JPH0156101B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel thermoplastic polymer composition having excellent impact resistance, interfacial peeling resistance, and paintability, and more particularly, to a vinyl aromatic compound-conjugated diene composition modified with a dicarboxylic acid or a derivative thereof. Compound block copolymers or ionic crosslinked products thereof, polyoxymethylene polymers, polycarbonate polymers or modified products thereof, polysulfone polymers or modified products thereof, nitrile polymers, polyphenylene ether polymers or a modified product thereof, and a thermoplastic polymer comprising any one or a mixture of two or more of polyarylene sulfide polymers or modified products thereof, and is suitable for use in molded articles. Regarding. As is well known, polyoxymethylene resins, polycarbonate resins, polysulfone resins, nitrile resins, polyphenylene ether resins, and polyarylene sulfide resins are generally called engineering resins and have high mechanical properties, heat resistance, durability, etc. It is widely used as an alternative material to metals in required mechanical and electrical parts. Particularly recently, as part of energy saving measures, efforts have been made to reduce the weight of automobile bodies in order to improve their fuel efficiency, and the above-mentioned engineering resins are attracting attention as effective materials in this field. However, even with such excellent properties, engineering resins have several drawbacks that prevent them from fully satisfying the properties required in other aspects of the application fields in which they are utilized. For example, polyoxymethylene resins and nitrile resins have extremely high tensile strength, bending strength, and elastic modulus, making extremely tough molded products, and have the advantage of being excellent in solvent resistance. Its use as a material is restricted. Further, although polycarbonate has very strong mechanical strength and shows very high impact strength, it has the disadvantage that its coating properties are rather poor. Furthermore, polysulfone resins, polyphenylene ether resins, and polyarylene sulfide resins have good heat resistance and strong mechanical strength, but have the disadvantage of poor impact resistance. Various attempts have been made to improve these drawbacks; for example, in the case of polyphenylene ether resins, an attempt has been made to improve the impact resistance by blending a block copolymer consisting of rubber-modified impact-resistant polystyrene and butadiene. ing. Although the above-mentioned drawbacks have been considerably improved by such improvement methods, there is still a need for a modifier that has a greater effect on improving impact resistance. As a result of intensive studies to solve these problems, the present inventors have found that a vinyl aromatic compound-conjugated diene compound block copolymer modified with dicarboxylic acids or an ionic crosslinked product thereof has been added to the above-mentioned engineering resin. It has been discovered that the objective can be achieved by blending, and the present invention has been achieved. That is, the thermoplastic polymer composition of the present invention comprises (i) a polyoxymethylene polymer, a polycarbonate polymer and its modified product, a polysulfone polymer and its modified product, a nitrile polymer, a polyphenylene ether; 100 parts by weight of a thermoplastic polymer consisting of one or a mixture of two or more of the following: (ii) a vinyl aromatic compound; A block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound in a weight ratio of 5/95 to 70/30 (hereinafter simply referred to as a block copolymer)
A modified block copolymer formed by bonding a molecular unit containing a dicarboxylic acid group or a derivative group thereof, or a monovalent, divalent,
Any one of valent and trivalent metal ions
Ionic crosslinked product with species or mixture of two or more species 1
Consists of at least 100 parts by weight. Generally, different types of polymers are not miscible with each other;
Even when they are forcibly mixed by melt kneading or the like, adhesion at their mutual interfaces is poor. Therefore,
The interface between different types of polymers in the mixture is extremely vulnerable to external impacts, and scratches and cracks can easily occur there, leading to the destruction of the entire mixture. Improving the adhesion of the interface between different polymers is an important factor in improving the mechanical strength and impact strength of a mixture of different polymers, and as a means to improve this property, It is common practice to further incorporate compatible additives. However, in the present invention, even without using such special additives, component (i) and component (ii) exhibit strong adhesion at the interface, resulting in a composition with excellent impact resistance. In the present invention, the adhesiveness of the interface between component (i) and component (ii) is large, as stated in the specification of Japanese Patent Application No. 53-99102 (filed on August 16, 1978), which we filed earlier. As shown, this is thought to be due to the same phenomenon as component (ii) exhibiting extremely good adhesion to different materials. Therefore, in the present invention, even if component (i) is a mixture of different polymers, component (ii) acts as a binder for the mixture, and the whole is closely integrated to improve interphase peeling resistance. A composition is obtained. In addition, component (ii) has a great effect on improving adhesion to coating materials, and can form a strongly adherent coating film when applied. Furthermore, the composition of the present invention using an ionic crosslinked product of a modified block copolymer as component (ii) also has the advantage of being excellent in gloss. The composition of the present invention has excellent physical properties and appearance properties as described above, and can be said to be a composition suitable for use in molded products. Component (i) used in the present invention consists of any of the above-mentioned polymer groups, and examples of polyoxymethylene polymers include homopolymers produced by polymerization of formaldehyde or trioxane;
Alternatively, copolymers containing the above monomers as main components can be mentioned. For homopolymers, the end groups of the polymer are generally converted into ester groups or ether groups to improve heat resistance and chemical resistance.
Examples of the copolymer include copolymers of formaldehyde or trioxane with other aldehydes, cyclic ethers, cyclic carbonates, epoxides, isocyanates, vinyl compounds, and the like. Polycarbonate polymer has the general formula or (In the above formula, A ¹ _r represents a phenylene group or a phenylene group substituted with an alkyl group, a substituted alkyl group, an alkoxy group, a halogen or a nitro group, and A is an alkylene group, an alkylidene group, a cycloalkylene group, a cycloalkylidene group, It is an aromatic polycarbonate having a structural unit of sulfur, oxygen, sulfoxide group or sulfone group. A preferred example is poly-4,4'-dioxyphenyl-2,2'-propane carbonate. The modified polycarbonate polymer is obtained by blending a styrene polymer with an aromatic polycarbonate having the structural unit of the above general formula to improve its properties. Styrenic polymers used for modification include polymers containing 50% by weight or more of styrene, such as polystyrene, styrene-α-methylstyrene copolymer, butadiene-styrene block copolymer, and impact-resistant rubber-modified styrene polymer. Acrylonitrile-styrene copolymer, styrene-
Methacrylic acid ester copolymer, styrene-maleic anhydride copolymer, acrylonitrile-butadiene-styrene copolymer, acrylic acid ester
Examples include butadiene-styrene copolymer, methacrylate ester-butadiene-styrene copolymer, and mixtures of these polystyrene polymers. The polysulfone polymer has the general formula [-A ² _r -A ² _r -SO ₂ ]- or [-A ² _r -SO ₂ ]- (In the above formula, A ² _r represents a phenylene group,
B represents oxygen, sulfur or an aromatic diol residue. ) is a thermoplastic polysulfone having the following structural units. Preferred examples include poly(ether sulfone) and poly(4,4-bisbisphenol ether sulfone). A modified polysulfone polymer is a thermoplastic polysulfone having the structural unit of the above general formula mixed with the above styrene polymer to improve its properties. Nitrile polymers contain 50% by weight or more of α, β-
It is a thermoplastic homopolymer and/or copolymer synthesized using olefinic unsaturated mononitrile as a constituent monomer. Examples of α,β-olefinic unsaturated mononitriles include acrylonitrile, methacrinitrile, α-bromoacrylonitrile, and the like. These monomers may be used as a mixture of two or more. Monomers to be copolymerized with this α,β-olefinic unsaturated mononitrile include lower α-olefins such as ethylene, propylene, isobutylene, pentene-1, vinyl chloride, and vinylidene chloride, styrene, α-methylstyrene, and vinyltoluene. , vinyl aromatic compounds such as chlorostyrene, methylstyrene,
Vinyl ester compounds such as vinyl acetate, α, β- such as methyl acrylate, methyl methacrylate, etc.
Examples include lower alkyl esters of olefinic unsaturated carboxylic acids and vinyl ether compounds such as vinyl methyl ether. Polyphenylene ether polymer has the general formula (In the above formula, R ¹ and R ² are C ₁ to C ₄ alkyl groups,
Indicates a substituted alkyl group or halogen. ), or a polyphenylene ether graft copolymer obtained by graft polymerizing a styrene compound to the phenylene ether polymer. Styrene compounds used for graft modification include styrene, α-methylstyrene, methylstyrene, tert-butylstyrene, chlorostyrene, etc., and two or more of these may coexist during graft polymerization. If desired, other copolymerizable vinyl compounds such as acrylic esters, methacrylic esters, acrylonitrile, methacrylonitrile, etc. may be used in combination for cograft polymerization. A preferred phenylene ether polymer is poly(2,6-dimethyl-1,4-phenylene) ether, and a preferred graft modification thereof is a styrene graft copolymer of the polymer. In addition, the modified polyphenylene ether polymer is obtained by blending the above styrene polymer into a phenylene ether polymer or polyphenylene ether graft copolymer having the structural unit of the above general formula to modify its properties. This is what I asked. The polyarylene sulfide polymer has the general formula [-A ³ _r -S]- (in the above formula, A ³ _r represents a phenylene group, an alkyl group, or a phenylene group substituted with a substituted alkyl group). It is an arylene sulfide polymer or copolymer having a structural unit. Suitable examples include polyphenylene sulfide and poly4,4'-diphenylene sulfide. In addition, the modified polyarylene sulfide polymer is obtained by blending the above styrene polymer into an arylene sulfide polymer or copolymer having the structural unit of the above general formula to modify its properties. It is. In the polymer group of component (i) used in the present invention, styrene constituting each modified product of polycarbonate polymer, polysulfone polymer, polyphenylene ether polymer, and polyarylene sulfide polymer Suitable examples of the polymer include polystyrene, impact-resistant rubber-modified styrene polymer, acrylonitrile-butadiene-styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer, and any mixture thereof. . Generally, the content of styrenic polymer constituting the modified product is 70% by weight or less, more typically 50% by weight. In addition, in the polymer group of component (i) used in the present invention, polycarbonate polymers, polysulfone polymers, polyphenylene ether polymers, and polyarylene sulfide polymers have a molecular weight of
A value of 5,000 or more, preferably 10,000 or more is suitable. Next, to explain the modified block copolymer which is the other component of the thermoplastic polymer composition of the present invention, the modified block copolymer of component (ii) is composed of a vinyl aromatic compound as a base and a conjugated diene A molecular unit containing a dicarboxylic acid group or its derivative group is bonded to a block copolymer consisting of a compound. The block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound, which serves as a base, has one or more, preferably two or more, polymer blocks mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound. It contains one or more combined blocks. The weight ratio of the vinyl aromatic compound to the conjugated diene compound in this block copolymer is 5/95 to 70/30, preferably 10/90 to 70/30.
30, more preferably a composition range of 15/85 to 70/30. If the weight ratio is less than 5/95, the dispersibility in component (i) will be poor. In the composition of the present invention, the vinyl aromatic compound content of the block copolymer serving as the base is 5 or more and 60
In a range of less than % by weight, the effect of improving impact resistance is particularly large. The polymer block mainly composed of vinyl aromatic compounds in the above block copolymer is the hard segment of the block copolymer, and its glass transition point is
In this block whose temperature is 40°C or higher, preferably 60°C or higher, the weight ratio of the vinyl aromatic compound to the conjugated diene compound is 60/40 to 100/0, preferably
Composition range from 80/20 to 100/0, more preferably
It is 100/0. The distribution of the minor component conjugated diene compound in this block may be random, tapered (increasing or decreasing monomer component along the molecular chain), partially block-like, or any combination thereof. . On the other hand, a polymer block mainly composed of a conjugated diene compound is a soft segment of a block copolymer, and its glass transition point is 0°C or lower, preferably -20°C or lower. In this block,
The weight ratio of the vinyl aromatic compound to the conjugated diene compound is 0/100 to 40/60, preferably 0/100 to 30/
70 composition range. The distribution of the minor vinyl aromatic compound in this block may be random, tapered, partially block-like, or any combination thereof. A polymer block mainly composed of a vinyl aromatic compound or a polymer block mainly composed of a conjugated diene compound is
When more than one block is contained, each block may have the same structure or different structures. As the vinyl aromatic compound constituting the block copolymer, one or more types are selected from, for example, styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc.
Styrene is particularly preferred. In addition, examples of conjugated diene compounds include butadiene, isoprene, 1,
One or more types are selected from 3-pentadiene and the like, and among them, butadiene or a combination of conjugated diene compounds mainly composed of butadiene is preferred, and butadiene is particularly preferred. The average molecular weight of the block copolymer is 10,000~
The range is 1,000,000, preferably 20,000 to 800,000, more preferably 30,000 to 500,000. Furthermore, the molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof. Further, the above block copolymer may be slightly modified with an organic compound or an inorganic compound as long as its properties are not lost. The various polymer structure limitations regarding the block copolymer described above are necessary for the modified block copolymer to maintain its mechanical properties as a thermoplastic polymer. The block copolymer used in the present invention is usually produced by anionic polymerization of a vinyl aromatic compound and a conjugated diene compound using an organic lithium compound such as butyllithium as a polymerization catalyst in an inert hydrocarbon solvent such as penzene, hexane, or cyclohexane. A branched or radial block copolymer can be obtained by combining the block copolymer having a lithium active terminal obtained by the above method with a polyfunctional coupling agent such as tetrachloride. . In addition, any vinyl aromatic compound-conjugated diene compound block copolymer obtained by any production method may be used as long as it falls within the range of the above limitations. The above-mentioned block copolymer is not limited to only one type, but also has a polymer structure, such as styrene content, molecular weight,
It is also possible to combine two or more types of block copolymers having different numbers of blocks. In the present invention, a preferred modified block copolymer in which a molecular unit containing a dicarboxylic acid group or a derivative thereof is bonded to the above-mentioned block copolymer is a modified block copolymer in which a conjugated diene portion of the base block copolymer is bonded to a molecular unit containing a dicarboxylic acid group or its derivative. It is a polymer obtained by adding an unsaturated dicarboxylic acid or its derivative. The molecular unit containing a dicarboxylic acid group or its derivative group contained in the modified block copolymer is 0.05 to 20 parts by weight per 100 parts by weight of the base block copolymer,
Preferably 0.05 to 10 parts by weight, more preferably 0.1
~2 parts by weight. If the molecular unit containing a dicarboxylic acid group or its derivative group is less than 0.05 part by weight,
Almost no improvement effect is observed compared to the unmodified block copolymer, and even when the amount exceeds 20 parts by weight, the improvement effect is not as remarkable as when it is less than 20 parts by weight. Examples of the unsaturated dicarboxylic acids or derivatives thereof are maleic acid, fumaric acid, chloromaleic acid, itaconic acid, cis-4-cyclohexene-
1,2-dicarboxylic acid, endo-cis-bicyclo[2,2,1]-5-hepetene-2,3-dicarboxylic acid, acid anhydrides of these dicarboxylic acids,
There are esters, amides, imides, etc. The unsaturated dicarboxylic acid derivative may be added to the block copolymer as it is, or it may be converted into the corresponding derivative by an appropriate reaction after adding the unsaturated dicarboxylic acid to the block copolymer. Often, such reactions can be carried out after mixing with component (i) into the composition. Suitable unsaturated dicarboxylic acids or derivatives thereof include α,β-unsaturated dicarboxylic acids or derivatives thereof, specifically maleic acid, fumaric acid, and maleic anhydride. The modified block copolymer of the present invention can be obtained by subjecting the block copolymer to an addition reaction with an unsaturated dicarboxylic acid or a derivative thereof in a molten state or a solution state, with or without the use of a radical initiator. can get. The method for producing these modified block copolymers is not particularly limited in the present invention, but the modified block copolymers obtained may contain undesirable components such as gel, or may have poor flowability and poor processability. Manufacturing methods that result in poor quality should be avoided. A particularly preferred production method is a method in which the block copolymer serving as a base is melted using an extruder or the like without using a solvent, and then an unsaturated dicarboxylic acid or a derivative thereof is reacted in the absence of a radical initiator. (For more details, see the specification of Japanese Patent Application No. 53-99102). The thermoplastic polymer composition of the present invention comprises component (i) 100
Component (ii) is comprised of at least 1 part by weight and less than 100 parts by weight, preferably from 3 to 70 parts by weight. Ingredient (i)
If the ratio of component (ii) to 100 parts by weight is less than 1 part by weight, the effect of improving impact resistance and paintability will not be exhibited, and if it is more than 100 parts by weight, the rigidity of the composition will decrease, so it is preferable. do not have. In the present invention, the modified block copolymer described above can also be mixed in the thermoplastic polymer composition as an ionic crosslinked product. This ionic crosslinked product is obtained by crosslinking the above-mentioned modified block copolymer with one or a mixture of two or more of monovalent, divalent, and trivalent metal ions through ionic bonds. It can be obtained by reacting a modified block copolymer with any one or a mixture of two or more of monovalent, divalent and trivalent metal compounds as a crosslinking agent compound. In the above ionic crosslinked product, the dicarboxylic acid group or its derivative group of the modified block copolymer is
Ionization occurs by adding a crosslinker compound. The amount of ionization can be controlled by adjusting the amount of the crosslinking agent compound added, and the amount is measured using, for example, an infrared spectrophotometer. The amount of the crosslinking agent compound to be added is such that part or all of the dicarboxylic acid groups or derivative groups thereof contained in the modified block copolymer are ionized, and the ionization reaction proceeds almost quantitatively. In some cases, an excess of the crosslinking agent over the theoretical amount may be necessary to obtain the desired amount of ionization. In order to effectively obtain an ionic crosslinked product, it is preferable that the molar ratio between the metal compound and the dicarboxylic acid group or its derivative group contained in the modified block copolymer is 0.1 to 3.0. The crosslinking agent compound used to obtain the ionic crosslinked product by adding it to the modified block copolymer may be any one of the metal compounds of Groups 1, 2, and 3 of the periodic table; A mixture of two or more types is preferred, and specific examples thereof include sodium compounds, potassium compounds, magnesium compounds, calcium compounds, zinc compounds, and aluminum compounds. Preferred examples of these metal compounds are hydroxides, alcoholates, and carboxylates. A specific method for obtaining an ionic crosslinked product of a modified block copolymer is to add a crosslinking agent compound to a molten modified block copolymer, or to dissolve the modified block copolymer in an appropriate solvent. Examples include a method in which a crosslinking agent compound is added to this solution to cause a crosslinking reaction, and a method in which a modified block copolymer is used as a latex and a crosslinking agent is added thereto. It can be used as a method to obtain Furthermore, in the present invention, the crosslinking agent compound is added to the mixture consisting of the thermoplastic polymer of component (i) and the modified block copolymer of component (ii) in a molten state or in a state dissolved in an appropriate solvent. It is also possible to adopt a method of causing a crosslinking reaction to form an ionic crosslinked product. The ionic crosslinked modified block copolymer used in the present invention is thermoplastic and can be processed at high temperatures, and the ionic crosslinking is reversible. These features are unique to the crosslinked vinyl aromatic compound-conjugated diene compound block copolymer obtained by commonly used irreversible crosslinking such as sulfur crosslinking, peroxide crosslinking, or radiation crosslinking, and the present invention. This is essentially different from the ionic crosslinked modified block copolymer used. If necessary, thermoplastic polyamide, thermoplastic polyester, etc. may be added to the thermoplastic polymer composition of the present invention in an amount of 100 parts by weight or less based on 100 parts by weight of component (i) to modify its properties. can do. The reason why a composition that is closely integrated as a whole can be obtained even when such a resin is blended is considered to be because the effect of component (ii) as a binder is fully exhibited as described above. Examples of thermoplastic polyamide include nylon 6, 6-6, 7, 6-10,
6-12, 11, 12, etc., and known thermoplastic polyesters such as ethylene glycol terephthalate polyester or butanediol terephthalate polyester can be used, and the molecular weight is 5000.
or more, preferably 10,000 or more. The thermoplastic polymer composition of the present invention also includes silica, carbon black, clay, glass fiber,
It is possible to add organic fibers, reinforcing agents and fillers such as calcium carbonate, antioxidants, ultraviolet absorbers, pigments, lubricants, flame retardants and other additives. In particular, a composition containing 150 parts by weight or less, preferably 10 to 100 parts by weight of glass fiber per 100 parts by weight of the thermoplastic polymer composition of the present invention has improved rigidity, heat resistance, and mechanical strength. We provide superior materials for molded products. Glass fibers are usually used for resin mixing, with a diameter of 2 to 20μ and a length of 50 to 20,000μ.
are used. The thermoplastic polymer composition of the present invention can be prepared using various mixing devices commonly used for mixing polymeric substances, such as a single-screw or multi-screw extruder, a mixing roll, and a Banbury mixer, depending on the composition ratio of each component. , a kneader, etc., and it is preferable to mix in a molten state. Moreover, the composition of the present invention can also be obtained by a method of mixing solutions of each component and then removing the solvent by heating. The resin composition of the present invention can be formed into sheets, foams, films, injection molded products of various shapes, blow molded products by any conventionally known molding method, such as extrusion molding, injection molding, blow molding, rotation molding, etc. It can be easily molded into a wide variety of practically useful products such as molded products, air pressure molded products, and rotary molded products, and can be used for automobile parts, electrical parts, mechanical parts, etc. The molded article made of the thermoplastic polymer composition of the present invention thus obtained can be painted or plated as necessary. When painting, any known paint such as acrylic or vinyl-modified acrylic resin paint, alkyd resin paint, polyurethane resin paint, epoxy resin paint, phenol resin paint, melamine resin paint, urea resin paint, etc. Paint can also be used. In addition, when producing a metallic feel by plating, the thermoplastic polymer composition of the present invention using an ionic crosslinked modified block copolymer is particularly suitable for component (ii) in a highly irregular shape. ), so when chemically etched and plated, a plated molded product with a large anchoring effect and high adhesion strength can be obtained. As the plating method, any conventionally known method such as chemical plating or electric plating can be used. Examples will be shown below to explain the present invention in more detail, but it goes without saying that the content of the present invention is not limited to these Examples. Reference Example [Preparation of modified block copolymer] Using sample a, which is a tapered styrene-butadiene block copolymer having the structure B ₁ -S ₁ -B ₂ -S ₂ , maleic anhydride was prepared by the method shown below. A modified block copolymer (Sample A) grafted with was prepared. ). Note that sample a was n- in a hexane solution.
It was obtained using butyllithium as a polymerization catalyst, and had a styrene content of 40% by weight and a blocked styrene content of 33% by weight. Next, 1.5 parts by weight of maleic anhydride and 0.3 parts by weight as an anti-gelling agent were added to 100 parts by weight of sample a.
BHT (butyl hydroxytoluene) and 0.2 parts by weight of phenothiazine were added, and these were mixed uniformly using a mixer. This mixture was supplied to a 40 mm extruder (single screw, full-flight screw, L/D=24) under a nitrogen atmosphere, and a modification reaction was carried out at a cylinder temperature of 190 to 210°C. The obtained polymer was dried under reduced pressure to remove unreacted maleic anhydride. The analysis results of the modified block copolymer (sample A) showed that the toluene insoluble content was 0.05% by weight, and the amount of maleic anhydride added was 0.7 parts by weight per 100 parts by weight of the block copolymer, as measured by titration with sodium methylate. Ta. Examples 1 to 10 and Comparative Examples 1 to 6 10 parts by weight of the modified block copolymer (sample A) prepared in the reference example or an unmodified block copolymer as a comparative example based on 100 parts by weight of the thermoplastic polymer. (Sample a) 10 parts by weight, 2,6-di- as a stabilizer
1 part by weight of tert-butyl-4-methylphenol and 1 part by weight of trisnonyl phenyl phosphorite were thoroughly mixed in a Henschel mixer, and then pelletized using a 40 mm extruder in a conventional manner. The obtained pellets were injection molded to 120×120×
A 3 mm flat plate was created. After degreasing this flat plate with methyl alcohol, it was spray-painted with a commercially available acrylic resin paint and air-dried. In the case of flat plates made of compositions using polyoxymethylene and nitrile resins as thermoplastic polymers, instead of being degreased with methyl alcohol, they were immersed in a hydrochloric acid solution for 30 seconds and then spray cleaned with water. The results of the paint film adhesion test on the painted flat plate are shown in Table 1, and it can be seen that the composition of the present invention has extremely good paint film adhesion.

【table】

【table】

[Table] Examples 11 to 14 (S ₁ −B ₁ ) _—4 Radial type styrene-butadiene block copolymer with Si structure (styrene content 30% by weight, blocked styrene content 30% by weight, blocked styrene A modified block copolymer grafted with maleic anhydride (sample B) was obtained in the same manner as in the reference example (the amount of maleic anhydride added was 100 parts by weight of the block copolymer). (1.5 parts by weight). Next, the thermoplastic polymer and the modified block copolymer (Sample B) were pelletized in the same manner as above according to the processing method shown in Table 3. This pellet was injection molded to prepare a test piece, and the impact strength was measured. The results are shown in Table 3, and it can be seen that the present invention provides a composition with extremely excellent impact resistance.

[Table] Example 15 A composition of a thermoplastic polymer of the present invention containing glass fibers and a modified block copolymer was pelletized according to the process shown in Table 4. This pellet was injection molded to prepare a test piece, and the impact strength was measured. The results are shown in Table 4.

【table】

[Table] Used.

Claims (1)

[Scope of Claims] 1 (i) Polyoxymethylene polymers, polycarbonate polymers and modified products thereof, polysulfone polymers and modified products thereof, nitrile polymers, polyphenylene ether polymers and modified products thereof. 100 parts by weight of at least one thermoplastic polymer selected from synthetic materials, polyarylene sulfide polymers, and modified products thereof, and (ii) a weight ratio of a vinyl aromatic compound to a conjugated diene compound of 5. 1 part by weight or more of a modified block copolymer made by bonding a molecular unit containing a dicarboxylic acid group or a derivative group thereof to a block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound having a ratio of /95 to 70/30. A thermoplastic polymer composition comprising less than 100 parts by weight. 2 The modified block copolymer of component (ii) has its dicarboxylic acid group or its derivative group as a crosslinking site,
The composition according to claim 1, which is an ionic crosslinked product in which one or more of monovalent, divalent, or trivalent metal ions are ionicly crosslinked. 3. Claim 1, wherein the polyoxymethylene polymer of component (i) is a homopolymer produced by polymerization of formaldehyde or trioxane, or a copolymer containing the above monomer as a main component.
The composition according to item 1 or 2. 4 The polycarbonate polymer of component (i) has the general formula or (In the above formula, A ¹ _r represents a phenylene group or a phenylene group substituted with an alkyl group, a substituted alkyl group, an alkoxy group, a halogen or a nitro group, and A is an alkylene group, an alkylidene group, a cycloalkylene group, a cycloalkylidene group. ,sulfur,
Indicates oxygen, sulfoxide group or sulfone group. ) The composition according to claim 1 or 2, which is an aromatic polycarbonate having the structural unit. 5 The modified polycarbonate polymer of component (i) is a mixture of the aromatic polycarbonate and styrenic polymer described in claim 4, as set forth in claim 1 or 2. Composition. 6 The polysulfone polymer of component (i) has the general formula [-A ² _r -B-A ² _r -SO ₂ ]- or [-A ² _r -SO ₂ ]- (in the above formula, A ² _r is represents a phenylene group,
B represents oxygen, sulfur or an aromatic diol residue. ) The composition according to claim 1 or 2, which is a thermoplastic polysulfone having the structural unit. 7. The modified polysulfone polymer of component (i) is a mixture of the thermoplastic polysulfone described in claim 6 and a styrenic polymer as claimed in claim 1 or 2. Composition. 8 A patent claim in which the nitrile polymer of component (i) is a thermoplastic homopolymer and/or copolymer synthesized using 50% by weight or more of α,β-olefinic unsaturated mononitrile as a constituent monomer. Range 1
The composition according to item 1 or 2. 9 The polyphenylene ether polymer of component (i) has the general formula (In the above formula, R ¹ and R ² are C ₁ to C ₄ alkyl groups,
Indicates a substituted alkyl group or halogen. ) The composition according to claim 1 or 2, which is a phenylene ether polymer having the structural unit. 10 The polyphenylene ether polymer of component (i) has the general formula (In the above formula, R ¹ and R ² are C ₁ to C ₄ alkyl groups,
Indicates a substituted alkyl group or halogen. 3. The composition according to claim 1 or 2, which is a polyphenylene ether graft copolymer obtained by graft-polymerizing a styrene compound to a polyphenylene ether polymer having the following structural units. 11 The modified polyphenylene ether polymer of component (i) is the phenylene ether polymer according to claim 9 or the polyphenylene ether graft copolymer according to claim 10. 3. The composition according to claim 1 or 2, which is a mixture consisting of a styrenic polymer and a styrene polymer. 12 The polyarylene sulfide polymer of component (i) has the general formula [-A ³ _r -S]- (in the above formula, A ³ _r is substituted with a phenylene group, an alkyl group, or a substituted alkyl group). The composition according to claim 1 or 2, which is an arylene sulfide polymer or copolymer having the structural unit (representing a phenylene group). 13 A patent claim in which the modified polyarylene sulfide polymer of component (i) is a mixture consisting of the arylene sulfide polymer or copolymer described in claim 12 and a styrene polymer. The composition according to range 1 or 2. 14 Styrenic polymer is polystyrene, impact-resistant rubber-modified styrene polymer containing 50% by weight or more of styrene, acrylonitrile-butadiene-styrene copolymer, methacrylic acid ester.
Claims 5 and 7 are butadiene-styrene copolymers and any mixtures thereof.
The composition according to item 1, item 11 or item 13. 15 The modified block copolymer of component (ii) is a block copolymer containing one or more polymer blocks mainly composed of a vinyl aromatic compound and one or more polymer blocks mainly composed of a conjugated diene compound. The composition according to claim 1 or 2, which is a modified polymer. 16. The composition according to claim 15, which is a modified block copolymer in which the content of vinyl aromatic compounds in the modified block copolymer is 10% by weight or more and less than 60% by weight. 17 A patent in which the modified block copolymer of component (ii) is a modified block copolymer containing 0.05 to 20 parts by weight of a molecular unit containing a dicarboxylic acid group or its derivative group per 100 parts by weight of the block copolymer. A composition according to claim 1 or 2. 18. The composition according to claim 1 or 2, wherein the modified block copolymer of component (ii) is a modified block copolymer obtained by adding an unsaturated dicarboxylic acid or a derivative thereof to a block copolymer. . 19 Claims in which the modified block copolymer is a modified block copolymer obtained by reacting a molten block copolymer with an unsaturated dicarboxylic acid or a derivative thereof in the absence of a radical initiator. Composition according to item 18. 20 Unsaturated dicarboxylic acid or its derivative is
The composition according to claim 18 or 19, which is an α,β-unsaturated dicarboxylic acid or a derivative thereof. 21. The composition according to claim 20, wherein the α,β-unsaturated dicarboxylic acid or its derivative is maleic acid, fumaric acid or maleic anhydride. 22 A patent in which the ionic crosslinked product of component (ii) is an ionic crosslinked product crosslinked with any one type or a mixture of two or more metal ions from Group 3, Group 3, and Group 3 of the Periodic Table. The composition according to claim 2. 23 The ionic crosslinked product is an ionic crosslinked product crosslinked with any one or a mixture of two or more of sodium compounds, potassium compounds, magnesium compounds, calcium compounds, zinc compounds, and aluminum compounds. A composition according to Range 22. 24. The composition according to claim 1 or 2, which contains glass fiber in an amount of 150 parts by weight or less based on 100 parts by weight of the total amount of component (i) and component (ii). 25 For 100 parts by weight of component (i), 100 parts of thermoplastic polyamide and/or thermoplastic polyester
The composition according to claim 1 or 2, wherein the composition is blended in an amount of not more than 1 part by weight. 26. The composition according to claim 1 or 2, wherein the composition is in the form of a coated molded article.