of monovinyl aromatic block polymer. 99-55% by weight of monovinyl aromatic pro-link polymer having at least one monovinyl aromatic block comprising WI%
A thermoplastic composition containing a block copolymer containing 80% by weight of a vinyl aromatic compound is disclosed. However, such compositions have a problem in that they have poor impact resistance and are susceptible to microcranks when bent. Also, JP-A-61
No. 223054 and JP-A-62-70448 disclose (a) polyphenylene ether resin, (b)
A high impact polyphenylene ether containing an A-B-A' type block copolymer (where the molecular weight of the B block is less than the combined molecular weight of the A and A' blocks) and (c) an elastomer. based resin compositions are described. However, although such compositions have excellent impact resistance, they have problems in that they are inferior in transparency and surface hardness.

Furthermore, JP-A-50-71742, JP-A-53-9
No. 4540 and Japanese Patent Application Laid-open No. 56-95949 describe compositions comprising (a) a polyphenylene ether resin, (b) a styrene resin, and (c) a hydrogenated block copolymer. However, the block copolymers used in such compositions have a vinyl aromatic hydrocarbon content of 60% by weight or less, and are poor in transparency, surface hardness, heat resistance, and gloss.

[Problem to be solved by the invention]

The present inventors have solved the problems of conventionally proposed compositions as described above, and have achieved excellent transparency, impact resistance, surface hardness, heat resistance (heat deformation resistance), and gloss, and less warpage. We conducted extensive research to find a thermoplastic polymer composition.

[Means for Solving the Problems] The present invention provides a composition comprising a block copolymer and a polyphenylene ether resin, in which the vinyl aromatic hydrocarbon content and the vinyl aromatic hydrocarbon present as a vinyl aromatic hydrocarbon polymer block are reduced. We have discovered that the above objectives can be achieved by using a block copolymer in which the proportion of group hydrocarbons and the ratio of the weight average molecular weight to number average molecular weight of the vinyl aromatic hydrocarbon polymer block are within specific ranges, respectively. It is what was done.

That is, the present invention provides (i) (a) a block copolymer consisting of a small number (both of which are two) of polymer segments mainly composed of vinyl aromatic hydrocarbons and at least one polymer segment mainly composed of a conjugated diene; In the copolymerization, (i) the vinyl aromatic hydrocarbon content is more than 60% by weight and not more than 95% by weight; The ratio of hydrogen to the total vinyl aromatic hydrocarbons contained in the copolymer is more than 75% by weight and not more than 98% by weight, (Ii+) The weight of the vinyl aromatic hydrocarbon polymer block in the copolymer Thermoplastic polymer composition (2) consisting of 10 to 95 parts by weight of a block copolymer having an overall average molecular weight to number average molecular weight ratio of 1.2 to 2.0 (b) 5 to 90 parts by weight of polyphenylene ether 100 parts by weight (c
) A thermoplastic polymer composition consisting of 3 to 400 parts by weight of polystyrene.

The present invention will be explained in detail below.

The block copolymer of component (a) used in the present invention consists of at least two vinyl aromatic hydrocarbon-based polymer segments and at least one conjugated diene-based polymer segment. The vinyl aromatic hydrocarbon content is more than 60% by weight and not more than 95% by weight, preferably from 65 to 90 Mm%. If the vinyl aromatic hydrocarbon content is less than 60% by weight, the surface hardness, heat resistance, and gloss will be poor, and if it exceeds 95% by weight, the impact resistance will be poor, which is not preferable. In the present invention, a polymer segment mainly containing vinyl aromatic hydrocarbons is a polymer segment containing vinyl aromatic hydrocarbons in an amount of 50% by weight or more, preferably 70% by weight or more. This is a segment composed of a copolymer block of hydrogen and a conjugated diene and a vinyl aromatic hydrocarbon homopolymer block, or a segment composed of a vinyl aromatic hydrocarbon homopolymer block. In addition, a polymer segment mainly containing conjugated diene is a polymer segment in which the content of conjugated diene is more than 50% by weight, preferably 70% by weight or more, and the content of conjugated diene is more than 70% by weight. A segment composed of a copolymer block and/or a conjugated diene homopolymer block. The vinyl aromatic hydrocarbons copolymerized in the copolymer blocks in these segments may be uniformly distributed or tapered, and There may be a plurality of portions in which vinyl aromatic hydrocarbons are uniformly distributed and/or a plurality of portions in which vinyl aromatic hydrocarbons are distributed in a tapered manner.

The block copolymer of component (a) used in the present invention comprises a vinyl aromatic hydrocarbon contained in the copolymer, which is present as a vinyl aromatic hydrocarbon polymer block in the copolymer. Percentage of total vinyl aromatic hydrocarbons (
Hereinafter referred to as the block rate of vinyl aromatic hydrocarbons) is 7.
More than 5% by weight and not more than 98% by weight, preferably 77-9
It is 6% by weight.

If the block rate of the vinyl aromatic hydrocarbon is less than 75% by weight, the surface hardness and heat resistance will be poor, and if it exceeds 98% by weight, the impact resistance will be poor, which is not preferred. The block rate of vinyl aromatic hydrocarbons can be determined by oxidative decomposition of the copolymer with di-tert-butyl hydroperoxide using osmium tetroxide as a catalyst (for example, L, M, K
orthoff et al.

J. Polymer Sci., 1, 429
(i946)). That is, after oxidatively decomposing a block copolymer by the above method, a large amount of methanol is added to the decomposed product to obtain a vinyl aromatic hydrocarbon polymer component (generally, the number average molecular weight is about 1
000 or more, usually about 3000 to about 1, OOO,000
) can be divided by the total amount of vinyl aromatic hydrocarbons contained in the block copolymer to determine the block rate of vinyl aromatic hydrocarbons.

In addition, the block copolymer of component (a) used in the present invention has the M weight average molecular weight (hereinafter referred to as Mw) and the number average molecular weight (hereinafter referred to as Mw) of the vinyl aromatic hydrocarbon polymer block in the cough copolymer.
The overall ratio of Mn (hereinafter referred to as Mn) is in the range of 1.2 to 2.0, preferably 1.3 to 1.8. M w /
If the ratio of M n is less than 1.2, it is inferior to Zaijikai and is 2.0.
If it exceeds this, molding anisotropy will occur, resulting in the problem of warping of the molded product. Mw/Mn of the vinyl aromatic hydrocarbon polymer block in the block copolymer can be measured as follows. The vinyl aromatic hydrocarbon polymer component obtained by oxidative decomposition of the block copolymer by the above method is measured by gel vermiacedine chromatography (c; PC), It can be calculated according to the method described in "Kin" published by Kodansha). The calibration curve for GPC is prepared using standard polystyrene commercially available for GPC.

A particularly preferred block copolymer as component (a) used in the present invention is the glass transition temperature (Tg
) is a block copolymer having a temperature of 65 to 98°C, preferably 75 to 96°C. When a block copolymer having a Tg in this range is used, a composition with less occurrence of micro-cranks that appears when the composition is folded can be obtained. Note that Tg referred to here is the dynamic elastic modulus (E
′) or the temperature determined from the inflection point of differential scanning calorimeter (
Dynamic viscoelasticity, which refers to the temperature determined from the inflection point of temperature change in DSC), can be measured using a Rheopybron (Model DDV-3) manufactured by Toyo Baldwin Co., Ltd. or the like.

The block copolymer of component (a) used in the present invention has a polymer structure of the general formula: CA-B)n+t, Ai-A)n, B(A-
B) n (In the above formula, A is a polymer block mainly composed of vinyl aromatic hydrocarbons, and B is a polymer block mainly composed of conjugated dienes. The boundary between A block and B block is not always clear. (In the above formula, A and B are the same as above, and represents, for example, the residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, epoxidized soybean oil, polyhalogenated hydrocarbon, carboxylic acid ester, or polyvinyl compound, or the residue of an initiator such as a polyfunctional organolithium compound. 0m and n are integers of 1 or more, preferably m is an integer of 1 to 1O, and n is an integer of 1 to 5. The copolymer may be any mixture of block copolymers represented by the above-mentioned formula.

Vinyl aromatic hydrocarbons used in the method of the present invention include styrene, O-methylstyrene, p-methylstyrene, p-methylstyrene,
Examples include -tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, and vinylanthracene, among which styrene is particularly suitable for boat fishing.

These may be used not only alone, but also as a mixture of two or more.

The conjugated diene used in the present invention is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3- Dimethyl-1,3-butadiene, 1.
Examples include 3-penkdiene and 1,3-hexadiene, and particularly those used in boat fishing include 1,3-butadiene and isoprene. These may be used not only alone, but also as a mixture of two or more.

The block copolymer used in the present invention is prepared in a hydrocarbon solvent.
Obtained by polymerization using an organic lithium compound as an initiator.

Hydrocarbon solvents include aliphatic hydrocarbons such as butane, pentane, hexane, impentane, heptane, octane, and isooctane; alicyclic hydrocarbons such as cyclobencune, methylcyclopancune, cyclohexane, methylcyclohexane, and ethylcyclohexane; tel Alternatively, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene can be used. Organolithium compounds are
An organic lithium compound with one or more lithium atoms bonded in the molecule, such as ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, 5ec-butyllithium, tert-butyllithium, hexamethylene dilithium, Examples include butadienyl dilithium and isoprenyl dilithium.

In the block copolymer of component (a) used in the present invention, the number average molecular weight of segment A is s, oo.

~500,000, preferably 70,000-300.
000, and the number average molecular weight of segment) B is i, oo
o~400.000, preferably 3.000~300,
It is 000. The number average molecular weight of the block copolymer as a whole is 10,000 to 1.000.000, preferably 30,000 to 500.000.

As the block copolymer used in the present invention, a block copolymer in which a polar group-containing atomic group is bonded to at least one polymer chain terminal can be used. Here, the polar group-containing atomic groups include nitrogen, oxygen, silicon, phosphorus, sulfur,
An atomic group containing at least one atom selected from tin. Specifically, carboxyl group, carbonyl group,
Thiocarbonyl group, acid halide group, acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, Phosphate ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothioneanate group, silicon halide group, alkoxy silicon group, tin halide group Examples include atomic groups containing at least one polar group selected from , alkyltin groups, phenyltin groups, and the like. More specifically, the terminal-modified block copolymer described in Japanese Patent Application No. 60-224806 can be used.

In the present invention, a hydrogenated product of the above-mentioned block copolymer or terminal-modified block copolymer can be used. Catalysts used in the hydrogenation reaction include (i) Ni,
A supported heterogeneous catalyst in which metals such as PT, Pd, and Ru are supported on a carrier such as carbon, silica, alumina, and diatomaceous material, and (2) organic acid salts such as Ni, Co, Fe, and Cr, or acetylaton. The so-called Ziegler type catalyst using a salt and a reducing agent such as an organic compound, or Ru, R
Homogeneous catalysts such as so-called organic complex catalysts such as organometallic compounds such as h are known. As a specific method,
-8704 Publication, Japanese Patent Publication No. 43-6636, or Japanese Patent Application Publication No. 59-133203, Japanese Patent Application Publication No. 60-2
According to the method described in Japanese Patent No. 20147, hydrogenation is performed in an inert solvent in the presence of a hydrogenation catalyst to obtain a hydrogenated product, and the hydrogenated polymer used in the present invention can be synthesized.

At that time, the hydrogenation rate of aliphatic double bonds based on the conjugated diene compound in the polymer is determined by the reaction temperature, reaction time, hydrogen supply amount,
By adjusting the amount of catalyst, etc., it can be controlled to any desired value.For example, when improving heat deterioration resistance while maintaining the properties of an unhydrogenated polymer, the aliphatic double bond based on the conjugated diene can be % or more and less than 80%, preferably 59
It is recommended to hydrogenate 6 or more and less than 75%, particularly preferably 10 to 45%, and to improve heat deterioration resistance and weather resistance, to hydrogenate 80% or more, preferably 90% or more. In this case, a homopolymer consisting of a repeating unit represented by a polymer block A4 mainly composed of a vinyl aromatic compound and, if necessary, a polymer mainly composed of a conjugated diene compound; Although there is no particular restriction, the hydrogenation rate is preferably 20% or less.The amount of unhydrogenated aliphatic double bonds contained in the hydrogenated block copolymer is determined by infrared spectroscopy. This can be easily determined using a magnetic resonance analyzer, nuclear magnetic resonance apparatus, etc.

Next, the polyphenylene ether of the component (b) used in the present invention has the form: The remaining alkyl groups, aryl groups, and halogen atoms in ~4 are hydrogen atoms, which may be the same or different from each other. (R3, Ra, Rs, and R& in the formula are Each of them is a linear, primary or secondary branched alkyl group having 1 to 4 carbon atoms, an aryl group, a halogen atom, a hydrogen atom, etc., which may be the same or
(Although they may be different from each other, R3 and R4 cannot be hydrogen atoms at the same time) A copolymer consisting of the repeating unit shown in These include graft copolymers.

Representative examples of homopolymers of polyphenylene ether include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, and poly(2,6-dimethyl-1,4-phenylene) ether. -diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-
di-n-propyl-1,4-phenylene) ether, poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-itubroby-1,4-phenylene) ether, poly(2-methyl-6
-chloro-1,4-phenylene)ether, poly(2-
methyl-6-hydroxyethyl-1,4-phenylene)
ether, poly(2-methyl-6-chloroethyl-1,
Examples include homopolymers such as 4-phenylene) ether.

The polyphenylene ether copolymer is an alkyl compound such as 0-cresol or 2,3,6-drimethylphenol represented by the formula (R, , R, , R, and R6 have the same meanings as above). It includes a polyphenylene ether copolymer mainly having a polyphenylene ether structure obtained by copolymerizing with a substituted phenol.

The number average degree of polymerization (n) of polyphenylene ether is 50
-500, preferably 75-250. If the number average degree of polymerization is less than 50, the physical properties such as impact strength of the obtained composition will significantly deteriorate, making it difficult to put it into practical use.
If it exceeds 0, the processing fluidity of the obtained composition will be poor and gelation will occur easily, which is undesirable.

As the polyphenylene ether used in the present invention, a modified polyphenylene ether obtained by adding and/or graft polymerizing a radically polymerizable vinyl compound to the above homopolymer or copolymer can be used. Examples of vinyl compounds include the above-mentioned vinyl aromatic hydrocarbons and their halogen-substituted products, unsaturated monocarboxylic acid esters such as acrylic acid esters and methacrylic acid esters, unsaturated carboxylic acid amides such as acrylamide and meccrylic acid amide, Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, or acid anhydrides of these unsaturated dicarboxylic acids,
Examples include ester, amide, imide, and nitrile yarns such as acrylonitrile and methacrylonitrile.

In the present invention, a polymer of the above vinyl aromatic hydrocarbon or a copolymer of a vinyl compound copolymerizable with the above vinyl aromatic hydrocarbon (hereinafter referred to as component (c)) may be used. Can be done.

As the copolymerizable monomer, the above-mentioned vinyl compounds can be used. Preferred (co)polymers as component (c) are:
Polystyrene, styrene-α-methylstyrene copolymer, acrylonitrile-styrene copolymer, styrene-methacrylic acid ester copolymer1. Examples include styrene-maleic anhydride copolymer, which can be used alone or as a mixture of two or more. These (co)polymers are effective in further improving the surface hardness and rigidity of the composition.

Further, in the present invention, a rubber-modified vinyl aromatic fluorocarbon polymer (hereinafter referred to as component (D)) can be blended. The rubber-modified vinyl aromatic hydrocarbon polymer is obtained by polymerizing a mixture of the vinyl aromatic hydrocarbon or a monomer copolymerizable therewith with an elastomer, and polymerization methods include suspension polymerization, emulsion polymerization, Bulk polymerization, bulk-suspension polymerization, etc. are generally carried out. Monomers copolymerizable with vinyl aromatic hydrocarbons include α
- Examples include the above-mentioned vinyl compounds such as methylstyrene, acrylonitrile, acrylic esters, methacrylic esters, and maleic anhydride. In addition, as elastomers, natural rubber, synthetic isoprene rubber, butadiene rubber,
Styrene-butadiene rubber, high styrene rubber, polybutadiene rubber, chloroprene rubber, polybutene rubber, rubbery ethylene-propylene copolymer, rubbery butadiene-acrylonitrile copolymer, butyl rubber, various nitrile rubbers, rubbery ethylene-acetic acid Vinyl copolymers, rubbery ethylene-acrylic acid ester copolymers, rubbery active polypropylene resins, rubbery ethylene-acrylic acid ionomers, and the like are used.

These elastomers are generally 2 to 70 parts by weight, more preferably 3 to 50 parts by weight, per 100 parts by weight of the vinyl aromatic hydrocarbon or a monomer copolymerizable therewith, or dissolved in the cough suppressor. It is used in the form of latex for bulk polymerization, bulk-Qi polymerization, emulsion polymerization, etc.

Particularly preferred rubber-modified polymers include impact-resistant rubber-modified styrene polymers, acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, and methacrylic ester-butadiene-styrene copolymers.
Examples include styrene copolymers, impact-resistant rubber-modified styrene-maleic anhydride copolymers, and these can be used alone or as a mixture of two or more.

In the present invention, the blending weight ratio of component (a) and component (°C) is 10 to 95% by weight, preferably 20 to 8% by weight.
It is 5% by weight, more preferably 30 to 80% by weight. If component (a) is less than 10% by weight, the impact resistance and processability will be poor, and if it exceeds 95% by weight, the heat resistance and surface hardness will be poor, which is not preferable. A particularly preferable blending weight ratio is
Component (a) is valuable at 35 to 75 percent, and in this range, the impact strength is superior to that of component (a) and component (b) alone. ,! A completely unexpected effect is achieved, in that a composition with excellent shadow strength can be obtained.

Furthermore, in the present invention, 50ON or less, preferably 3 to 400 parts by weight, more preferably 5 to 300M, per 100 parts by weight of the composition consisting of component (a) and component (t)l.
The above component (c) can be blended in the proportion of parts by weight. Processability can be improved by using component (c). If the amount of component (c) exceeds 500 parts by weight, impact resistance and heat resistance will decrease, which is not preferable.

Furthermore, in the present invention, 500 parts by weight or less, preferably 3 to 400 parts by weight, more preferably 5 to 300 parts by weight, per 100 parts of the composition consisting of component (a) and component (°C).
The impact resistance can be improved by blending the component (D) in a certain amount. If the blending amount of component CD) exceeds 500 parts by weight, it is not preferable because heat resistance decreases. still,
In order to obtain a composition with good transparency, it is recommended that the amount of component (D) be 50 to 11 parts by weight or less, preferably 25 parts by weight or less.

Other thermoplastic resins and rubber-like polymers can be blended into the thermoplastic polymer composition of the present invention.

As the thermoplastic resin, polyethylene and ethylene are used at 50%
Copolymers of ethylene and other monomers copolymerizable with ethylene containing 50% or more, polypropylene, propylene
% or more of propylene and a monomer copolymerizable with it, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin and its hydrolyzate, polyacrylate resin, acrylonitrile resin, polyamide resin, polyester resin, polyphenylene sulfide resin, polyacetal resin, polycarbonate resin, polysulfone resin, thermoplastic polyurethane resin, polybutadiene resin, polyacrylate resin, fluorine resin, polyoxybenzoyl resin, polyimide Examples include resins. In addition, examples of the rubbery polymer include polybutadiene, polyisoprene, styrene-butadiene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene copolymer, ethylene-propylene copolymer, and ethylene-propylene-diene copolymer. , silicone rubber, shrimp chloride rubber, acrylic rubber, ethylene-vinyl acetate copolymer, and the like.

The thermoplastic polymer composition of the present invention can contain any additives, if necessary. The type of additive is not particularly limited as long as it is commonly used in plastic formulations, but examples include glass fiber, glass beads, silica,
Inorganic reinforcing agents such as charcoal and talc, organic fibers, growth reinforcement agents such as coumaron indene resin, organic peroxide,
Crosslinking agents such as inorganic peroxide, pigments such as titanium white, carbon black, iron oxide, dyes, flame retardants, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, other fillers, or mixtures thereof. Examples include.

The thermoplastic polymer composition of the present invention can be produced by any conventionally known compounding method.

For example, melt-kneading methods using general kneading machines such as open rolls, intensive mixer internal mixers, co-kneaders, continuous kneaders with two-wheel low-cooking, extruders, etc., heating the solvent after dissolving or dispersing each component in a solvent. A method of removing it is used.

〔Example〕

Examples are shown below, but these are representative of the present invention and are not intended to limit the scope of the present invention.

Example 1 and Comparative Examples 1 to 7 In cyclohexane, using n-butyllithium as a catalyst, the polymer structure was one-ship type A, -B-A! A styrene-butadiene block copolymer was produced. M w / M n ! in the production of block copolymers! ,tA
The blocking rate of styrene is adjusted by changing the ratio of the amount of styrene used in part r and the amount of styrene used in part A2. It was adjusted by continuously supplying the water and at the same time changing the ratio. Further, the melt flow index (~11 (G)) was adjusted by changing the amount of n-butyllithium. The obtained block copolymer was formed into pellets using an extruder, and then melted together with polyphenylene ether and polystyrene using a twin-screw press ratio machine. Thereafter, a flat plate with a thickness of 3 mm was injection molded at 250''C using Is~80A (50 g injection molding machine) manufactured by Toshiba Machine Co., Ltd.

Table 1 shows the physical properties of the injection molded product obtained.

The block copolymer composition within the scope of the present invention had excellent transparency, impact resistance, heat resistance, and surface hardness, and was also a molded article with good microcrack resistance and less warpage.

(Left below) (Note 1) (Note 2) (Note 3) (Note 4) (Note 5) (Note 6) (Note 7) Polyphenylene ether resin with intrinsic viscosity of 0°57 dl/g (25°C, chloroform) use.

Uses Styron 685 manufactured by Asahi Kasei.

Conforms to ASTM D-1709 and JIS K-5400! Based on JIS K-6714 Based on JIS K-6871 Based on the bending test method based on ASTM D-790, we observed the occurrence of micro-cracks when the test piece was bent and deformed, and determined the point at which micro-crank occurred. Microcrankability was evaluated based on the amount of deformation at the center of the test piece.

O: Deformation amount when micro cracks occur More than 10ais+.

O: Microcracks occur in a range where the amount of deformation exceeds 311IIi1 and is 10+a+ or less.

×: Microcracks occur when the amount of deformation is 3m111 or less.

(Note 8) The warpage of an injection molded product is closely related to the difference in molding shrinkage between the flow direction of the molded product and the direction perpendicular thereto, and the larger the difference, the greater the warpage of the injection molded product. Judgment was made based on the difference in rates.

Run as follows depending on the difference in molding shrinkage rate. It was divided into groups.

0.2% or less 0 More than 0.012% and less than 0.4% 0 0.4% to 0.6% or less Δ Exceeding 0.6% × In addition, the molding shrinkage rate in the direction perpendicular to the flow direction measured the molding shrinkage rate on the side opposite to the gate side.

Example 2.3.4 and Comparative Example 8.9 By the same method as in Example 1, the polymer structure was changed to one-soft type A,
-B-A! A styrene-butadiev block copolymer represented by: Mixing with polyphenylene ether and polystyrene and molding were performed in the same manner as in Example 1. The physical properties of the obtained injection molded product are shown in Table 2. The block copolymer composition within the scope of the present invention has good impact resistance, pencil hardness, and heat resistance, and the molded product does not warp and has excellent gloss. It was something.

(The following is a blank space) (Note 9) Using a dumbbell test piece according to ASTM D638, using a gloss meter manufactured by Suga Test Instruments, at an incident angle of 60°
The dead end part was measured.

Evaluation rank ○: 95% or more 6285% or more, less than 95% It exhibited excellent physical properties such as high impact resistance, high heat resistance, and good scratch resistance, as well as flame retardancy.

(Left below) Examples 5 to 9 Polymer structure is general 2B, -A, -B□-A, ,A, -
B+ Ax Bt A3 and (A+ B+
A block copolymer represented by (X represents a residue of 5iC1) was produced in the same manner as in Example 1.

Mixing with polyphenylene ether and polystyrene and molding were performed in the same manner as in Example 1. Table 3 shows the physical properties of the injection molded product obtained.

Example 10 Using 100 parts of the block copolymer composition of Example I, 3 parts by weight of antimony trioxide, and decabromo Example 11 Using n-butyllithium as a catalyst in cyclohexane, the polymer structure had the general formula At B-A A styrene-butadiene block copolymer was produced. Thereafter, this block copolymer was hydrogenated using a Tt-based hydrogenation catalyst described in JP-A-59-133203 to obtain a hydrogenated block copolymer in which about 99% of the aliphatic double bonds in the butadiene moiety were hydrogenated. was created.

Next, the obtained hydrogenated block copolymer was melt-kneaded with polyphenylene ether and polystyrene in a twin-screw presser.

The physical properties of the obtained composition are shown in Table 4.

(Left below) 2nd Example 12 In the composition of Example 1, instead of polystyrene,
Styrene/methyl methacrylate copolymer, impact-resistant rubber-modified styrene polymer (IIIPS), acrylonitrile/butadiene/styrene copolymer (ABS), methyl methacrylate/butadiene/styrene copolymer (MB)
The six compositions obtained using each of S) were excellent in impact resistance, surface hardness, and heat resistance.

Examples 13-17. Comparative Examples 10 to 11 A polymer composition was prepared in the same manner as in Example 1 except that the polystyrene used as component (c) in Example 1 was excluded from the composition, injection molded, and its physical properties were evaluated. did. The obtained evaluation results are shown in Table 5.

The composition of the present invention was excellent in transparency, impact resistance, heat resistance, and surface hardness even in a two-component system of (a) block copolymer and (b) polyphenylene ether.

〔Effect of the invention〕

The thermoplastic polymer composition of the present invention can be used for various purposes by taking advantage of its excellent transparency, impact resistance, surface hardness, heat resistance, and gloss. The composition of the present invention can be formed by extrusion molding, injection molding,
Can be formed into sheets, films, foams, injection molded products of various shapes, blow molded products, pressure molded products, vacuum molded products, etc. by blow molding, etc. Food packaging containers, home appliances, automobile parts, industrial products, toys, etc. It can be used for. especially,
Since the composition of the present invention causes less warpage when injection molded, it is suitable for injection molding of flat molded products, molded products with many flat parts, and large molded products.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] 1. (a) A block copolymer consisting of at least two polymer segments mainly composed of vinyl aromatic hydrocarbons and at least one polymer segment mainly composed of conjugated dienes, (i) the vinyl aromatic hydrocarbon content is more than 60% by weight and not more than 95% by weight; (ii) the vinyl aromatic hydrocarbon is present as a vinyl aromatic hydrocarbon polymer block in the copolymer; The proportion of the total vinyl aromatic hydrocarbon contained in the copolymer is more than 75% by weight and 98% by weight or less; (iii) the weight average molecular weight of the vinyl aromatic hydrocarbon polymer block in the copolymer; A thermoplastic polymer composition comprising 10 to 95 parts by weight of a block copolymer having a total number average molecular weight ratio of 1.2 to 2.0 (b) 5 to 90 parts by weight of polyphenylene ether. 2. A thermoplastic polymer composition according to claim 1, comprising 100 parts by weight of a thermoplastic polymer composition comprising (a) and (b) and (c) 3 to 400 parts by weight of polystyrene.