JPS6381154A - Modified block copolymer composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent impact resistance, interfacial peeling resistance, paintability, weather resistance and thermal aging resistance, by compounding a thermoplastic polymer such as polyoxymethylene polymer with a specific modified block copolymer. CONSTITUTION:The objective composition is produced by compounding (A) 95-5wt% polymer selected from polyoxymethylene polymer, (modified) polycarbonate polymer, (modified) polysulfone polymer, nitrile polymer, (modified) polyphenylene ether polymer and polyarylene sulfide polymer with (B) 10-95wt% modified block copolymer produced by bonding 0.05-20pts.wt. of a molecule containing carboxylic acid (derivative) group to 100pts.wt. of a block copolymer containing 60-90wt% vinyl aromatic hydrocarbon and composed of a vinyl aromatic compound polymer block A and an olefin compound polymer block B having an unsaturation degree of <=20wt%.

Description

Detailed Description of the Invention The present invention provides impact resistance, interfacial peeling resistance, paintability, weather resistance,
Regarding a resin-like modified block copolymer composition having excellent heat aging resistance, more specifically, a block copolymer having a vinyl aromatic compound polymer block and an olefin compound 1 combined block has a carboxylic acid group or its derivative group. Modified block copolymers in which molecular units containing are bonded, polyoxymethylene polymers, polycarbonate 1 polymers or modified products thereof, polysulfone 1 polymers or modified products thereof, nitrile polymers, polyphenylene ether polymers or a modified product thereof, and a thermoplastic polymer made of any one or a mixture of two or more of polyarylene sulfide polymers or modified products thereof, and a polymer composition 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 are required to have high mechanical properties, heat resistance, durability, etc. It is widely used as an alternative material for metals in applications such as 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 though engineering resins have such excellent properties, they cannot sufficiently satisfy the properties required in other aspects of the application fields in which they are utilized.
There were some drawbacks.

For example, polyoxymethylene resins and nitrile resins have extremely high tensile strength, bending strength, and elastic modulus, and while they have the advantage of being able to produce extremely tough molded products and have excellent resistance to corrosion agents, they have the advantage of being easy to paint. Its use as an exterior material is limited. 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, attempts have been made to improve the impact resistance of polyphenylene ether resins by blending rubber-modified impact-resistant polystyrene or block copolymers of styrene and butadiene. It is being With this improvement method, the above drawbacks can be overcome.
・Although improvements have been made to this material, there is a need for a modified material that has an even greater impact resistance improvement effect.

On the other hand, a block copolymer composed of a vinyl aromatic compound and a conjugated diene compound exhibits good elasticity at room temperature without vulcanization when the content of the vinyl aromatic compound is relatively small. When the content of the compound is relatively high, it has excellent transparency and impact resistance, and both exhibit fluidity similar to that of thermoplastic resins at high temperatures, so they can be easily molded using general extruders and injection molding machines. It can be molded and is widely used for footwear, food packaging containers, etc.

However, despite having such excellent properties, a major reason why the scope of use of such block copolymers is limited is because of their poor heat resistance. Another drawback is that it is inferior in abrasion resistance and compressive strain resistance compared to materials using vinyl chloride polymers, especially in footwear applications.

Many attempts have been made to improve these shortcomings. For example, in Japanese Patent Publication No. 54-27025, an attempt has been made to incorporate polyarylene oxide into a block copolymer as a method of improving the heat resistance of the block copolymer. Although the heat resistance of the block copolymer was improved by this method, the effect of improving heat resistance was not sufficient depending on the ratio of the amount of polyarylene oxide blended.

In addition, as a method for improving the abrasion resistance and compression strain resistance of block copolymers, there is a method of crosslinking using peroxide and sulfur-vulcanization accelerator systems, but how do these properties improve? Although this is improved to some extent, problems such as the inability to recycle after molding occur, and another problem arises in that the advantage of using a thermoplastic block copolymer is lost. Another method is to add an inorganic photoresist to increase hardness and improve wear resistance, but in this case, compression strain resistance is impaired and this method is not practical. Ta. In short, no effective method has been found for improving the abrasion resistance and compressive strain resistance of block copolymers without impairing their processability.

As a result of intensive studies to solve such problems, the present inventors have discovered that a vinyl aromatic compound-conjugated diene compound block copolymer modified with dicarboxylic acids or an ionic crosslinked product thereof, and the thermoplastic monomer described above It was discovered that the object could be achieved by combining the above, and was proposed in Patent Application No. 55-17216 and Japanese Patent Application No. 55-17217. Subsequently, the present inventors conducted further studies on improving the properties of compositions using such modified block copolymers, and as a result, a block copolymer composed of a vinyl aromatic compound polymer block and an olefin compound polymer block was developed. Using a modified block copolymer in which a molecular unit containing a carboxylic acid group or its derivative group is bonded is unlikely to solve the above problems. The present inventors have discovered that a composition with excellent properties can be obtained, and have completed the present invention.

That is, the present invention provides (a) polyoxymethylene polymers, polycarbonate polymers or modified products thereof, polysulfone polymers or modified products thereof, nitrile polymers, polyphenylene ether polymers or modified products thereof, polyoxymethylene polymers, polycarbonate polymers or modified products thereof, At least one thermoplastic polymer selected from arylene sulfide polymers or modified products thereof (b) The content of vinyl aromatic hydrocarbons is more than 601% by weight and not more than 90% by weight, and at least A block copolymer having one vinyl aromatic compound polymer block A and at least one olefin compound polymer block B, in which the degree of unsaturation of block B does not exceed 20%. A modified block copolymer in which 0.05 to 20 parts by weight of molecular units containing a dioxylic acid group or a derivative group thereof are bonded as an average value to 100 parts by weight of the "substrate block copolymer" The present invention relates to a modified block copolymer composition having an amount of 10 to 954.

Generally, different types of polymers are not miscible with each other, and even when they are forcibly mixed together by melt-kneading or the like, they have poor adhesion at their mutual interfaces. Therefore, mutual characteristics are rarely expressed effectively.

In order to effectively express mutual properties by mixing different types of polymers, improving the adhesion at the interface between different types of polymers is one of the important factors. Attempts have been made to further incorporate additives that have an affinity for monomerization. However, in the present invention, °C is
Component (a) and component (
In b), the interface exhibits strong adhesion, resulting in a novel composition with properties unforeseeable by conventional methods.

In the present invention, when the composition ratio is high in the thermoplastic polymer of component (a), a tough resinous composition having good interfacial peeling resistance and excellent impact resistance etc. can be obtained.

The composition of the present invention has a great effect of improving adhesion to coating materials, and can form a strongly adherent coating film when applied.

In addition, the modified block copolymer used in the present invention is limited so that the degree of unsaturation of one olefin compound block does not exceed 20%, so it can be used in combination with conventional block copolymers with a high degree of unsaturation, such as A molded article with excellent weather resistance and heat aging resistance can be obtained compared to when a styrene-butadiene block copolymer is used.

Furthermore, the composition of the present invention using an ionic crosslinked modified block copolymer as component (b) 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 articles.

The present invention will be explained in detail below.

The component (a) used in the present invention consists of any one of the above-mentioned polymer groups, and among these, examples of polyoxymethylene-based polymers include homopolymers produced by polymerization of formaldehyde or trioxane, or the above-mentioned polymers. Examples include copolymers whose main components are monomers. 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.

The polycarbonate-based 1-unit is expressed by the general formula or O (In the above formula, Ar is a phenylene group,
It represents a substituted alkyl group, an alkoxy group, a phenylene group substituted with a halogen or a nitro group, and A represents an alkylene group, an alkylidene group, a cycloalkylene group, a cycloalkylene group, sulfur, oxygen, a syaphooxide group or a sulfone group. ) is an aromatic polycarbonate having the following structural units. A preferred example is poly-4,41-dioxydiphenyl-2,2'-propane carbonate.

In addition, the polycarbonate-based polymer modification substance is obtained by blending a styrene-based polymer with an aromatic polycarbonate having the structural unit of the above general formula to modify its properties. Styrenic polymers used for modification include monomers containing 50% styrene, such as polystyrene, styrene-α-methylsf and 7coM polymers, butadiene-styrene block copolymers, 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-butazoene Examples include styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer, and mixtures of these polystyrene polymers.

A polysulfone polymer is a thermoplastic polysulfone having a structural unit of the general formula (in the above formula, A represents a phenylene group, and B represents oxygen, sulfur, or an aromatic diol residue).

Preferred examples include poly(ether sulfone),
J (4,4-??sphenol ether ν sulfone) is mentioned.

A modified polysulfone polymer is a thermoplastic polysulfone having the structural unit of the general formula - above, blended with the styrene polymer described above to modify its properties.

The nitrile polymer is a thermoplastic homopolymer and/or copolymer synthesized using α,β-olefin thread unsaturated mononitrile having a weight coefficient of 50 or more as a constituent monomer.

Examples of α,β-olefinically unsaturated mononitriles include acrylonitrile, methacrylonitrile, and α-bromoacrylonitrile. These monomers may be used as a mixture of two or more. This α, β−
Monomers to be copolymerized with the olefinically unsaturated mononitrile include lower α-olefins such as ethylene, zolopyrene, isofluorene, pentene-1, vinyl chloride, vinylidene chloride, styrene, α-methylstyrene, vinylene, Vinyl aromatic compounds such as chlorostyrene and methylstyrene, vinyl nitrous compounds such as vinyl acetate, lower alkyl esters of α,β-olefinically unsaturated carabonic acids such as methyl acrylate and methyl methacrylate, vinyl n,-mechaate! Shino Vinny I
Examples include rhetheia compounds.

The polyphenylene ether polymer is a phenylene ether polymer having a structural unit of the general formula (in the above formula, R1 and R2 represent a C1 to C4 alkyl group, a substituted alkyl group, or a halogen), or a phenylene ether polymer having This is a polyphenylene ether graft copolymer obtained by graft polymerizing a styrene compound. Styrenic compounds used for graft modification include styrene, α-methylstyrene, methylstyrene, and TJert.
Examples include l-butylstyrene, chlorstyrene, etc.
Two or more of these may coexist during graft polymerization, and if desired, other copolymerizable vinyl compounds,
For example, acrylic acid ester and methacrylic acid ester,
It is also possible to carry out co-graft polymerization by using acrylonitrile and methacrylonitrile in combination. Preferred phenylene ether polymers include poly(2,6-dimethe-7-ray-1-4-)unicine) ether, and preferred graft modified products thereof include styrene graft copolymers of the polymers. can give.

In addition, the polyphenylene ether-based polymer modified product is obtained by blending the above-mentioned styrene-based 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 did.

The polyarylene diphyto polymer is an arylene diphyto polymer or copolymer having a structural unit of the general formula (in the above formula, AF represents a phenylene group or a phenylene group substituted with an alkyl group or a substituted alkyl group). It is a polymer. Suitable examples include polyphenylene sulfide and poly-4,4'-diphenylene sulfide.

In addition, the modified polyarylene sulfite polymer is obtained by blending the above styrene polymer into an arylene sulfite polymer or copolymer having the structural unit of the above general formula to modify its properties. be.

In the polymer group of component (a) used in the present invention, modified products of a polycarbonate polymer, a polysulfone polymer, a polyphenylene ether V polymer, and a polyarylene diphyte polymer are included. Preferred examples of the styrene polymer include polystyrene, impact-resistant rubber-modified styrene polymer, acrylonidriabbutadiene-styrene copolymer, and methacrylic acid ester-butadiene.

Styrene copolymers, and any mixtures thereof. Generally, the content of the styrene polymer constituting the modified product is 70% by weight or less, and generally 50% by weight or less! 1
% or less.

In the polymer group of component (a) used in the present invention, polycarbonate polymers, polysulfone polymers, polyphenylene ether polymers, and polyarylene sulfide polymers have a molecular weight of 5.000 or more. , preferably 10,000 or more.

The modified block copolymer which is the component (b) of the composition of the present invention comprises at least one vinyl aromatic compound polymer block A and at least one olefin compound polymer block in which the degree of unsaturation does not exceed 20. A modified block copolymer in which a molecular unit containing a levonic acid group or its fatty conductor group is bonded to a block copolymer consisting of B (hereinafter referred to as "substrate block copolymer"). It is. Here, the olefin compound polymer block refers to monoolefins such as ethylene, fluoropylene, 1-butene, isobutylene, or butadiene, isopre7.1.3-
Conjugated diolefins such as pentagene, 1,4-he'
It is a polymer block having a polymerized or copolymerized form of one or more olefin compounds selected from non-conjugated diolefins such as Ff diene, norbornene, and tulbolenene derivatives, and the degree of unsaturation of the block is is 2
It is 0% or less.

Therefore, when the above-mentioned diolefins are used as constituent monomers of an olefin compound polymer block, measures are taken to reduce the degree of unsaturation by methods such as hydrogenation until the degree of unsaturation in the block portion does not exceed 20%. must be applied. Further, a vinyl aromatic compound may be randomly copolymerized in the olefin compound polymer block. In the present invention, examples of the "substrate block copolymer" include hydrogenated block copolymers consisting of a vinyl aromatic compound and a conjugated diene compound, block copolymers of a vinyl aromatic compound and a monoolefin, etc. Can be mentioned. The modified block copolymer used in the present invention is
It can be produced by adding an unsaturated carboxylic acid or a derivative thereof to a block copolymer serving as a base.

In the present invention, the most preferable modified block copolymer as component (b) is a block copolymer (hereinafter referred to as The conjugated diene moiety of the block copolymer (referred to as the "precursor block copolymer") is selectively hydrogenated to an extent that the degree of unsaturation does not exceed 20%, and then the unsaturated carboxylic acid or its derivative is dissolved by an addition reaction. This is a modified block copolymer obtained by bonding.

"Block copolymer as a precursor" is at least one
2, preferably 2 or more vinyl aromatic compound polymer blocks and at least one conjugated diene-based polymer block. Here, the polymer block mainly composed of conjugated diene has a weight ratio of vinyl aromatic compound to conjugated diene compound of 0/100 to 50150.
．． Preferably, it is a polymer block having a composition range of 0/100 to 30/70, and the distribution of the vinyl aromatic compound in this block is random, tapered (monomer component increases or decreases along the molecular chain), It may be partially block-shaped or any combination thereof. In addition, in the "block copolymer as a precursor" in the present invention, the content of the vinyl aromatic compound is contained in the transition region between the vinyl aromatic compound polymer block and the polymer block mainly composed of a conjugated diene compound. Although there may be a copolymer block of a vinyl aromatic compound and a conjugated diene compound with a weight ratio of more than 50, such a polymer block shall be included in the above-mentioned polymer block mainly composed of a conjugated diene compound. .

In the "block copolymer as a precursor", the N ratio of the vinyl aromatic compound content to the conjugated diene compound content is in the range of more than 60/40 and 90/10 or less, preferably 65/65 to 85. /15 range.

As the vinyl aromatic compound constituting the "block copolymer as a precursor", one or more kinds are selected from styrene, α-"methylstyrene, vinyltoyaene, etc., and styrene is particularly preferred. Conjugated diene compounds include butadiene, isoprene, 1,6-
(One or more selected from among pentagene, etc.)
Particular preference is given to temophtadiene and/or imprene. The above block copolymer has a number average molecular weight of 20.
000 to 50 mouths, preferably 40,000 to 30
The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably in the range of 1.05 to 10. Further, the molecular structure of the block copolymer may be linear, branched, radial, or a combination thereof. Furthermore, when butadiene is used as the conjugated diene compound in the block copolymer, the amount of 1.2 bonds in the microstructure of the butadiene moiety is preferably in the range of 10 to 80%. If the modified block copolymer needs to have rubber elasticity, the 1.2 bond content should be 25 to 65%.
, more preferably in the range of 35 to 55%.

In the case where the above block copolymer contains two or more vinyl aromatic compound polymer blocks or polymer blocks mainly composed of a conjugated diene compound, each block may have the same structure and temperature, and the monomer components may be Each structure such as content, distribution in their molecular chains, molecular weight of the block, microstructure, etc. may be different.

As for the production method of "block copolymer as #J precursor", for example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 4
3-14979, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 48-4106
Examples include methods that are fully described in publications. All of these methods use an organic lyticum compound or the like as an anionic polymerization initiator in a hydrocarbon solvent, and if necessary, an ether compound such as diethyl ether, tetrahydrofuran, triethyl amine, N, N, N as a vinylating agent.
'.

Using a tertiary amine such as N'-tetramethylethylenecyamine, a Lewis base such as a phosphine compound such as hexamethylene phosphoamide, and a polyfunctional compound such as silicon tetrachloride or epoxidized soybean oil as a coupling agent,
This is a method of block copolymerizing a vinyl aromatic compound and a conjugated diene compound, resulting in a block copolymer having a linear, branched, or radial structure. In the present invention, no matter what polymerization method is used,
Anything within the above range can be used. Furthermore, it is also possible to use not only one type of block copolymer but also a mixture of two or more types.

By hydrogenating the above-mentioned "block copolymer as a precursor" by a known method, for example, the method described in Japanese Patent Publication No. 42-8704, a "block copolymer as a base material" is obtained.
is obtained. The "base block copolymer" means that at least 80% of the aliphatic double bonds based on the conjugated diene compound in the polymer block mainly composed of the conjugated diene compound of the "precursor block copolymer" In other words, the degree of unsaturation in the block morphologically converted into olefin compound polymer block B by hydrogenation of a polymer block mainly composed of a conjugated diene compound does not exceed 20 parts. It is necessary. If the degree of unsaturation of the olefin compound polymer block exceeds 20%, it is not preferred because the weather resistance and heat aging resistance of the molded article of the unsaturated polynisture resin composition will be poor. On the other hand, the hydrogen of the aromatic double bond based on the vinyl aromatic compound copolymerized in the vinyl aromatic compound polymer block and the vinyl aromatic compound copolymerized in the polymer block mainly composed of a conjugated diene compound as required. Although there is no particular restriction on the addition rate, it is preferable that the hydrogenation rate is 20% or less. The degree of unsaturation of the combined block of olefin compound 1 can be measured by instrumental analysis using an infrared spectrophotometer (Engineering R), JP nuclear magnetic resonance apparatus (NMR), etc., titration analysis using iodometric titration method, etc.

The "substrate block copolymer" is then modified by an addition reaction with an unsaturated levonic acid or a derivative thereof to synthesize the modified block copolymer used in the present invention. Examples of unsaturated carboxylic acids or derivatives thereof include:
Maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-, cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo[2,2,1:1-5-
Examples include hebutene-2,3-dicarboxylic acid, acid anhydrides, esters, amides, imides, etc. of these dicarboxylic acids, acrylic acid) methacrylic acid, etc., and nisters and amides of these monocasipic acids. These can be used not only alone but also as a mixture of two or more. Among these, unsaturated cyclorvyfenic acid or its derivatives are preferred;
Particularly preferred is maleic anhydride.

Modified block copolymers are obtained by adding unsaturated carabonic acid or its derivatives to a "substrate block copolymer" in a solution or melt state, with or without the use of a radical initiator. . The method for producing these modified block copolymers is not particularly limited in the present invention, but if the obtained modified block copolymers contain undesirable components such as Del, their melt viscosity increases significantly. A manufacturing method that deteriorates workability is not preferred. A preferred method includes, for example, a method in which a "substrate block copolymer" is reacted with an unsaturated carboxylic acid or a derivative thereof in an extruder in the presence of a radical initiator.

The amount of molecular units containing a carboxylic acid group or its derivative group contained in the modified block copolymer, that is, the amount of unsaturated V-carboxylic acid or its derivative added, is determined based on the total amount of the modified block copolymer used in the present invention. As an average value, 0.0 per 100 parts by weight of [base block copolymer]
The amount is 5 to 20 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.6 to 5 parts by weight. If the molecular unit containing a dicarboxylic acid group or its derivative group is less than 0.05 parts by weight, little improvement effect will be observed compared to the unmodified block copolymer, and even if it exceeds 20 parts by weight, less The improvement effect is not as remarkable as in the case.

The content of molecular units containing carboxylic acid groups or derivative groups thereof in the modified block copolymer can be easily determined by a method using an infrared spectrophotometer, titration, or the like.

In addition, in the present invention, it is preferable that the added cap of unsaturated levonic acid or its derivative in the modified block copolymer used as component (b) at O May Contain Block Copolymer In the present invention, the modified block copolymer described above can also be mixed in the composition as an ionic crosslinked product.

This ionic crosslinked product is made by combining the modified block copolymer with any one of monovalent, divalent and hexavalent metal ions.
The modified block copolymer is crosslinked by ionic bonding with a species or a mixture of two or more species, and any one of monovalent, divalent, and trivalent metal compounds (18k or 2) is added to the modified block copolymer.
It is obtained by reacting a mixture of more than one species as a crosslinking agent compound.

In the above ionic crosslinked product, the carboxylic acid group or its derivative group of the modified block copolymer is ionized by adding a crosslinking agent compound. The amount of ionization can be adjusted by adjusting the amount of crosslinking compound added.
The amount is measured, for example, by an infrared spectrophotometer.

The amount of the crosslinking agent compound to be added is such that a part or all of the carboxylic acid groups or derivative groups thereof contained in the modified block copolymer are ionized, and the above ionization reaction is carried out by
Although the process proceeds approximately quantitatively, an excess of the crosslinking agent over the theoretical amount may be necessary in order 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 carboxylic acid group or its derivative group contained in the modified block copolymer is 0°1 to 6.0. .

The crosslinking agent compound used to obtain the ionic crosslinked product by adding it to the modified block copolymer is any one of the metal compounds of Group 1, Group II, and Group 1 of the Periodic Table. Or a mixture of 281 or more is preferable, and specific examples include sodium compounds, potassium compounds, magnesium compounds, calcium compounds, zinc compounds, and aluminum compounds. Preferred examples of these metal compounds are hydroxides, alcoholades, and carboxylates.

Specific methods for obtaining ionic crosslinked products of modified block copolymers include adding a crosslinking agent compound to the modified block copolymer in a molten state, or dissolving 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 way to obtain things.

In addition, in the present invention, the crosslinking agent compound is added to the mixture of the thermoplastic polymer of component (a) and the modified block copolymer of component (b) in a bath-melted state or in a state dissolved in an appropriate solvent. It is also possible to adopt a method in which an ionic cross-linked product is formed by adding it to cause a cross-linking reaction.

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 characteristics are characterized by the crosslinking of block copolymers obtained by irreversible crosslinking such as commonly used ionic crosslinking, peroxide crosslinking, or radiation crosslinking, and the ionic crosslinking of modified block copolymers used in the present invention. This is the point in which things are essentially different.

In the present invention, the weight ratio of component (a) to component (b) is 9°/10 to 5/95, preferably 85/15 to 10/90.
More preferably, it is in the range of 80/20 to 15/85. If the amount of component (b) is less than the above range, the effect of improving impact resistance and paintability will be small, whereas if it is too large, the rigidity will decrease.

The modified block copolymer composition of the present invention may optionally contain thermoplastic polyamide, thermoplastic polyester, etc. in an amount of 100 parts by weight or less per 100 parts by weight of component (a). can be modified. The reason why a composition that is closely integrated as a whole can be obtained even when such other polymers are blended is thought to be because the good adhesion of component (b) is fully demonstrated as described above. . Examples of thermoplastic polyamide include nylon 6, 6-6,
7, 6-10゜6-12, 11 and 12, etc., and thermoplastic polyester and L-C can be known ones such as ethylene glycol terephthalate type or butanedi-l-reterephthalate type polyester, and molecular weight The preferred value is 5,000 or more, preferably i o, o o o or more.

The modified block copolymer composition of the present invention also contains silica, carbon black, clay, glass fiber, organic fiber, carbonic acid! It is possible to add reinforcing agents and fillers such as resicum, antioxidants, UV absorbers, stabilizers, pigments, lubricants, flame retardants and other additives.

For example, 150 parts by weight or less of glass fiber per 10* parts of the resinous modified block copolymer composition of the present invention,
A composition containing preferably 10 to 100 parts by weight has improved rigidity, heat resistance, and mechanical strength, and provides an excellent material for molded articles. Glass fibers typically used for resin mixing are 2 to 20μ in diameter and 50 to 20,000μ in length.
are used.

The modified block copolymer composition of the present invention can be prepared using various types of mixing equipment that are commonly used for mixing polymeric substances, such as a -screw or multi-screw extruder, a mixing glow v , Banbury mixer, kneader
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 modified block copolymer composition of the present invention can be produced into sheets, foams, films, injection molded products of various shapes, etc. by any conventionally known molding method, such as extrusion molding, injection molding, blow molding, rotational molding, etc. It can be easily molded into a wide variety of practically useful products such as blow molded products, pressure molded products, rotary molded products, etc., and is used for automobile parts, electrical parts, J&N machine parts, footwear, electric wire caps, food packaging containers, etc. can do.

The molded article made of the modified block copolymer composition of the present invention thus obtained can be painted or plated as required.

When painting, the paint may be acrylic or vinyl-modified acrylic resin paint, alkyd resin paint, polyurethane resin paint, epoxy resin paint, phenolic resin paint, melamine resin paint, area resin paint, etc. Any paint can be used.

Additionally, plating can give it a metallic feel. As the plating method, any conventionally known method such as chemical plating or electroplating can be used. In particular, component (b
In the resin-like modified block copolymer composition of the present invention using an ionic crosslinked modified block copolymer as ), when the amount of component (a) is large, component (b) is in an extremely irregular shape. Since it is dispersed in component (a), when chemically etched and plated, a plated molded product with a large anchoring effect and high plating adhesion strength can be obtained.

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. The modified block copolymers used in the following examples were prepared as follows.

(1) Preparation of hydrogenated block copolymer Anionic block polymerization of butadiene and styrene using n-butyllithium as a polymerization catalyst and tetrahydrofuran as a vinyl content regulator in n-hexane or cyclohexane solvent. A block copolymer as shown in Table 1 was synthesized by the following steps.

Table I (Note 1) B indicates a butadiene-1 combined block, B' indicates a butadiene-styrene random copolymer block, and S indicates a styrene-1 combined block. In sample A-4, silicon tetrachloride was used as the coupling agent.

(Note 2) Measured using a nuclear magnetic resonance apparatus.

Next, the block copolymers shown in Table I were heated in a cyclohexane solvent using cobalt naphthenate, tri, Z f & aluminum mocum as catalysts at a hydrogen pressure of 7/bo 2 and a temperature of 50
Hydrogenation was carried out at °C for 5 hours, and about 90% of the double bonds in the butadiene block were hydrogenated, and the benzene ring in the styrene block remained almost unhydrogenated, indicating that it was selectively hydrogenated. A block copolymer was synthesized. The metal remaining on the catalyst was removed by washing with an aqueous hydrochloric acid solution and methanol.

(2) Preparation of modified block copolymer 6 parts per 100 TL of the hydrogenated block copolymer synthesized in (1) above
Parts by weight of maleic anhydride, 0.1 parts by weight of Perhexa2
5B (manufactured by Nihon Yushi Co., Ltd.) was mixed uniformly, and then a screw type extruder (single screw, screw diameter 20 m) was used under nitrogen atmosphere.
11sL/D=24, Hunflite type screw), and the maleation reaction was carried out at a cylinder temperature of 250°C. From the obtained modified block copolymer, unreacted maleic anhydride was removed under reduced pressure by heating to give 2,6-jetasha IJ--butyl-4-methylpheno-1-BH'r)t,X copolymer 100 as a stabilizer. 90.5 parts by weight was added per part. When this hydrogenated block copolymer was analyzed, the results shown in Table 2 were obtained.

Table 2 (Note 6) The amount of maleic anhydride added was measured by titration with sodium methylate.

The amount of maleic anhydride added is maleic anhydride.

Adjustments were made by changing the amounts of inic acid and Barhexa 25B added.

In the examples of the present invention, the thermoplastic resins listed in Table 3 were used.

Examples 1 to 4 and Comparative Examples 1 to 4 50 parts by weight of the modified block copolymer or unmodified block copolymer shown in Table 4 was blended with 100 parts by weight of the thermoplastic polymer shown in Table 4. Pellets of each composition were obtained. This pellet was injection molded to prepare a test piece, and the impact strength and surface gloss were measured.

The results are shown in Figure 4. Table 4 also shows the gloss of a test piece of a composition containing an ionic crosslinked modified block copolymer (sample B-4) as a block copolymer. It was a completely unexpected fact that there would be further improvements.

The ionic crosslinked modified block copolymer used in this experiment was prepared as follows. Sample B-4 was dissolved in toluene to make a 2.0% by weight solution, and sodium methylate was added as a crosslinking agent to this bath solution. Sample B-4 was mixed with 100 parts by weight of 0.6 parts per liter of renin-methanol mixed bath. Ionic crosslinking was performed by adding it as a bath medium and reacting at room temperature, and removing the bath medium to obtain an ionic crosslinked product of sample B-4. It was confirmed by infrared spectroscopy that the acid anhydride groups in Sample B-4 were ionized by this treatment.

Next, a weather resistance test and a heat aging resistance test were conducted using the same molded plates as those used in the Examples and Comparative Examples.

In the weather resistance test, the Izot impact strength of the molded piece was measured after being exposed to a Uedeometer i ooo time. In the heat aging resistance test, the molded pieces were left in an atmosphere of about 120'C for about one month, and then the Izot impact strength was measured.

As a result, the molded pieces of Examples 1 to 4 were 70% lower than those before the test.
% or more, but Comparative Example 1
The molded specimens No. 4 to 4 exhibited an Izot impact strength of less than 60% of that before the test, demonstrating that the composition of the present invention has excellent weather resistance and heat aging resistance.

(Hereinafter referred to as "light color") Examples 5, 6 and Comparative Example 5.6 200 parts by weight of a modified block copolymer (sample B-5) or an unmodified block copolymer as a comparative example based on 100 parts by weight of po or NR. (Sample A-5) in 200ml
After mixing with part t using a Henschel mixer, the mixture was pelletized using an extruder. The obtained pellets were injection molded to make a flat plate, and the dart 'rjfi impact strength of the plate was measured. The results are shown in Table 5. The composition of the present invention had better impact resistance than the composition of the comparative example, and while the composition of the comparative example showed remarkable interfacial peeling, the composition of the present invention It was confirmed that the product had a tight composition with little interfacial peeling.

(Hereinafter referred to as Ryoiro) Table 5 (Note 8) A flat plate was fixed and weights of various weights were dropped from a height of 1 m, and the energy required to destroy 50% of the flat plate was determined.

Example 7 A composition of a thermoplastic monomer and a modified block copolymer of the present invention containing glass fibers was pelletized according to the formulation shown in Table 6. This pellet was injection molded to prepare a test piece, and the impact strength was measured.

The results are shown in Table 6.

Table 6 (Note 9) Nittobo Co., Ltd., trade name C899A-401 was used.

Claims (1)

[Claims] 1. (a) Polyoxymethylene polymer, polycarbonate polymer or modified product thereof, polysulfone polymer or modified product thereof, nitrile polymer, polyphenylene ether polymer or modified product thereof , 90 to 5% by weight of at least one thermoplastic polymer selected from polyarylene sulfide polymers or modified products thereof; (b) the content of vinyl aromatic hydrocarbons exceeds 60% by weight; 90% by weight or less, and has at least one vinyl aromatic compound polymer block A and at least one olefin compound polymer block B, and block B
The block copolymer is an olefin compound polymer block in which the degree of unsaturation does not exceed 20%, and the average molecular unit containing a carboxylic acid group or its derivative group is 100% by weight of the "base block copolymer". 0.0 per part
Modified block copolymer 10-9 combined with 5-20 parts by weight
A modified block copolymer composition consisting of 5% by weight. 2. The modified block copolymer of component (b) contains any one or two of monovalent, divalent or trivalent metal ions.
The composition according to claim 1, which is an ionic crosslinked product obtained by ionic crosslinking by more than one species.