GB2053238A - Thermoplastic polymer composition - Google Patents

Abstract

The composition comprises (i) a block copolymer of an aromatic vinyl compound and a conjugated diene compound, which is modified by reaction with an unsaturated dicarboxylic acid or a derivative thereof, or an ionically cross-linked product of the modified block copolymer with univalent, bivalent or trivalent metal ions, (ii) a thermoplastic polymer having (polar) functional groups and optionally (iii) a styrene or olefin polymer. The composition has excellent mechanical and other properties and is used in moulding and other applications. Components (i) and (ii) may be reacted together when component (ii) contains groups reactive with carboxylic groups, e.g. hydroxyl groups.

Description

SPECIFICATION Thermoplastic polymer composition The present invention relates to a novel thermoplastic polymer composition. More specifically, it relates to a thermoplastic polymer composition containing (i) a modified block copolymer of an aromatic vinyl compound and a conjugated diene compound, which is modified with a dicarboxylic acid or the derivative thereof, or the ionically crosslinked product thereof and (ii) a thermoplastic polymer having polar groups containing polar atoms, such as oxygen, nitrogen, sulfur and halogen atoms and, optionally, (iii) styrene polymers or polyolefins. This thermoplastic polymer composition has excellent properties including mechanical properties and the compatibility of each component in the thermoplastic polymer composition is remarkably improved.

Various polymer substances have heretofore been used as fibers, films, sheets, molded articles and the like. However, desired products having a desired property or properties cannot be obtained by the use of a single polymer substance. For this reason, various attempts to improve the processability of products, to adjust the balance of the physical properties of products or to lower the cost of products have been made by, for example, the combination of two or more polymer substances having different properties, the mixing or blending of various polymer substances together with low - molecular weight substances or inorganic substances, or the laminating of two or more layers. However, in the case where various polymeric substances are mixed to prepare compositions, the compatibility of the different polymer substances to be mixed is not necessarily good.As a result, in many cases, the desired modification of certain polymer substances by these attempts cannot be readily obtained due to, for example, the non-uniformity or non-homogeneity and the delamination, based on the poor intermixing properties and compatibilities.

Copolymers of aromatic vinyl compounds and conjugated diene compounds, typically including styrene-butadiene block copolymers, are one of the polymer substances which are recently noted in the art. Among the styrene-butadiene block copolymers, those containing two or more polystyrene blocks and one or more polybutadiene blocks and having a relatively small styrene content have rubber elasticity similar to that of conventional vulcanized rubbers and also have moldability and processability similar to those of conventional thermoplastic plastic materials. Therefore, these styrene-butadiene block copolymers are widely used in the fields of, for example, molding materials, such as soling materials (for shoes), the modification of polystyrene resins and the like, adhesives, bonding agents and the like.On the other hand, styrene-butadiene block copolymers having a high styrene content are used, as a clear high-impact styrene resin, in the field of, for example, packaging materials.

The block copolymers of aromatic vinyl compounds and conjugated diene compounds are useful by themselves and, also when they are mixed with, for example, styrene polymers and polyolefins, useful polymer compositions having desired properties can be obtained. However, since these block copolymer are composed of only hydrocarbon monomers and since they are not compatible with other thermoplastic polymer substances, especially those containing a polar group with a polar atom such as oxygen, nitrogen, sulfur or halogen atoms, useful polymer compositions having desired properties cannot be obtained when these block copolymers are mixed with the above mentioned otherthermoplastic polymer substances.

According to the present invention there is provided a thermoplastic polymer composition comprising: (a) 1 to 99% by weight of a component A which is, or consists essentially of, at least one modified block copolymer or the onically crosslinked product of at least one said modified block copolymer with at least one univalent, bivalentortrivalentmetal ion, said modified block copolymer comprising a block copolymer of at least one aromatic vinyl or vinylidene compound and at least one conjugated diene compound onto which at least one molecular unit containing at least one dicarboxylic acid group or a derivative thereof is grafted; (b) 99 to 1% by weight of a component B which is, or consists essentially of, at least one thermoplastic polymer having polar groups; the individual % by weight of components A and B being based on the combined weight of components A and B; and optionally (c) 0 to 100% by weight of component C which is, or consists essentially of, a styrene polymer or an olefin polymer; the % by weight of component C being based on the combined weight of components A and B.

In the following description and claims references to parts by weight of components A, B and Care relative to the combined weight of components A and B representing 100 parts by weight.

The above-mentioned thermoplastic polymers containing polymer groups of the component B include polyam ides, thermoplastic polyesters, polyurethanes, vinyl-alcohol polymers, polyacrylates, polymethacrylates, chlorinated hydrocarbon polymers, polyoxymethylene polymers, polycarbonates, polyarylene ethers, polyarylene sulfides, unsaturated nitrile polymers, polysulfones, ionomers and oligomers other than the above-mentioned polymers, said oligomers having at least one polar group which is reactive to the dicarboxylic acid or the derivative thereof and having a number average molecularweightof 100 through 10,000.

According to the present invention, since the modified block copolymers containing dicarboxylic acid groups or the derivatives thereof are used as the component A, the interaction of the component A with respect to the various thermoplastic polymers containing polar groups used as the component B becomes large, compared to the unmodified block copolymer. As a result, the mechanical and chemical properties of the present thermoplastic polymer compositions containing the components A and B are improved, compared to those of the compositions containing the unmodified block copolymers.

Especially, when the thermoplastic polymers containing polar groups of the component B contain polar groups such as an amino group, hydroxyl group, epoxy group and isocyanate group, which can be reacted or interacted with the dicarboxylic acid groups or the derivatives thereof contained in the modified block copolymers or the ionically crosslinked dicarboxylic acid or the derivatives thereof contained in the ionically crosslinked modified block copolymers of the component A, the abovementioned improvement effects are remarkably large. It should be noted that, as in those cases, the compositions containing the graft or block copolymers of the components A and B are also within the scope of the thermoplastic polymer compositions of the present invention.

As set forth above, the composition ratio of the component Ato the component B in the present polymer compositions is within the range of from 1/99 to 99/1, more preferably 5/95 to 95/5, based on a weight basis.

The properties of the present thermoplastic polymer compositions containing the components A and B and, optionally, the component C, may be widely varied, depending on the composition ratio of the components A and B orA, B and C and the properties of the components A and B orA, B and C.

However, according to the present invention, the properties of each component can be improved or modified by the combination of the components A andBorA, Band C.

For instance, when the present thermoplastic polymer compositions contain 50 through 99 parts by weight of the component A, relatively poor oil resistance and/or poor heat resistance of the com ponentAcan be improved by the addition of the polar component B. On the other hand, when the present thermoplastic polymer compositions contain 50 through 99 parts by weight of the component B, relatively poor impact resistance of the component B can be improved even by the addition of a relatively small amount of the component A, if the component B has a poor impact resistance. Furthermore, the present thermoplastic polymer composition of the components A and B can be used as a thermoplastic adhesive and also as a molding material in any compositions of the components A and B within the specified composition ratio.Although the various special characteristics of the present ther moplastic polymer compositions, which appear when the various polar polymer substances of the component B are used, are explained in detail hereinbelow, the effects due to the addition of the component A are more or less imparted to the com ponent B. In addition, the modification of the proper ties of the present compositions can be effected even by the addition of a small amount of the com ponent A, for example, 1 part by weight of the com ponent A. This is an important advantage of the present invention.

The component A used in the present thermoplastic polymer composition is at least one member selected from the group consisting of block copolymers of aromatic vinyl compounds and conjugated diene compounds (which are referred to as "block copolymers" or unmodified block copolymers hereinbelow) onto which molecular units containing dicarboxylic acid groups or the derivatives thereof are grafted (the produced grafted polymers are referred to as "modified block copolymers" hereinbelow} and the ionically crosslinked products of the modified block copolymers with at least one univalent, bivalent or trivalent metal ion (which are sometimes referred to as "ionically crosslinked products" or "ionically crosslinked modified block copolymers" hereinbelow).

The block copolymers which are base polymers of the modified block copolymers can be typically prepared by an anionic polymerization in which lithium compounds are used as a polymerization catalyst.

The content of the aromatic vinyl compounds in the block copolymers is generally within the range of from 5 to 95% by weight, preferably 10 to 90% by weight and, more preferably, 15to 85% by weight The block copolymers contain one or more, preferably two or more, of polymer blocks A, which mainly contain aromatic inyl compounds, and one or more of polymer blocks B, which mainly contain conjugated diene compounds. The weight ratio A/B of the polymer blocks A and B in the block copolymer is within the range of from 5/95 to 95/5, preferably 10/90 to 90/10. Among these block copolymers, those containing 70% by weight or less, preferably 60% by weight or less, of the aromatic vinyl compounds are rubber-like polymers and those containing more than 70% by weight of the aromatic vinyl compounds are resinous polymers.These conditions are maintained even after modification. Certain properties of the present thermoplastic polymer compositions also depend on the content of the aromatic vinyl compounds in the block copolymer.

The content of the aromatic vinyl compounds in the polymer blocks A of the block copolymers should be 60% by weight or more, preferably 80% by weight or more and, more preferably, 100% by weight and the content of the aromatic vinyl compounds in the polymer blocks B of the block copolymers should be 40% by weight or less, preferably 30% by weight or less. In the case where a minor component is present in each polymer block, the distribution ofthe minor component in the polymer block can be in the form of a tapered block (i.e. the content of the monomer component is gradually increased or decreased along the molecular chains), a partial block or any combination thereof. In the case where two or more of the polymer blocks are present in the block copolymer, they can be either in the same or in different structures.

The aromatic vinyl compounds used in the block copolymers include, for example, styrene, a-methylstyrene, vinyl toluene, p-tert-butylstyrene and the like. The conjugated diene compounds used in the block copolymers include, for example, butadiene, isoprene, 1,3-pentadiene and the like.

Preferable block copolymers used in the present invention are styrene-butadiene block copolymers.

The number-average molecular weights of the polymer blocks A and B are preferably within the range of from 1,000 to 300,000, more preferably 5,000 to 100,000 and the number-average molecular weight of the total block copolymer of the present invention is preferably within the range of from 10,000 to 500,000, more preferably 20,000 to 300,000.

The molecular weight distribution (i.e. the ratio of the weight-average molecular weight to the number-average molecular weight) of the block copolymer of the present invention is preferably within the range of from 1.01 to 10, more preferably within 1.01 to 5. In the case where butadiene is used, as the conjugated diene compound, the 1,2-vinyl content in the micro structure of the butadiene portions of the block copolymers is preferably within the range of from 5 to 50%. Furthermore, the molecular structure of the block copolymers can be in the form of a linear structure, a branched structure, a radial type structure, which is obtained by the use of a polyfunctional coupling agent, or any combination thereof.The above-mentioned limitations of the polymer structure of the block copolymers are preferably conditions to obtain the desired effects of the present invention. The block copolymers having different structures can be used in any combination thereof.

The block copolymers used in the present invention are generally prepared from the anionic copolymerization of the aromatic vinyl compounds and the conjugated diene compounds in an inert nactive hydrocarbon solvent, such as hexane, cyclohexane, benzene, toluene and the like, in the presence of, as a polymerization catalyst, an organic lithium compound, such as butyl lithium. In the anionic copolymerization, the block copolymers having various structures can be obtained by changing the monomer addition method or order or by using a polyfunctional lithium compound. Furthermore, the micro structure of the conjugated diene portion of the block copolymer can be changed by the addition of a small amount of polar compounds, such astet- rahydrofuran, diethylene glycol dimethylether and the like.In addition, the block copolymers having active lithium terminal groups, obtained from the above-mentioned methods, can be reacted with polyfunctional coupling agents, such as carbon tetrachloride, silicon tetrachloride and the like, to produce branched or radial type block copolymers.

However, it should be noted that the block copolymers of the aromatic vinyl compounds and the conjugated diene compounds derived from any other production processes can be used in the present invention, so long as the molecular structure of the block copolymers are within the range of the above-mentioned limitations.

Typical examples of the various structures of the block copolymers used in the present invention are as follow.

~ A i3 ( A - B#nA ( B - A#nB [( A - B )p]m-X [( B - A )p]m-X [( A - B )p-A]m-X and [( B - A )p-B]m-X wherein A is a polymer block containing the aromatic vinyl compound, B is a polymer block mainly containing the conjugated diene compound, Xis a residual group of a polyfunctional coupling agent having two or more functional groups, n and p are, independently, integers of 1 or more and m is an integer of 2 or more.

The modified block copolymers according to the present invention can be prepared by the addition reaction of unsaturated dicarboxylic acids, or the derivatives thereof, to the above-mentioned base block copolymers. These dicarboxylic acids, or the derivatives thereof, are addition reacted or grafted to the conjugated diene portions of the block copolymers at the active unsaturated positions thereof. These dicarboxylic acids, or the derivatives thereof, should be grafted to the block copolymer in an amount such that one or more dicarboxylic acids, or the derivatives thereof, on an average, are grafted to each molecule of the block copolymers and also such that 0.05 through 20 parts by weight, preferably 0.1 through 10 parts by weight, of the dicarboxylic acids, or the derivatives thereof, based on 100 parts by weight of the base block copolymer, are grafted to the block copolymer.When the amount of the grafted molecular units derived from the dicarboxylic acids, orthe derivatives thereof, is less than 0.05 parts by weight, the modification effects cannot be obtained, whereas, when the amount is more than 20 parts by weight, further improvement cannot be obtained.

Typical examples of the dicarboxylic acids, and the derivatives thereof, used in the present invention are maleic acid, fumaric acid, chloromaleic acid, itaconic acid, cis - 4 - cyclohexene - 1,2 - dicarboxylic acid, endo - cis - bicyclo L2,2,12 - 5 - heptene - 2,3 - dicarboxylic acid and the anhydrides, the esters, the am ides and the imides thereof. Preferable dicarboxylic acids, and the derivatives thereof, are maleic acid, fumaric acid and maleic anhydride. The most preferable one is maleic anhydride.

The modified block copolymers used in the present invention can be obtained by reacting the above-mentioned base block copolymers with the dicarboxylic acids, or the derivatives thereof, in a molten state or in a solution with or without using a free-radical initiator. Although there is no limitation in the production processes of the modified block copolymers in the present invention, production processes which produce the modified block copolymers containing undesirable materials, such as gels or having a poorflowability, are not preferable for use in the present invention.For instance, as disclosed in the specification of our prior co-pending application, U.S.S.N. 089,237, the modified block copolymers can be preferably produced in a manner such that the addition reaction can be conducted by using, for example, an extruder in a molten state under the condition that no substantial amount of free radicals is generated in the system by using a free-radical inhibitor.

Further, the onically crosslinked products of the modified block copolymers with at least one univalent, bivalentortrivalentmetal ion can be used as the component A of the present thermoplastic polymer compositions. These ionically crosslinked modified block copolymers especially improve the impact resistance of the component B of the present thermoplastic polymer compositions.

These ionically crosslinked modified block copolymers are obtained by crosslinking the modified block copolymers via ionic bondingswith at least one metallic compound containing at least one univalent, bivalent or tribalent metal ion can be used as a crosslinking agent.

In the ionically crosslinked modified block copolymers, the dicarboxylic acid groups, or the derivatives thereof, are ionized by the addition of the crosslinking agent compounds. The ionization degree or amount of the dicarboxylic acid groups, or the derivatives thereof, can be controlled by the addition amount of the crosslinking agent compounds. The ionization amount can be determined by the use of, for example, an infrared spectrophotometer.

The addition amount of the crosslinking agent compounds is determined so that the partial orthe total amounts of the dicarboxylic acid groups, or the derivatives thereof, contained in the modified block copolymers are theoretically ionized. The ionization reaction substantially quantitatively proceeds.

However, an excess amount of the crosslinking agents may be preferably used to obtain the desired ionization amount In orderto effectively obtain the ionically crosslinked modified block copolymers, the mol ratio of the metal components in the metallic compounds (i.e. the crosslinking agent) to the dicarboxylic acid groups, or the derivatives thereof, contained in the modified block copolymers is preferably within the range of from 0.1 to 3.0.

The crosslinking agent compounds used for the production of the onically crosslinked modified block copolymers include the compounds of metals of Groups l, ll, III, IV and VEIL, of the Periodic Table.

These metallic compounds can be used alone or in any mixtures thereof. Typical examples of the crosslinking compounds are sodium compounds, potassium compounds, magnesium compounds, calcium compounds, zinc compounds, aluminum compounds and iron compounds. Preferable metallic compounds are hydroxides, oxides, alcoholates and carboxylates of the above-mentioned metals.

The ionically crosslinked products of the modified block copolymers can be prepared by various methods. For instance, the crosslinking agent compounds can be added to the molten modified block copolymers to effect the crosslinking reaction. Alter natively, the modified block copolymers are dissolved in an appropriate solvent and, then, the crosslinking agent compounds are added to the resultant solution to effect the crosslinking reaction. Furthermore, the crosslinking agent compounds can be added to the modified block copolymers in the form of a latex to effect the crosslinking redaction.

The above-mentioned modified block copolymers, and the ionically crosslinked products thereof, can be used as the component A of the present thermoplastic polymer compositions, alone or in any mixtures thereof.

The component B of the present thermoplastic polymer compositions will now be explained in detail hereinbelow.

As mentioned hereinabove, thermoplastic polymer substances having polar groups containing oxygen, nitrogen, sulfur and halogen atoms can be used as the component B of the presentthermoplastic polymer compositions. Examples of the thermoplastic polymers having polar groups are: polyamides; thermoplastic polyesters; polyurethanes; vinylalcohol polymers; polyacrylates; polymethacrylates; chlorinated hydrocarbon polymers; polyoxymethylene polymers; polycarbonates; polyarylene ethers; polyarylene sulfides; unsaturated nitrile polymers; polysulfones; ionomers; and oligomers, other than the above-mentioned polymers, having at least one polar group which is reactive to the dicarboxylic acid or the derivative thereof and having a number-average molecular weight of 100 through 10,000.

Each thermoplastic polymer having polar groups used as the component B in the present invention, as well as the unique advantages of each composition and the optimum conditions, will now be described in detail hereinbelow.

The polyamides used as the component B in the present invention are polymer substances having amide bonds in the molecule thereof, which include, for example, ring opening polymers of cyclic lactums, polycondensates of a-amino carbonic acids, polycondensates of dicarboxylic acids and diamines and copolymers of these monomers. Typical examples of the polyamides are nylon-6, nylon-11, nylon-12, nylon-6,6, nylon-6, 10, copolymers of nylon-6 and nylon-6,6, copolymers of nylon-6 and nylon-i 2, copolymers of dimer acids and fatty diamines and the low-molecularweight compounds thereof. The polyamides obtained by any conventional production processes can be used in the present invention. The number-average molecular weight of these polyamides can be preferably within the range of from 100to 30,000. The polyamides having various molecular weights and having different molecular structures can be used, depending upon the desired types of the compositions.

In the case where the component A is a main constituent of the present thermoplastic polymer compositions, the heat resistance, the oil resistance and the adhesive properties to polar materials of the component A can be advantageously improved by the blending of the polyamides. In this case, polyamides having various structures and having a wide range of molecular weight, such as from a relatively low molecular weight up to a high molecular weight, can be used. When the moldability and the processability of the composition are important, the use of the polyamides having a relatively low molecular weight or low melting point is desirable.

On the other hand, in the case where the polyamides are a main constitutent of the present thermoplastic polymer compositions, the impact resistance of the polyamides, especially nylon-6 and nylon-6,6, which have a high crystallizability and a poor impact resistance, can be effectively improved by the use of the component A, especially the use of the ionically crosslinked modified block copolymers.

Furthermore, the thermoplastic polymer compositions containing the modified block copolymers and the polyamides, in any composition ratio, are suitable for use, as an adhesive composition, in the adhesion of, for example, polyamides with nonpolar polymer substances, such as styrene polymers and olefin polymers, and various metals. The present thermoplastic polymer compositions containing polyamides can also be used as useful molding materials and modifiers for other thermoplastic polymer substances.

The polyesters which can be used as the component B in the present invention should be thermoplastic polyesters. The thermoplastic polyesters are polymer substances containing ester bonds in the molecule thereof. Typical thermoplastic polyesters have the structures in which dicarboxylic acids and glycols are polycondensed. These polymers can be obtained by the polycondensation reaction of dicarboxylic acids, the lower esters thereof, acid halides thereof, or anhydrides thereof, and glycols.

The aromatic or aliphatic dicarboxylic acids which can be used as the starting materials of the polyesters include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, adipic acid, sebacic acid, azelaic acid, 1,9-nonane dicarboxylic acid, 1,1 0-decane dicarboxylic acid, 1,16-hexadecane dicarboxylic acid, terephthalic acid, isophthalic acid, p,p'-dicarboxy diphenyl, p-carboxyphenoxy acetic acid, 2,6-naphthalene dicarboxylic acid and the like. These dicarboxylic acids and the derivatives thereof can be used alone or in any mixtures thereof. Among these dicarboxylic acids, terephthalic acid and isophthalic acid can be preferably used.

The aliphatic or aromatic glycols (or diols) which can be used as the other starting materials of the polyesters include, for example, ethylene glycol, 1,3-propane diol, 1,2-propane diol, 1,4-butane diol, 1,6-hexane diol, lAcyclohexane diol, 1, 10 < lecane diol, neopentyl glycol, p-xylene glycol and the like. These glycols can be used alone or in any mixtures thereof.

Among these glycols, alkylene glycols having 2 to 10 carbon atoms can be preferably used in the present invention. The most preferable glycols are ethylene glycol and 1,4-butane diol.

Preferable polyesters are poly(ethylene terephtha late), poly(butylene terephthalate) and the polyesters in which a portion of the monomer units is replaced with other monomer units. The numberaverage molecular weight of the polyesters is preferably within the range of from 500 to 100,000, more preferably 5,000 to 50,000.

The polyesters used in the present invention can be produced by any conventional technique. For instance, the above-mentioned acid components, such as terephthalic acid, isophthalic acid, aliphatic dicarboxylic acids, or the ester derivatives thereof, are subjected to a direct esterification or an ester exchange reaction, together with one or more ofthe above-mentioned glycols and, then, polymerization is effected. In the course of the production of the polyamides, various conventional additives, such as a catalyst, stabilizers, modifiers and other additives, can be used.

Examples of other useful polyesters which can be used as the component B in the present invention are polylactones derived from the ring opening polymerization of cyclic lactones, such as pivalolactone, p-propiolactone, e-caprolactone and the like.

The terminal groups of the polyester molecules are hydroxyl groups or carboxyl groups. Optionally, these terminal groups are further reacted with mono-functional alcohols or carboxylic acids to deactivate the active terminal groups. In the present invention, the polyesters having, in the terminal portions of the molecules thereof, functional groups, which can be reacted with the functional groups contained in the modified block copolymers, can be preferably used. In the case where the polyesters having at least partially such functional groups in the terminal portions of the molecules thereof are used in the present polymer compositions, the compatibility of the compositions is remarkably improved. The above-mentioned polyesters can be used, as the component B of the present polymer composition, alone or in any mixtures thereof.

In addition to the polyesters such as poly(ethylene terephthalate) and poly(butyrene terephthalate), which are widely used as fibers, films and resins, low-crystallizable polyesters having a low melting point and polyether-ester block polymers containing hard segments and soft segments in the same molecules thereof are also contained in the polyesters used as the component B in the present invention.

Especially, in the case where the thermoplastic polyesters are used, as the component B, in the present compositions, the compatibility between the thermoplastic polyesters and the modified block copolymers in the compositions is extremely improved, compared to compositions in which the unmodified base block copolymers are used in lieu of the modified block copolymers. As a result, the mechanical properties of the present polymer composition are remarkably improved. The properties of the present thermoplastic polymer compositions can be widely varied, from rubber-like materials to resinous materials, by adjusting the composition ratio of the modified block copolymers and the polyesters.

The polymer compositions containing 50 through 99% by weight of the component A and 1 through 50% by weight of the thermoplastic polyesters (i.e.

the component B) are useful as the compositions in which the properties of the block copolymers are modified. On the other hand, the polymer compositions containing 1% by weight through less than 50% by weight of the component A and more than 50% by weight through 99% by weight of the thermoplastic polyesters (i.e. the component B) are useful as the compositions in which the properties, especially the impact resistance, of the polyesters are improved.

Furthermore, the present polymer compositions containing, as the component B, the thermoplastic polyesters have good adhesiveness, in any composi tion ratio.

It should be noted that the polymer compositions partially containing the graft copolymers derived from the reaction of the reactive functional groups contained in the modified block copolymers and the reactive functional groups contained in the thermop lastic polyesters are also within the scope of the pre sent compositions.

The above-mentioned present polymer com posi tions containing the thermoplastic polyesters can also be used as useful molding materials and modi fiers for other thermoplastic polymer substances.

The polyurethanes which can be used as the com ponent B in the present invention include polymer substances containing urethane bonds, as the repeating unit, in the molecule thereof. These polyurethanes are widely used as foams, adhesives, coating compositions, synthetic leathers and elas tomers and are typically obtained from the polyaddi tion reaction of diisocyanates, polyols, polyamines, glycols and the like. The kinds of the polyurethanes are typically classified into casting type, blend type and thermoplastic type polyurethanes. Any type of the polyurethanes can be used as the component B in the present invention. However, among these polyurethanes, the thermoplastic type polyurethanes can be advantageously used in the present invention from the processing point of view.

Thethermoplastictype polyurethanes can be divided into complete thermoplastic type polyurethanes and incomplete thermoplastic type polyurethanes, based on the synthetic conditions thereof. These two types are determined by the molar ratio of the hydroxyl (OH) groups contained in the starting bifunctional polyols and glycols and the isocyanate (NCO) groups contained in the starting diisocyanates. That is, the molar ratio (NCO/OH) of the complete thermoplastic type polyurethanes is approximately 0.95(NCO/OH1 and the molar ratio (NCO/OH) of the incomplete thermoplastic type polyurethanes is approximately 1 < NCO/OH < 1 .1.

Examples of the thermoplastic type polyurethanes are those containing, as soft segments, blocks of polyols (i.e. polyesters or polyethers) and diisocyan ates. and, as hard segments, blocks of diisocyanates and glycols.

The polyesterdiols used as the starting material in the production of the polyurethanes include, for example, poly(1,4-butyrene adipate), poly(1,6 hexane adipate), polycaprolactone and the like.

Examples of the polyether diols are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol and the like. Examples of the glycols are ethylene glycol, 1,4-butane diol, 1,6-hexane diol and the like.

The isocyanates used as the starting material in the production of the polyurethanes include aroma tic, alicyclic and aliphatic isocyanates, such as, for i example, tolylene diisocyanate, 4,4'diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like.

In addition to the above-mentioned thermoplastic type polyurethane elastomers, polyurethanes used as adhesive foams, coating compositions and the like have good compatibility with the modified block copolymers the ionically crosslinked products thereof (i.e. the component A) and, therefore, can also be used as the component B in the present invention.

The number-average molecularweight ofthe thermoplastic type polyurethanes used as the component B in the present invention are preferably within the range of from 1,000 to 500,000, more preferably 10,000 to 300,000, from the point of view of the mechanical properties of the polymer compositions.

In the case where the polyurethanes are used, as the component B, in the present polymer compositions, the compatibility between the polyurethanes and the modified block copolymers in the compositions is improved. As a result, the modification in the properties of the compositions can be effectively effected by the blend of both components, compared to compositions in which the unmodified base block copolymers are used in lieu of the modified block copolymers. That is to say, when the compositions contain, as a main constituent, the polyurethanes, the poor hydrolytic stability of the polyurethanes can be improved in the compositions and, the flexibility is imparted to the polymer compositions by the use of the component A containing a small amount of the aromatic vinyl content, while the hardness is maintained in the compositions.

On the other hand, when the present polymer compositions contain, as a main constituent, the component A, the oil resistance, the abrasion resistance and the like are improved in the present compositions, compared to those of the unmodified base block copolymers and the compositions thereof containing the polyurethanes. Furthermore, as mentioned hereinabove, the present polymer compositions can also be useful as adhesives for metals and thermoplastic polymer substances and as modifiers for other thermoplastic polymer substances.

The vinyl alcohol polymers which can be used as the component B in the present invention include polymer substances having, in the molecular structure, a repeating unit containing vinyl alcohol. The vinyl alcohol polymers can be obtained by the partial or complete saponification of vinyl ester polymers, such as polyvinyl acetate, and olefin-vinyl ester copolymers, such as ethylene-vinyl acetate copolymers, and propylene-vinyl acetate copolymers by the use of alkaline compounds. Among these vinyl alcohol polymers, it is known that polyvinyl alcohol must be used, together with processing aids, plasticizers andlorwater, in the processing thereof, since the melting point of the polyvinyl alcohol is close to the degradation temperature thereof.

Ethylene-vinyl copolymers are improved polymer substances in which the mechanical strength and the processability are improved, while the gas barrier properties, the antistatic properties and the oil resis tance, which are characteristics of the polyvinyl alcohol, are maintained. These polymers are commercially available as, for example, "Eval" (manufactured by Kurare Co. Japan) and are widely used as films and sheets.

The ethylene-vinyl alcohol copolymers are generally derived from the corresponding ethylene-vinyl acetate copolymers. Preferable vinyl acetate content in the ethylene-vinyl acetate copolymers is within the range of from 0.5 to 80 mol %. These copolymers are saponified to such a degree that 10 through 100 mol % of the vinyl acetate unit are saponified.

Although various kinds of vinyl alcohol polymers and olefin-vinyl alcohol copolymers can be used in the present invention, ethyiene-vinyl alcohol copolymers are preferably used from the point of view of the processability and the mechanical properties. However, other vinyl alcohols also have good compatibility with the component A of the present invention.

In the case where the present polymer compositions contain the vinyl alcohol polymers as a main constituent, preferably when the content of the component A is within the range of from 2 to 40% by weight, the impact resistance of the vinyl alcohol polymers is remarkably improved in the composition. As will be shown in the Example hereinbelow, in the case where the present polymer composition contains 75% by weight of ethylene-vinyl alcohol copolymer and 25% by weight of styrene-butadiene block copolymer modified with maleic an hydride, a remarkable improvement in the impact resistance is observed. That is, the izod impact strength of the composition is higher by more than 10 times that of the ethylene-vinyl copolymer. In addition, the addition of a small amount of the component A in these compositions improves the adhesiveness to various materials.

On the other hand, when the present compositions contain the component A as a main constituent, preferably when the content of the component A in the present polymer composition is 60% by weight or more, the mechanical strength, the oil resistance, the weathering resistance and the like of the modified block copolymers are improved in the composition by the addition of the component B. Furthermore, as mentioned hereinabove, the present polymer compositions containing, as the component B, the vinyl alcohol polymers can also be useful as adhesives for, for example, metals and thermoplastic resins, especially as adhesives between vinyl alcohol polymers and other materials, such as polyolefins, and as modifiers for other thermoplastic polymer substances.

The polyacrylates or polymethacrylates which can be used as the component B in the present invention include polymer substances mainly containing alkyl acrylates or alkyl methacrylates having alkyl groups of 1 to 12 carbon atoms. These polymer substances are usually called "acrylic resins or methacrylic resins". Generally speaking, the polyacrylates contain 50% by weight or more of alkyl acrylates oralkyl methacrylates. The polyacrylates or polymethacrylates can be generally produced by a radical polymerization method.

Examples of acrylic esters used in the production of the polyacrylates are methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate and (2-ethyl)hexyl acrylate. Examples of methacrylic esters used in the production of the polymethacrylates are methyl methacrylate, ethyl methacrylate and butyl methacrylate. Especially, polymethyl methacrylate or copolymers containing, as a main constituent, methyl methacrylate and a minor amount of methyl acrylate and/or butyl acrylate are useful as methacrylic resins and these polymer substances can be preferably used as the component B in the present invention. However, any other polyacrylates, polymethacrylates and the copolymers thereof can also be used as the component B in the present invention.

Furthermore, the polyacrylate or polymethacrylate polymer compositions in which other components having a low glass transition temperature are blended to modify the properties of the polyacrylates or the polymethacrylates, orthe polyacrylate or polymethacrylate copolymers containing a minor amount of monomers, otherthan acrylates and methacrylates, such as ethylene, acrylic acid, methacrylic acid, styrene and maleic anhydride, can also be used as the component B in the present invention.

The number-average molecular weight of the polyacrylates or polymethacrylates used in the present invention is preferably within the range of from 500 to 1,000,000, more preferably 100,000 to 500,000.

In the case where the present polymer compositions contain, as a main constituent, 50% by weight or more, especially 60% by weight or more, of the polyacrylates or polymethacrylates (i.e. component B), the impact resistance of the component B is improved in the composition by the addition of the component A and the generation of cracks by solvents is also decreased. On the other hand, when the present polymer compositions contain, as a main constituent, the component A, especially when the content of the component A in the composition is more than 60% by weight, the heat resistance and the oil resistance of the component A are improved in the composition.Furthermore, as mentioned hereinabove, the present polymer compositions containing, as the component B, the polyacrylates or polymethacrylates can be also be useful as adhesives for various metals and thermoplastic polymer substances and as modifiers for other thermoplastic polymer substances.

The chlorinated hydrocarbon polymers (or chlorine-containing hydrocarbon polymers) which can be used as the component B in the present invention include hydrocarbon polymer substances containing chlorine atoms in the molecules thereof.

Examples of such chlorinated hydrocarbon polymers are: vinyl chloride homopolymers; copolymers of vinyl chloride and other monomers copolymerizable therewith, such as, vinyl chloride-vinylidene chloride copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene copolymers, vinyl chloride-acrylic esters copolymers, vinyl chloride-maleic esters copolymers; graft copolymers based on the above-mentioned chlorinated hydrocarbon ho polymers or copolymers; chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene; and the like. The prefer ably number-average molecular weight of these chlorinated hydrocarbon polymers is within the range of from 500 to 500,000, more preferably 10,000 to 200,000.

In the case where the chlorinated hydrocarbon polymers, especially polymers containing vinyl chloride, are used as the component B in the present invention, conventional plasticizers, such as dibutyl phthalate, dibutyl sebacate, diethyl carbonate, dibutylphenyl phosphate, dihexyl phthalate, dioctyi adipate, dioctyl phthalate, triphenyl phosphate, tricredyl phosphate and the like, can be added to the present polymer compositions. The addition amount of the plasticizers is preferably within the range of from 1 to 100 parts by weight based on 100 parts by weight of the component B.

In the present polymer compositions containing the modified block copolymers (orthe ionically crosslinked products thereof), as the component A and the chlorinated hydrocarbon polymers as the component B, the combatibility between the components A and B in the composition can be advantageously improved, as mentioned above.

In the case where the present polymer compositions contain, as a main constituent, the abovementioned component A, preferably 60% by weight or more of the component A, the oil resistance and the fire retardance of the present composition are remarkably improved, compared to polymercompositions containing the unmodified base block copolymer and the chlorinated hydrocarbon polymers. On the other hand, when the present polymer compositions contain, as a main constituent, the above-mentioned component B, preferably 60% by weight or more of the component B, the impact resistance and the processability of the component B are improved in the compositions. Furthermore, as mentioned hereinabove.The present polymer composition containing the chlorinated hydrocarbon polymers as the component B, in any composition ratio, can also be useful as adhesives, especially adhesives for chlorine-containing polymers or polyurethanes and non-polar polyolefins or styrene polymers, and as modifiers for other thermoplastic polymer substances.

The polyoxymethylene polymers which can be used as the component B in the present invention include homopolymers derived from the polymerization of formaldehyde ortrioxane and copolymers containing, as a main constituent, said monomers.

The homopolymers are generally treated in a man ner such that the terminal groups of the polymer molecules are converted to ester groups or ether groups, so that the heat resistance and the chemical resistance of the homopolymers are improved.

Examples of the copolymers are those in which the other aldehydes, cyclic ethers, cyclic carbonates, epoxides, isocyanates, vinyl compounds and the like are copolymerized with formaldehyde or trioxane.

In the case where the present polymercomposi- tions contain the polyoxymethylene polymers (i.e.

the component B) as the main constituent, the impact resistance is improved, compared to the polyoxymethylene polymers or polymer compositions thereof with the unmodified block copolymers.

In addition, the materials of the present polymer compositions can be desirably coated with coating compositions. Especially, when the ionically crosslinked modified block copolymers are used as the component A, the gloss of the compositions is remarkably improved. On the other hand, when the component A is contained in the present compositions as a main constituent, the oil resistance, the heat resistance, the abrasion resistance and the compression strain resistance are improved, compared to the unmodified block copolymers or the compositions thereof with the polyoxymethylene polymers.

The polycarbonates which can be used as the component B in the present invention include aromatic polycarbonates having a structural unit,

wherein Art is a phenylene group or a phenylene group substituted with an alkyl group, a substituted alkyl group, an alkoxy group, a halogen atom or a nitro group, A is an alkylene group, an alkylidene group, a cycloalkylene group, a cycloalkylidene group, sulfur, oxygen, a sulfoxide group or a sulfone group. Preferable examples of the polycarbonates are poly - 4,4' - dioxydiphenyl - 2,2' - propane carbonate, poly - 4,4' - dioxydiphenyl - 2,2' - butane carbonate and the like.

In the case where the present polymer compositions contain the polycarbonates as a main constituent, the impact resistance and the applicability of coating compositions, especially the applicability of coating compositions of the polycarbonates, are remarkably improved. In addition, when the ionically crosslinked modified block copolymers are used as the component A, the gloss of the materials obtained from the present polymer compositions is improved.

On the other hand, when the component A is used in the present polymer compositions as a main constituent, the heat resistance, the oil resistance, the abrasion resistance and the compression strain resistance are improved, compared to the unmodified block copolymers or the compositions thereof with the polycarbonates.

Furthermore, in the case where the polycarbonates are used as the component B in the present polymer compositions, the use of the polycarbonates previously blended with styrene polymers (i.e.

the component C) is in some cases desirable from the processing point of view.

The polyarylene ethers which can be used as the component B in the present invention include polyarylene ethers having a structural unit,

wherein R1 and R2 are, independently, alkyl groups having 1 to 4 carbon atoms, substituted alkyl groups or halogen atoms, and grafted polyarylene ethers derived from the graft polymerization of aromatic vinyl compounds onto polyarylene ethers having the afore-mentioned structural unit. Examples ofthe aromatic vinyl compounds used in the graft polymerization are styrene, a-methylstyrnne, methylstyrene, tert.-butvlstyrene, chlorostyrene and the like.These aromatic vinyl compounds can be used alone or in any mixtures thereof or, optionally, in mixtures thereof with other copolymerizable vinyl compounds such as acrylic esters, methacrylic esters, acrylonitrile, methacrylonitrile and the like.

Preferable polyarylene ethers are poly(2,6 - dimethyl -1,4- phenylene)ether, poly(2,6 - dichloromethyl 1,4 - phenylene)ether and the like, and the graft polymers thereof grafted with, for example, styrene.

In the case where the present polymer compositions contain the polyarylene ethers as a main constituent, the impact resistance and the applicability of coating compositions of the component B are improved in the composition by the addition of the component A. In addition, when the ionically crosslinked modified block copolymers are used as the component A, the gloss of the materials obtained from the present polymer compositions is improved.

On the other hand, when the component A is used as a main constituent in the present polymer compositions, the oil resistance, the heat resistance, the abrasion resistance and the compression strain resistance are improved, compared to the unmodified block copolymers or the compositions thereof with the component B. Furthermore, as in the case of polycarbonates, in the case where the polyarylene ethers are used as the component B in the present polymer compositions, the use of the polyarylene ethers previously blended with styrene polymers (i.e. the component C) is in some cases desirable from the processing point of view.

The polyarylene sulfides which can be used as the component B in the present invention include homopolymers and copolymers of arylene sulfide having a structural unit, tAr2 - Sf wherein Ar2 is a phenylene group or a phenylene group substituted with alkyl groups or substituted alkyl groups. Typical examples of the polyarylene sulfides are polyphenylene sulfide, poly(4,4' - diphenyl sulfide) and the like.

The advantages of the present polymer compositions containing polyarylene sulfides as the component B are similar to those of the compositions containing polyarylene ethers as the component B.

Especially, when the component A is contained as a main constituent in the present polymer compositions, the heat resistance and the oil resistance are remarkably improved. Also in the case where the polyarylene sulfides are used as the component B in the present polymer compositions, the use of styrene polymers as the component C is in some cases desirable from the processing point of view.

The unsaturated nitrile polymers which can be used as the component B in the present invention include t he the thermoplastic homopolymers and copolymers derived from the polymerization of monomers containing 50% or more of a,ss olefinically unsaturated mononitriles. Typical examples of such a,P-olefinically unsaturated mononitriles are acrylonitrile, methacrylonitrile, a-bromoacrylonitrile and the like. Those monomers can be used alone or any mixtures thereof.The monomers copolymerizable with the a,/3- unsaturated mononitriles include: for example, lower a-olefins such as ethylene, propylene, isobutyrene, pentene-1, vinyl chloride, vinylidene chloride and the like; aromatic vinyl compounds such as styrene, a-methylstyrene, vinyltoluene, chlorostyrene, methylstyrene and the like; vinyl ester compounds such as vinyl acetate and the like; the lower alkyl esters of a,p-ethylenically unsaturated carboxylic acids such as methyl acrylate, methyl methacrylate and the like, and; vinyl ether compounds such as nivyl methyl ether and the like.

In the case where the present polymer compositions contain, as a main constituent, the unsaturated nitrile polymers, the impact strength and the applicability of coating compositions are improved, as in the case of the above-mentioned polycarbonates. On the other hand, when the component A is contained as a main constituent in these compositions, compositions having a good heat resistance, oil resistance, abrasion resistance and compression strain resistance are obtained.

The polysulfones which can be used as the component B in the present invention include thermoplastic aromatic polysulfones having a structural unit, t Ar3 - B - Ar3 - SO2 ' or 5 Ar3 - S02+ wherein Ar3 is a phenylene group or a phenylene group substituted with alkyl groups or substituted alkyl groups, B is sulfur, oxygen or a residual group of aromatic diols. Typical examples of the polysulfones are poly(ether sulfone), poly(4,4 - bisphenol ether sulfone) and the like.

In the case where the polysulfones are used as the component B in the present invention, advantages similar to those in the case of the above-mentioned polycarbonates can be obtained. Especially, when the component A is contained as a main constituent in the present polymer compositions containing the polysulfones as the component B, the heat resistance is remarkably improved. Also in the case where the polysulfones are used in the present polymer compositions as the component B, the use of styrene polymers as the component C is in some cases desirable from the processing point of view.

The ionomers which can be used as the component B in the present invention are ionically crosslinked polymer substances in which base copolym ers of er,ss-unsaturated carboxylic acids and other monomers copolymerizable therewith are ionically crosslinked with at least one metallic ion selected from the group consisting of univalent, bivalent and trivalent metallic ions.

Typical examples of the base copolymers are those derived from (i) non-polar monomers such as olefins (e.g. ethylene, propylene, butene and the like) and styrene, and (ii) a,ss-unsaturated monocarbox ylic acids such as acrylic acid, methacrylic acid and the like, and/or a,ss-unsaturated dicarboxylic acids such as maleic acid. Preferable base polymers are olefin-unsaturated carboxylic acid copolymers, especially containing 50 mol % or more of olefins and 0.2 through 25 mol % of cu,p-unsatu rated carboxylic acids.

As disclosed in, for example, United States Patent 3,264,272, the ionomers can be obtained by the reac tion of the above-mentioned base polymers, for example, olefin - et"S - unsaturated carboxylic acid copolymers, with metallic compounds containing univalent, bivalent or trivalent metals. The metallic compounds are generally used in an amount such that 10 through 100 mol % of the carboxylic acid groups contained in the base polymers are neutral ized and ionically crosslinked with the metal ions.

Typical examples of the olefin - tr,ss - unsaturated carboxylic acid copolymers are ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-itaconic acid copolymer, ethylene-maleic acid copolymer, ethylene-acrylic acid-methacrylic acid copolymer and ethylene - propylene - methac rylic acid copolymer. The most preferable base polymer is ethylene-acrylic acid copolymer or ethylene-methacrylic acid copolymer.

The metal ions used in the formation of the above-mentioned monomers include univalent, bival ent and trivalent ions of the metals belonging to the Groups I, 11, III, IV-A and VIII of the Periodic table.

Typical examples of the metal ions are univalent metal ions such as Na , Li , K , Cs , Ag and the like, bivalent metal ions such as Mg2', Ca2', Ba24, Zn2+, Sir2+, Hug' , Fe' and the like, and trivalent metal ions such as Awl3 , Fe3' and the like. These metal ions can be reacted with the base polymers, in the form of, for example, hydroxides, alcoholates and lower carbox ylic acid groups.

Furthermore, the above-mentioned ionomers used in the present invention can be prepared by the saponification of the olefin - u,p - unsaturated car boxylic acid ester copolymers, such as ethylene methyl methacrylate copolymer and ethylene methyl acrylate copolymer, with the hydroxides of univalent, bivalent and trivalent metals, and also, by the partial neutralization of the saponified base polymers. In the latter case, carboxylic acid groups are partially contained in the resultant ionomers.

Commercially available ionomers such as "Sur lynx" (Du Pont) and "Copolenes" (Asahi Dow, Japan), can also be used in the present invention.

The above-mentioned ionomers can be used alone or in any mixtures thereof. In the case where the ionomers are used as the component B in the pres ent polymer compositions, since the metal ions con tained in the component B are reacted with the dicarboxylic acid groups or the derivatives thereof contained in the modified block copolymers (i.e. the component A) by the mixing of the components A and B, the compatibility of the components A and B in the present polymer compositions is remarkably improved. This co-ionic crosslinking between the components A and B can be readily detected by an infrared spectrophotometer.

In addition, when the onically crosslinked modified block copolymers are used as the component A in the present polymer compositions, the hardness and the tensile strength of the compositions are further improved, and therefore, extremely tough materials can be obtained.

In the case where the present polymer compositions contain the component A as a main constituent, preferably 1 through 40% by weight of the component A, the heat-sealing properties, the abrasion resistance and, especially, the oil resistance, of the block copolymer are improved.

Furthermore, as mentioned hereinabove, the present polymer compositions, in any composition ratio, have good adhesive or bonding properties to various materials such as metals, various thermopiastic polymers and paper, and therefore, can be used as laminating layers or adhesive layers in laminates of the above-mentioned various materials.

Especially, the high water resistance of the present polymer compositions is effective for use in the production of the laminates.

In addition, the present polymer compositions are useful molding or processing materials by then selves and, also, useful as modifiersforotherthermoplastic polymer substances.

The oligomers having polar groups, which can be used as the component B in the present invention, include oligomers of thermoplastic polymers, other than the above-mentioned polymers, having polar groups which are reactive to the dicarboxylic acids or the derivatives thereof contained in the component A. The number-average molecular weight of the oligomers is preferably within the range of from 100 to 10,000, more preferably 500 to 5000.

Typical examples of the reactive polar groups contained in the oligomers are an amino group, a hydroxyl group, an epoxy group, an isocyanate group and the like. These reactive polar groups are reacted with the molecular units containing the dicarboxylic acid groups or the derivatives thereof contained in the component A to form the reaction products of the components A and B. The polymer compositions of the present invention desirably contain these reaction products of the components A and B.

The reaction products of the components A and B include: graft copolymers comprising the component A, as a backbone component, and the component B, as a superstrate component, grafted onto the component A; crosslinked polymers comprising the component A crosslinked with the component B, and; mixtures thereof. These reaction products of the components A and B can be obtained by adjusting the number of the reactive polar groups contained in the component B or adjusting the mol ratio of the reactive polar groups contained in the compo nent B to the functional groups contained in the component A. Among these reaction products, those containing the graft copolymers are preferably used, and only the graft copolymers are more preferably used, in the present invention.In order to prepare the graft copolymers of the components A and B, the use of the oligomers having one reactive polar group in each molecule thereof, more preferably, one reactive polar group as one of the terminal groups in one molecule, is effective.

Typical examples of the oligomers used as the component B in the present invention are: conjugated diene type oligomers such as amineterminated conjugated diene type oligomers, hydroxy-terminated conjugated diene type oligomers, isocyanated conjugated diene type oligomers, epoxidized conjugated diene type oligomers and the like, which can be derived from conjugated diene oligomers such as 1,2-polybutadienes, 1,4polybutadienes, butadiene-acrylonitrile copolymers, polychloroprenes and the like; polyether type oligomers such as polyethylene glycols, polypropylene glycols, polybutyrene glycols and mono-or di-esters thereof and the like; polyisocyanate oligomers; polyethylene imine oligomers; glycidyl methacrylate copolymer type oligomers.Examples of the most preferable oligomers having the reactive polar group in one end of the molecules thereof are alkyl, aryl or aralkyl ethers of dihydroxyl oligomers (e.g. dihydroxyl polyethers) having a hydroxyl group in one end of the molecules thereof and oligomers having an ioscyanate group in one end ofthe molecules thereof.

Furthermore, the oligomers having more than one reactive polar group in one molecule thereof can also be used for the preparation of the present polymer compositions, so long as the oligomers having an excess amount of the reactive polar groups with respect to the functional groups contained in the modified block copolymers are used under certain reaction conditions.

The above-mentioned various oligomers can be used alone or in any mixtures thereof in the present invention.

The composition ratio of the component A and the component B (i.e. the oligomers) can be widely varied depending upon, for example, the mole ratio of the reactive groups contained in the components A and B, in accordance with the application purpose of the polymer compositions. However, in orderto obtain the polymer compositions having desirable properties, 0.5 through 100 parts by weight, more preferably 1 through 50 parts by weight, of the component B (i.e. the oligomers), based on 100 parts by weight of the component A can be preferably used in the present invention. If the amount of the component B is too large, the properties of the resultant compositions, for example the mechanical strength, are unpreferably decreased. It should be noted that the present polymer compositions can contain the unreacted component A and/or the unreacted component B.These compositions are obtained in the case where an excess amount of either the component A or B is used or where both the components A and B remain in the system because the reaction of the components A and B does not completely take place. Even in these cases, the polymer compositions having the desirable properties can be obtained. In addition, the by-products produced by the reaction ofthe components A and B (e.g. water is formed by the esterification reaction of the dicarboxylic acid group and the hydroxyl group) and the unreacted components A and/or B may be removed from the present polymer composition in any known manner.

The characteristics of the present polymer compositions containing the oligomers as the component B can be readily controlled by adjusting the composition ratio of the components A and B, the content of the aromatic vinyl compounds in the component A, the kind of the oligomers of the component B and the like. In any case, desirable characteristics which are not possessed by the corresponding modified block copolymers, for example, the compatibility with polar high-molecular weight polymers, the oil resistance, the processability, the surface characteristics and/orthe abrasion resistance are imparted to the polymer compositions.

The thermoplastic polymers which can be optionally used as the component C in the present invention include styrene polymers and olefin polymers.

The component C can optionally be incorporated into the present polymer compositions containing the components A and B to improve the processability of the composition. The amount of the component C is preferably 100 parts by weight or less, more preferably 1 to 50 parts by weight, based on 100 parts by weight of the total amount of the components A and B.Examples of the styrene polymers are those containing 50% by weight or more of styrene, such as polystyrene, styrene - er - methylstyrene copolymers, butadiene-styrene block copolymers, rubber modified high impact polystyrenes, acrylonitrile-styrene copolymers, styrenemethacrylic ester copolymers, styrene-maleic an hydride copolymers, acrylonitrile - butadiene styrene copolymers, acrylic acid ester - butadiene styrene copolymers, methacrylic ester - butadiene styrene copolymers and mixtures thereof.

The olefin polymers are polymer substances containing 50% by weight or more of an olefin monomer unit containing ethylene, propylene, butene and the like. Typical examples of such polymers are lowdensity polyethylene, high-density polyethylene, polypropylene, polybutene, ethylene-propylene copolymers, ethylene-vinyl acetate copolymers and the like.

The component C optionally used in the present invention may be added to the present polymer compositions in a manner such that the component C is added to the mixture of the components A and B afterthe blending ofthe components A and B or that the component C is previously added to the component A or B before the blending of the components A and B. Especially when polymers having a relatively high processing temperature are used as the component B, the blending of the components B and C prior to the blending of the components A and B is desirable from the processing point of view.

The polymer compositions of the present invention can further contain other conventional addi tives. Examples of such additives are reinforcing materials such as silica, carbon blacks, clays, glass fibers, organic fibers, calcium carbonate and the like, as well as fillers, antioxidants, UV absorbers, pigments, lubricants, fire retardants and other additives. Especially, when 150 parts by weight or less, preferably 10 through 100 parts by weight, of the glass fibers, based on 100 parts by weight of the thermoplastic polymer compositions of the present invention, are incorporated into the present compositions, the stiffness, the heat resistance and the mechanical strengths are improved to present molding or processing materials having excellent properties.Glass fibers having a diameter of2 through 20 microns and a length of 50 through 20,000 microns, which are conventionally used in the reinforcement of resins, can be advantageously used in the present invention.

The thermoplastic polymer compositions of the present invention can be readily prepared by using any conventional mixing apparatus which is usually used for mixing or blending of polymer substances.

Example of such apparatus are single or multiple screw extruders, mixing rolls, Banbury mixers, kneaders and the like. Although the mixing or blending of the present polymer composition can be preferably effected in the molten state, the mixing can be also effected by using the solution of each component, followed by the removal of the solvents in any known manner.

The polymer compositions of the present invention can be readily molded or formed into various kinds of useful articles by using any conventional molding or forming techniques, including extrusion molding, injection molding, blow moulding, pressure forming, rotational molding and the like. Examples of the articles are sheets, films, foamed products as well as injection-molded articles, blowmolded articles, pressure-formed articles and rotational-molded articles having various kinds of shapes. These articles can be used in the fields of, for example, automobile parts, electrical parts, mechanical parts, footwear, medical equipment and accessories, packaging materials, building materials and the like.Furthermore, the polymer compositions of the present invention are suitable for use, in the form of solutions, in the fields of adhesives, surface coating compositions, sealing agents and the like.

The present invention will now be further illustrated by, but is by no means limited to, the Examples set forth below.

In the Examples set forth below, modified block copolymers, in which the commercially available styrene-butadiene block copolymers shown in Table 1 as base block copolymers and, further, styrenebutadiene block copolymers shown in Tables 2 to 4, which were experimentary prepared, as base block copolymers, were modified with maleic an hydride were employed. In the comparative Examples, the unmodified styrene-butadiene block copolymers shown in Tables 1 to 4 were employed.

Furthermore, a process for producing modified block copolymers obtained from the grafting of the maleic an hydride onto the styrene-butadiene block copolymers and employed in the Examples are shown in the Modified Block Copolymer Production Examples below.

Table 1 Commercial Styrene-Butadiene Block Co polymer Sample Styrene MeltElow) No. Trade Name Content Index Manufacturer (wt%) (gliomin) SB-1 Tufprene A 40 11.0 Asahi Chemical Industry SB-2 Solprene 40 5.3 Japan ElastomerCompany T414 SB-3 Asaprene 30 10.3 Japan ElastomerCompany T931 SB4 KR-01 80 5.3 Phillips Petroleum Company 1) JIS-K-6870, 200 C, 5 kg Table 2 B1-S1-B2-S2 Type Styrene-Butadiene Block Copolymer Block Sample Styrene Styrene MW1) Mn2) Melt Flow3) No.Content Content Index Polymer Structure (wt%) (wt%) (g/10 min) SB-5 40 33 72,000 55,000 B1 = 15 wt%[B]/[S] = 12/3 (tapered) S1 = 17 wt%[B]/[S] = 0/17 B2 = 52 wt%[B] /LSU = 48/4 (tapered) S2 = 16 wt%[B]/[S] = 0/16 SB-6 42 37 81,000 62,000 12.1 B1 = 16 wt%[B]/[S] = 14/2 -(tapered) S1 = 19 wt%[B]/[S] = 0/19 B2 = 47 wt %[B] /[S] = 44/3 (tapered) S2 = 18 wt%[B] /LS] = 0/18 SB-7 38 33 79,000 61,000 11.0 B1 = 18 wt%[B]/[S] = 16/2 (tapered) S1 = 17 wt%[B]/[S] = 0/17 B2 = 49 wt%[B] /[Sj = 46/3 (tapered) S2 = 16 wt%[B]/[S] = 0/16 Remarks: Bn - Polymer block composed chiefly of butadiene.

Sn - Polymer block composed chiefly of styrene.

Integer n represents the order along the molecular chain.

[B] - Butadiene content 1) Mw : Weight average molecular weight [S] - Styrene content 2) Mn: Number average molecular weight 3) -JIS-K-6870, 200 Cm 5 Kg Table3 S,-B,-S2 Type Styrene-Butadiene Block Copolymer Block Sample Styrene Styrene Melt Flow Polymer Structure No. Content Content Index (wt%) (wt%) (g/10 min) SB-8 80 80 4.2 S1 = S2 = 40 wt% [B]/[S] = 0/40 B1 = 20 wt% [B]/[S] = 20/0 SB-9 80 80 7.2 S1 = S2 = 40 wt% [B]/[S] = 0/40 B1 = 20 wt % B / = 20/0 SB-10 74 74 8.4 S1 = S2 = 37 wt% [B]/[S] = 0/37 B1 = 26 wt% [B]/[S] = 26/0 SB-11 80 70 12.5 S1 = 37 wt% [B]/[S] = 0/37 B1 = 30 wt% [B]/[S] = 20/10 (random) S2 = 33 wt% [B]/[S] = 0/33 Table 4 Radial Type Styrene-Butadiene Block Co polymer Block Sample Styrene Styrene Melt Flow Polymer Structure, etc.

No. Content Content Index (wt %) (wt %) (g/10 min) SB-12 30 30 6.5 (S1-B1)4Si S1 = 6.25wt% B1 = 18,75 wt % Sl-B1-Li is coupled with SiCl4 Modified Block Copolymer Production Examples 1.5 parts by weight of maleic anhydride, 0.3 part by weight of BHT (butylhydroxytoluene) and 0.2 part by weight of phenothiazine which serve as a gellation preventing agent were added to 100 parts by weight of the styrene-butadiene block copolymer (SB-1), and the mixture was homogeneously blended together using a mixer. The mixture was supplied to a single screw extruder (full-flighted screw, screw diameter (D) = 40 mm, UD = 24) in a nitrogen atmosphere at a cylinder temperature of 190 to 210 C, to subject the mixture to the modification reaction.From the resulting polymer was removed the unreacted maleic anhydride under reduced pressure. The modified block copolymer (M-1 a) thus obtained has a melt index (JIS-K-6870, load of 5 kg, temperature of 200 C) of 7.2 9/10 min., a grafted amount of maleic anhydride of 0.70% by weight and a toluene-insoluble component of 0.03% by weight A variety of modified block copolymers shown in Table 5 were obtained from other styrene-butadiene block copolymers using the same extruder in a manner as described above. The results of analysis of these samples are shown in Table 5.

Table 5 Modified Block Copolymer Sample No. Base Block Copolymer Modified Block Copolymer of Modified Sample Type Styrene Amount of Maleic(1) Melt Flow (2) Block No. Content Anhydride Combined Index Copolymer (wt %) (parts by weight) (g/10 min) M-1a SB-7 Commercial 40 0.70 7.2 M-lb SB-1 Commercial 40 1.10 7.8 M-2a SB-2 Commercial 40 0.52 3.8 M-2b SB-2 Commercial 40 0.51 4.7 M-3a SB-3 Commercial 30 0.42 9.0 M4a SB4 Commercial 78 1.10 4.1 M-5a SB-5 B,-S1-B2-S2 40 0.25 18.2 M-5B SB-5 B1-S1-B2-S2 40 0.70 16.5 M-6a SB-6 B1-S1-B2-S2 42 0.53 9.3 M-7a SB-7 B1-S1-B2-S2 38 0.70 7.3 M-8a SB-8 S1-B1-S2 80 0.86 3.1 M-8b SB-8 D1-B1-S2 80 1.20 3.3 M-9a SB-9 S,-B1-S2 80 0.93 5.3 M-10a SB-10 S1-B,-S2 74 0.70 M-11a SB-11 S1-B1-S2 80 0.50 10.1 M-12a SB-12 Radial 30 1.5 4.2 (1) Based on 100 parts by weight of block copolymer (2) JIS-K-6870, 200 C, 5 kg Examples 1-1, 1-2 and Comparative Example 1-1 The compositions of Example 1-1 (using M-5a), Example 1-2 (using M-5c) and Comparative Example 1-1 (using SB-5) were obtained by kneading polymers shown in Table 6, using a Brabender Plastograph, at 220 Cf for 10 minutes. Namely, in Example 1-1 a modified block copolymer M-5a was employed as component A and in Example 1-2 an ionically crosslinked product of M-5a was employed.The ionically crosslinked product M-Sc was obtained by adding a mixture solvent solution of toluene and methanol of sodium methylate (CH3ONa) to a toluene solution containing 20% of M-5a in such an amount that CH3ONa/acid anhydride = 0.6 (in molar ratio), to react the mixture at room temperature, followed by the removal of the solvent. The ionic crosslinking was confirmed by the infrared spectrum), and in Comparative Example 1-1 an unmodified block copolymer SB-5 was employed as a component A, and nylon-6 (number-average molecular molecular weight of 18,000), which was a polar group-containing thermoplastic polymer, was employed as a component B. The physical properties of compression molded products obtained from these compositions are shown in Table 6.

It will be obvious from Table 6 that compositions obtained by using the modified block copolymer of Example 1-1 and the onically crosslinked product of the modified block copolymer of Example 1-2, exhibit improved tensile strength, heat resistance and oil resistance, as compared with the composition obtained by using the unmodified block copolymer of Comparative Example 1-1.

TableG Example No.

ltem Comparative Example 1-1 Example 1-2 Example 1-1 Composition: Modified block copolymer (M-5a) (parts by weight) 70 0 0 lonically crosslinked product (M-5c) (parts by weight) 0 70 0 Unmodified block copolymer (SB-5) (parts by weight) 0 0 70 - Nylon-6 (parts by weight) 30 30 30 Physical Properties: 25"C: Hardness (JIS) 94 96 93 25"C: Tensile strength (kg/cm2) 190 207 80 25"C: 300% Modulus (kg/cm2) 170 179 72 25"C: Elongation at break (%) 390 390 350 50"C: Tensile strength (kglcm2) 95 106 31 70 C: Tensile strength (kg/cm2) 60 72 12 Oil resistance, increase in volume 27 20 42 (oil No.JIS 3, at 23"C for 22 hours) (%) Transparency, Haze (%) 12.0 13.6 62.5 Examples 2-1,2-2 and Comparative Example 2- 7 The compositions of Example 2-1 (using M-5a), Example 2-2 (using M-5c) and Comparative Example 2-1 (using SB-5) were obtained by blending the modified block copolymer (M-5a), the ionically crosslinked product (M-5c) of the modified block copolymer (M-5a) and the unmodified block copolymer (SB-5) as component A, and the nylon-6 used in Example 1-1 as component B, at ratios shown in Table 7, using an extruder (LID = 28) of a size of 30 mm, followed by the pelletization. These compositions were injection-molded, and their physical properties are shown in Table 7.For the purpose of reference, the physical properties of a sample obtained by injection-molding the nylon-6 are also shown in Table 7.

As will be obvious from Table 7, the compositions obtained using the modified block copolymer of Example 2-1 and using the ionically crosslinked product of Example 2-2 exhibit greatly improved Izod impact strength, which results from the nylon-S, as compared with the composition of Comparative Example 2-1, which employs the unmodified block copolymer.

Table7 Example No.

Item Example Example Comparative Reference 2-1 2-2 Example 2-1 Example Composition: Modified block copolymer (M-5a) (parts by weight) 20 0 0 0 lonically crosslinked product (M-5c) (parts by weight) 0 20 0 0 Unmodified block copolymer (SB-5) (partsbyweight) 0 0 20 0 Nylon-6 (parts by weight) 80 80 80 100 Physical Properties:: (at 25"C) Izod impact strength (kg - cm/cm,with notch) 11.6 13.5 5.6 3.5 Tensile strength (kg/cm2) 580 596 450 760 Elongation {%) 110 105 60 130 Transparency, Haze (%) 14.3 16.4 55.2 Examples 3- 7, 3-2, 3-3 and Comparative Example 3-1,3-2 The resinous modified block copolymer (M-8a), and the jonically crosslinked product (M-8c) of the copolymer (M-8a) were used as component A.The ionically crosslinked product M-8c was obtained by adding magnesium acetate (tetrahydrate) in an amount of 0.4 mole with respect to acid anhydride groups contained in M-8a, to the M-8a which was melted buy a mixing roll heated at 180cm. For the purpose of comparison, the unmodified block copolymer (SB-8) was used as component A, and the nylon-6 used in Example 1-1 was used as component B. The compositions shown in Table 8 were obtained by kneading the above-mentioned components by using a Brabender Plastograph at 220"C. The physical properties of the compression molded products of these compositions are shown in Table 8.

As will be obvious from Table 8, the compositions obtained by using the modified block copolymer of Example 3-1 and the ionically crosslinked product of Example 3-2, exhibit excellent physical properties, as compared with the composition of Comparative Example 3-1, which employs the unmodified block copolymer. Furthermore, in Example 3-3 a composition consisting of the composition of Example 3-1 admixed with a high impact polystyrene (Styron 475D, a product of Asahi Dow Co.) was employed, and in Comparative Example 3-2 a composition consisting of the composition of Comparative Example 3-1 admixed with the high-impact polystyrene was employed. The composition of Example 3-3, in which the modified block copolymer was employed, exhibits excellent physical properties compared with those of the composition of Comparative Example 3-2.

Table8 Example No.

/tem Example Example Comparative Example Comparative 3-1 3-2 Example 3-1 3-3 Example 3-2 Composition: Component A: Modified block copolymer 70 0 0 70 0 (M-8a) (parts by weight) lonically crosslinked product 0 - -. 70 0 0 0 (M-8c) (parts by weight) Unmodified block copolymer 0 0 70 0 70 (SB-8) (parts by weight) Component B: Nylon-6 (parts by weight) 30 30 30 30 30 Component C: High impact polystyrene 0 0 0 15 15 (parts by weight) Physical Properties:: (at25 C) Izod impact strength (kg cmlcm,with notch) 4.0 4.6 2.3 4.7 2.5 Tensile strength (kg/cm2) 340 360 260 335 245 Elongation at break (%) 20 19 13 17 12 Transparency, Haze (%) 15.0 15.8 48.0 22.6 51.5 Examples 4-1,42,4-3 and Comparative Examples 4-1, 4-2,4-3 The compositions shown in Table 9 were prepared by kneading the modified block copolymer M2a as component A, the unmodified block copolymer SB2 as component A for comparison, and polymaides such as nylon lnylon6,6 copolymer (nylon-6 con tent of 70%, number-average molecular weight of 20,000) nylon-12 (RilsanBAMNO, a product of ATO Chemie Co.), and nylon-1 1 (RilsanBBMNO, a product of ATO Chemie Co.) as component B, using a Bra bender plastograph at 220"C. Table 9 shows the measured results of the impact strength of the com pression molded products of these compositions.

It will be understood that the compositions of Examples 4-1,4-2 and 4-3, employing the modified block copolymer, exhibit improved impact resis tance as compared with the compositions of Com parative Examples 4-1,4-2 and 4-3, which employ the unmodified block copolymer Table9 Example No.

Item Example Comparative Example Comparative Example Comparative 4-1 Example 4-1 1 42 Example 4-2 4-3 Example 4-3 Composition: Modified blockcopolymer 25 0 20 0 25 0 (M-2a) (parts by weight) Unmodified block copolymer 0 25 0 20 0 25 (SB-2) (parts by weight) N-6/N-6,6 copolymer 75 75 0 0 0 0 (parts by weight) Nylon-12 0 0 80 80 0 0 (parts by weight) Nylon-11 0 0 0 0 75 72 (parts by weight) Izod impact strength 9.5 4.3 7.8 3.1 9.4 3.2 (kg cm/cm, with notch) Example 5-1 A composition was prepared by kneading a polycaprolactam oligomer having terminal amino groups (an oligomer which has a number-average molecular weight of 950 based on the analysis of terminal amino groups, and which was obtained by polymerizing a ecaprnlactam with an n-butylamine as a molecular weight controlling agent) and a modified block copolymer (M-7b) at a ratio as shown in Table 10, using a Brabender plastograph, at 200"C, for 5 minutes. The composition was transparent and the reaction of acid anhydride groups in the modified block copolymer with the aminoterminated oligomerwas confirmed as analyzed by means of an infrared spectrophotometer.

Table 10 shows physical properties of the composition of Example 5-1. It will be understood thatthe composition of Example 5-1 exhibits improved mechanical properties and oil resistance, as compared with the block copolymer (SB-7) of the Reference Example.

Table 10 Item c Example 5-1 Reference Example Composition: Modified block copolymer (M-7a) (parts by weight) 100 0 Unmodified block copolymer (SB-7) (parts by weight) 0 100 Amino-terminated oligomer (parts by weight) 12.6 0 Physical Properties:: Hardness (JIS) 86 80 300% Modulas (kg/cm2) 33 21 Tensile strength 195 143 Elongation at break (%) 900 1,050 Oil Resistance (rate of weight increase) (%) 40 174 Melt index (g/10 min.) 3.1 11.0 Examples 6-1, 6-2 and Comparative Example 6-1 The compositions shown in Table 11 were prepared by using the modified block copolymer (M-1 a) and the ionically crosslinked product (M-1c)ofthe copolymer (M-la), as component A, the unmodified block copolymer SB1 as component A for comparison, and polybutyleneterephthalate (PBT-1041, a product of Toray Co.) which is a thermoplastic polyester as component B, by the method mentioned below.The ionically crosslinked product M-1c was obtained by reacting a toluene solution containing 20% of M-1a with CH3ONa at a ratio of CH3ONa/acid anhydride group = 1.5/1 (molar ratio).

80 parts by weight of polybutylene terephthalate pellets and 20 parts by weight of each of the above-mentioned specimens were supplied to a biaxial extruder having a diameter of 30 mm (which rotated in different directions, LID = 28), and were mixed at a temperature of 240 to 250"C and pelletized. The pellets of the compositions thus obtained were molded by an injection molder heated at 2400C to measure the properties ofthe molded products (Examples 6-1,6-2 and Comparative Example 6-1).

The results are shown in Table 11.

As will be obvious from the results of Table 11, the compositions of Example 6-1, which employs the modified block copolymer M-1a, and Example 6-2, which employs the onically crosslinked product of the modified block copolymer, exhibit improved resistance against impact as compared with the composition of Comparative Example 6-1, which employs the unmodified block copolymer SB-l or the PBT resin alone of the Reference Example.

Table 11 Example No, Item Example Example Comparative Reference 6-1 6-2 Example 6-1 Example Blending Ratio of Compositions: PBT (parts by weight) 80 80 80 100 Modified block copolymer (M-1a)(parts by weight) 20 0 0 0 Ionically crosslinked product (M-1c)(parts by weight) 0 20 0 0 Unmodified block copolymer (SB-1) 0 0 20 0 0 Physical block Properties: (SB-1) 0 0 20 0 (at 25 C) Tensile yield strenght (kg/cm) 512 531 500 565 Elongation at break (9G) 35 29 25 22 Izod impact strength (kg - cm/cm, with notch) 4.6 5.4 2.3 2.0 Thermal deformation temperature (4.64kg/cm2 load) 150 152 150 160 Example 7-1 and Comparative Example 7-1 Compositions were prepared by the method mentioned below using the modified block copolymer M-1 a and the unmodified block copolymer SB-1 as component A, and a component B consisting of a polyester (specimen P-l ) having an inherent viscosity of 0.75 (as measured in an orthochlorophenol solution at 35"C) and a softening point of 195"C with ethylene glycol as a diol component, and terephthalic acid and isophthalic acid as dicarboxylic acid components.

80 parts by weight of pellets of the specimen M-1 a or the specimen SB-l and 20 parts by weight of pellets of the specimen P-1 were supplied to an extruder of a diameter of 30 mm, mixed together at a temper ature of 200 to 210 C, and pelletized. The resulting pellets were compression-molded at 200 C and the properties of the molded products were measured.

The results are shown in Table 12 together with the results of the specimen M-1 a alone.

The results of Table 12 indicate that the composition of the modified block copolymer and the polyester of Example 7-1 presents excellent mechanical properties, such as tensile strength, 300% tensile stress, and the like, excellent oil resistance, and excellent heat resistance as represented by a tensile strength retaining factor at 50"C, over those of the composition consisting of the unmodified block copolymer and the polyester of Comparative Example 7-1 or the modified block copolymer alone of the Reference Example. Namely, the results of Table 12 indicate that the composition of the present invention is a useful material.

Table 12 Example No.

Item Example Comparative Reference 7-1 Example 7-1 Example Blending Ratio of Compositions: Modified block copolymer (M-1a) (parts byweight) 80 0 100 Unmodified block copolymer (SB-1) (parts by weight) 0 80 0 Polyester (P-1) (parts by weight) 20 20 0 Physical Properties: 25"C; Hardness (JIS) 93 92 84 300% Modulus (kg/cm2) 42 35 26 Tensile strength (kglcm2) 200 140 170 Elongation at break (%) 700 550 950 Oil resistance, rate of volume increase 28 53 70 (Oil No.JIS 3,22 hr) 50"C: Tensile strength (kg/cm2) 120 67 70 Tensile strength retaining factor (%) 60 48 41 Example & and Comparative Example 8-1 Compositions were prepared by the following method using the modified block copolymer M-1 a, the unmodified block copolymer SB-1, and a polyester (specimen P-2) having a softening point of 133"C (as measured by the ring and ball method in accordance with JIS K 2531) and an inherent viscosity of 0.50 (as measured in an orthochlorophenol solution art a polymer concentration of 1 gill 00 cc at 35"C) with 1,4-butane diol as a diol component, and terephthalic acid, isophthalic acid and adipic acid as dicarboxylic acid components. 20 parts by weight of pellets of the specimen M-1a or SB-1 and 80 parts by weight of pellets of the specimen P-2, were mixed together using a kneader (Model PBV-0.1) manufactured by Irie Shokai Co., at a temperature of 1200C for 60 minutes to obtain a mixture. The mixture was pulverized to measure its applicability as hot-melt adhesive agent. The results were as shown in Table 13.

(1) Melt viscosity (poises).

Melt viscosity at 200"C was measured using a Koka-type flow tester manufactured by Shimazu Mfg. Co.

(2) Adhesive strength under tensile shearing force.

A film-like adhesive agent was interposed betwees two aluminum plates (thickness 1.6 mm), preheated at 200"C for 3 minutes, and was compressed by the cold press under a load of 10 kg/cm2 for 5 minutes to prepare an adhesive test piece (adhesive area 25 x 12.5 mm, thickness of adhesive layer 0.1 mm). The shearing strength was measured when the aluminum plate was pulled at a rate of 10 mm/min, at ordinary temperature using a pulling tester.

(3) T-peeling adhesive strength.

The film-like adhesive agent was interposed between two aluminum plates (thickness 0.2 mm), preheated at 200"C for 3 minutes, and was compressed by the cold press under a load of 10 kg/cmZ for 5 minutes to prepare an adhesive test piece (adhesive area 25 mmx 100 mm, thickness of adhesive layer 0.1 mm). The T-peeling strength was measured when the aluminum plate was pulled at a rate of 200 mm/min. atordinarytemperature using a pulling tester.

As will be obvious from the results of Table 13, the composition of the modified block copolymer and the polyester of Example 8-1 exhibits well-balanced properties which are required for hot-melt adhesive agents, such as melt flowability, adhesive strength under tensile shearing force and T-peeling adhesive strength, which are greater than those of the composition of Comparative Example 8-1 or polymers of Reference Examples.

Table 13 Example No.

Item Example Comparative Reference Reference Reference 8-1 Example 8-1 Example Example Example Blending Ratio of Compositions: (parts by weight) Modified blockcopolymer (M-1a) 20 0 100 0 0 Unmodified block copolymer (SB-1) 0 20 0 100 0 Polyester (P-2) 80 80 0 0 100 Physical Properties: Melt viscosity (poises) 80 75 > 5,000 > 5,000 60 Adhesive strength under 70 38 23 20 96 tensile shearing force (kg/cm2) T-peeling adhesive strength 8.6 3.2 16.0 5.3 2.7 (kg/25 mm) Example 9-1 and Comparative Example 9-1 Compositions shown in Table 14 were prepared by kneading the modified block copolymer M-8b as component A, and the unmodified block copolymer SB-8 as component A for comparison, using a Brabender plastograph, at 180"C, for 15 minutes.

The compositions of Example 9-1 exhibited superior transparency to the composition of Comparative Example 9-1 as shown in Table 14. It is obvious that use of the modified block copolymer helps improve the compatibility.

Table 14 Example No.

Item Example Comparative 9-1 Example 9-1 Blending ratio of compositions (parts by weight) Modified block copolymer (M-8b) 80 0 Unmodified block copolymer (SIlls) 0 80 Specimen P-l (polyester) 20 20 Transparency, Haze (%) 25.6 47.6 Examples 10-1, 102, 10-3, and Comparative Examples 10-1, 10-2 Compositions were prepared by using the modified block copolymer M-6a and the unmodified block copolymer SB-1 at ratios shown in Table 15, as well as ELASTOLLAN E 185FNAT (a product of Nippon Elastollan Co.), which is an incomplete thermop lastictype polyurethane, and PARAPRENE P-22SM (a product of Nippon Polyurethane Co.), which is a complete thermoplastic type polyurethane, by using a mixing roll heated at 180"C. The properties of the compression molded products ofthese compositions were measured. The tensile strength retaining factor was also measured afterthe products were immersed in hot water maintained at 80 C for 30 days, to study the resistance against hydrolysis. The iou crosslicked product hi 6b used in Example 10-3 was obtained by adding sodium methylate to the modified block copolymer M4a in an amount of 0.5 mole based on the acid anhydride groups contained in the copolymer M6a.

As will be obvious from Table 15, the hardness of the compositions of Examples 10-1 to 10-3 is identical to that of the polyurethanes of the Reference Examples, and the decrease in the tensile strength of the present composition from the tensile strength of the polyurethane is not large. The 300% tensile stress was small, indicating increased flexibility. On the other hand, when the unmodified block copolymerwas used as in Examples 10-1 and 1Q-2, increased flexibility was exhibited but the tensile strength was greatly decreased. Further, use of the modified block copolymer improves the resistance against hydrolysis as compared with the compositions which employ polyurethanes or the unmodified block copolymer.

Table 15 Composition Item Comparative Comparative Reference Reference Reference Example 10-1 Example 10-2 Example 10-3 Example 10-1 Example 10-2 Example Example Example Blending Ratio of Compositions: Component B: Type ELASTOLLAN PARAPRENE ELASTOLLAN PARAPRENE ELSTOLLAN - E185FNAT P-22SM E185FNAT E185FNAT P-22SM E185FNAT Amount 75 75 75 75 75 100 - (parts by weight) Component A: Specimen No.M-6a M-6a M-6b SB-6 SB-6 - SB-6 M-6a (types) (modified) (modified) (ionically (unmodified) (unmodified) (unmodified) (modified) crosslinked) Amount 25 25 25 25 25 - 100 100 (parts by weight) Physical Properties: Hardness (JIS) 85 84 86 85 84 85 85 86 300% Modulus (kg/cm) 75 58 82 76 57 105 23 26 Tensile strength (kg/cm) 348 370 363 244 270 403 142 168 Elongation (%) 670 630 620 720 640 600 1,000 970 Tensile strength retaining factor after immersed in hot 83 85 84 74 75 69 - water (80 C) for 30 days Example 11-land Comparative Example 11-1 Compositions were prepared by kneading large amounts of the modified block copolymer or the unmodified block copolymer at the ratios shown in Table 16 using a mixing roll heated at 180"C. The properties of the compression molded products of these compositions were measured.Table 16 shows these results together with the results of a Reference Example.

As will be obvious from Table 16, the composition of Example 11-1 exhibits a tensile strength which is close to that of the block copolymer, and an improved reistance against oils and wear. The composition of Comparative Example 11-1, however, exhibits greatly deteriorated tensile strength and unchanged resistance against oils and wear.

Table 16 Composition Item Comparafive Reference Example 11-1 Example 11-1 Example Blending Ratio of Compositions: Component B : Type ELASTOLLAN ELASTOLLAN E180FNAT Ef 80FNAr Amount (parts byweight) 15 15 Component A: Specimen No.M-6a SB-6 SB-6 (type) (modified) (unmodified) (unmodified) Amount (parts by weight) 85 85 100 Physical Properties: Hardness (JIS) 84 84 85 Tensile strength (kg/cm2) 123 85 142 Oil resistance (rate of weight increase) (%) 36 54 73 Picco abrasion (ccl80times) 0.018 0.031 0.057 Example 12-1 and Comparative Example 12-1 The compositions shown in Table 17 were obtained by mixing a modified block copolymer (M-8b) containing large amounts of styrene and an unmodified block copolymer (SB-8) using a mixing roll heated at 170 C.

As will be obvious from the results of Table 17, the composition of Example 12-1 exhibits improved mechanical properties as compared with the block copolymer SB-8 of the Reference Example and the composition employing the unmodified block copolymer of Comparative Example 12-1.

Table 17 Composition No.

/tem Comparative Reference Example 12-1 Example 12-1 Example Blending Ratio of Compositions: Component B : Type ELASTOLLAN ELASTOLLAN' E195FNAT E195FNAT Amount (parts by weight) 20 20 Component A: Specimen No. M-8b 588 SB-8 (type) (modified) (unmodifed) (unmodified) Amount (parts by weight) 80 80 100 Physical Properties: Izod impact strength (kg - cm/cm, with notch) 2.8 2.1. 1.8 Tensile yield strength (kg/cm2) 330 3'it2 295 Elongation at break (%) 24 15 20 Examples 13-1, 13-2, 13-3 and Comparative Examples 13-1, 13-Z 13-3 The compositions shown in Table 18 were pre pared by kneading a modified block copolymer M-2b and an unmodified block copolymer SB-2 using a Brabender plastograph at a temperature of 1 80"C.

These compositions were adhered onto a polyvinyl chloride sheet and onto a high-density polyethylene sheet at 1800C, to measure the peeling strength. The results were as shown in Table 18.

As will be obvious from the results of Table 18, the compositions of the present invention exhibit excellent adhesiveness onto the polyvinyl chloride sheet and onto the polyethylene sheet over a wide composition range. The compositions of the Comparative Examples, ontheother hand, exhibit inferior adhesiveness to that of the compositions of the present invention.

Table 18 Example No.

Item Example Example Example Comparative Comparative Comparative 13-1 13-2 13-3 Example 13-1 Example 13-2 Example 13-3 Blending Ratio: (parts by weight) M-2b (modified) 10 60 90 - - - SB-2 (unmodified) - - - 10 60 90 Polyurethane 90 40 10 90 40 10 (ELASTOLLANE E180FNAT) 90" Peeling strength from 10.7 10.1 6.5 8.7 3.3 1.1 polyvinyl chloride (keg125 mm) 1800 Peeling strength from 7.8 11.3 12.5 1.6 2.5 4.1 polyethylene (kg/25 mm) Examples 141 to 14-5 and Comparative Examples 14-1 to 144 The compositions shown in Table 19 were obtained by kneading EVAL-EP-E (a product of Kuraray Co.) of an ethylene/vinyl alcohol copolymer, which is a saponified product of ethylene/vinyl acetate copolymer, as a vinyl alcohol-type polymer (component B), modified block copolymers M-7a, M-10a (component A), and unmodified block copolymers SB-7, SB-10 and SB-3 (component A) for comparison, using a mixing roll heated at 1600C.

Further, an onically crosslinked specimen M-7c was obtained by adding sodium methylate to the modified block copolymer M-7a in an amount of 1/4 mole with respect to the acid anhydride groups contained in the copolymer M-7a, to thereby prepare a composition. The physical properties of the compression molded products (molded at 1800C of these compositions and the adhesiveness to the high-density polyethylene, were measured as shown in Table 19.

As will be obvious from the results of Table 19, the composition of Example 14-1, to which was added the modified block copolymer M-7a, exhibits astonishingly increased notched Izod impact strength as compared with the corresponding composition of Comparative Example 14-1, to which was added the unmodified block copolymer. The tensile yield strength ofthe composition of Example 14-1 was nearly equal to that of the composition of Comparative Example 14-1. The ethylene/vinyl alcohol copolymer of the Reference Example exhibited a small notched Izod impact strength.

Observation of the specimen of Example 14-1 and the specimen of Comparative Example 141 by a phase contrast microscope indicated that the modified block copolymer was uniformly dispersed in the form of particles of about 0.5 to 2 microns in size in the matrix of the ethylene/vinyl alcohol copolymer in the specimen of Example 14-1, while block copolymer particles of a size of about 5 to 10 microns or greater were dispersed in the specimen of Comparative Example 14-1. Nameiy, the two specimens exhibit conspicuously different compatibilities.

Even when other modified block copolymers were employed, or even when different compositions were treated, the compositions of the present invention exhibited greatly improved Izod impact strength as compared with the corresponding compositions containing the unmodified block copolymers of the Comparative Examples. Furthermore, the compositions of the present invention exhibited improved adhesiveness with respect to the polyethylene.

From the aforementioned results, therefore, it is obvious that the present invention provides very useful compositions.

Table 19 Example No.

Item Example Example Example Example Example Comparative Comparative Comparative Comparative Reference 14-1 14-2 14-3 14-4 14-5 Example 14-1 Example 14-2 Example 14-3 Example 14-4 Example Blending Ratio of Compositions: Component A: Specimen No. M-7a M-7a M-10a M-3a M-7c SB-7 SB-7 SB-10 SB-3 Type modified modified modified modified ionically unmodified unmodified unmodified unmodified Amount (parts by weight) 25 10 25 30 25 25 10 25 30 Component B: (EVAL-EP-E) Amount (parts by weight) 75 90 75 70 75 75 90 75 70 100 Physical Properties: Melt index (200 C, load 5 kg) 5.8 10.2 7.3 43 3.6 26.8 28.5 27.8 23.3 28.4 (gr/10 min) Izod impact strength 97.5 16.5 11.3 104.1 91.5 6.3 3.3 3.4 6.8 2.4 (kg.cm/cm, with notch) Tensile yield strength 340 423 395 325 351 342 418 346 314 490 (kg/cm) Tensile breaking strength 285 336 320 261 290 315 390 312 309 450 (kg/cm) Elongation at break (%) 60 80 25 50 55 10 26 23 7 200 T-Peeling strength from* high-density polyethylene 3.3 1.8 - - 3.4 0.3 - 1.2 1.0 0.1 (kg/25 mm) or less * In accordance with JIS-K-6854 Examples 15-1, 15-2 and Comparative Examples 75-1, 15-2 Compositions composed mainly of the modified block copolymer of the component A shown in Table 20 were prepared using a mixing roll heated at a temperature of 160 C.The physical properties, oil resistance and adhesiveness of the compression molded products (molded at 180 C) of these compositions were measured to be as shown in Table 20.

It will be obvious from the results of Table 20 that the compositions of the present invention maintain sufficient machinability, while exhibiting high tensile stress and strikingly increased oil resistance with the addition of small amounts of the component B.

Further, the compositions of the present invention exhibit better adhesiveness to the polyethylene than those of the Comparative Examples.

Thus, even when the component A is chiefly employed, the compositions of the present invention are useful as the improved block copolymers.

Table 20 Example No.

item Comparative Comparative Reference Reference Example 15-1 Example 15-2 Example 15-1 Example 15-2 Example Example Blending Ratio of Compositions: Component A: Specimen No. M-7a M-7a SB-7 SB-7 M-7a 88-7 Type modified modified unmodified unmodified modified modified Amount (parts by weight) 75 90 75 90 100 100 Component B: (EVAL-EP-E) Amount (parts by weight) 25 10 25 10 - - Physical Properties: Melt index (200 C, load 5 kg) (grill min.) 5.4 6.6 19.0 14.5 8.2 11.0 Hardness (HS) (JIS) 88 86 85 84 84 81 300% Modulus (kg/cm2) 66 38 41 27 24 21 Tensile strength (kg/cm2) 121 142 95 118 163 143 Elongation at break (%) 900 950 1.000 1,000 1,010 1.050 Oil resistance, rate of weight increase(%)* 25 44 49 55 56 74 T-Peeling strength from high-density** 7.5 6.9 1.9 2.1 7.2 2.3 polyethylene (kg/25 mm) * Immersed in oil JIS No.3 for 24 hours.

** In compliance with JIS-K-6854.

Examples 16-1 to 16-3 and Comparative Examples 16-1, 16-2 Compositions were prepared by mixing the modified block copolymer M-7a, the modified block copolymer M-lOa, and specimens SB-7 and SB-10 for comparison, together with methyl methacrylate resin (DELPET 8 ON, a product of Asahi Kasei Kogyo Co.) at the ratios shown in Table 21, using a mixing roll heated at 1600C (Examples 16-1, 16-2 and Com parative Examples 16-1,16-2). In Examples 163, a composition was prepared by using the onically crosslinked polymer (M-7d) that was obtained by adding sodium methylate to the modified block copolymer M-7a in an amount of 0.5 mole with respectto the acid an hydride groups contained in the copolymer M-7a.The physical properties of the compression molded products of these compositions were measured, and cracking by the solvent was tested, as shown in Table 21.

The compositions of Examples 16-1 and 16-2 employing the modified block copolymers, and the compositions of Example 163, employing the ionically crosslinked product, exhibited improved impact resistance and good resistance against cracking by solvent as compared with the compositions of the Comparative Examples employing the unmodified block copolymers.

Table 21 Example No.

Item Example Example Example Comparative Comparative Reference 16-1 16-2 163 Example 16-1 Example 16-2 Example Component A: Specimen No. M-7a M-10a M-7d SB-7 SB-10 (type) (modified) (modified) (lonically (unmodified) (unmodified) crosslinked) Amount (parts by weight) 25 25 25 25 25 Component B: PMMA (parts by weight) 75 75 75 75 75 100 Physical Properties: Izod impact strength 4.5 2.1 5.0 3.2 1.5 1.3 (kg.cm/cm, with notch) Tensile yield strength (kg/cm2) 259 280 272 224 251 720 Elongation at break (%) 12 5 10 6 4 3 Corrosion bysolventt ++ ++ ++ + + * Surfaces of the molded products were coated with acetone and were observed after drying.

++ ... Good + ... Slightly improved - Poor Example 17-1 and Comparative Example 17-1 Compositions composed mainly of the modified block copolymer (M-7a) and the unmodified block copolymer (SB-7) for comparison, were mixed together at the ratios shown in Table 22 using a mixing roll heated at 1600C. The oil resistance and ten sile strengths at ordinary temperature and at 70"C of the compression molded products of these compositions were measured, and studied with regard to their resistance against oils and heat. The results were as shown in Table 22.

As will be obvious from the results of Table 22, the composition of Example 17-1 exhibited good resistance against oils and heat as compared with the composition of Comparative Example 17-1.

Table 22 Example No.

Item Example Comparative 17-1 Example 17-1 Component A: Specimen No. M-7a SB-7 (type) (modified) (unmodmad) Amount (parts byweight) 15 15 Component B: PMMA (parts by weight) 85 85 Physical Properties: Oil Resistance* 45 66 (rate of weight increase) (%) Tensile strength 112 95 Tensile strength retaining 18 10 factor at 70"C (%) * Immersed in an oil of JIS No.3 for 24 hours.

Examples 18-1, 18-2, 18-3 and Comparative Examples 18-1, 18-2, 18-3 The compositions shown in Table 23 were kneaded using a mixing roll heated at 1600C, placed and adhered with pressure onto an aluminum plate at 1800Cto measure the peeling strength with res pecttothe aluminum plate. The results were as shown in Table 23.

As will be obvious from the results of Table 23, the compositions of Examples exhibit good adhesiveness as compared with the compositions of the corresponding Comparative Examples.

Table 23 Example No.

Item Example Example Example Comparative Comparative Comparative 18-1 18-2 18-3 Example 18-1 Example 18-2 Example 18-3 Composition (parts by weight) M-7a (modified) 8 40 70 - - - SB-7 (unmodified) - - - 8 40 70 PMMA resin 92 60 30 92 60 30 Peeling strength:* 3.7 7.6 13.5 0.7 3.1 3.4 (kgl25 mm) * In compliance with JIS-K-6854 Examples 19-1 to 194 and Comparative Examples 19-1 to 19-3 Compositions were obtained by blending the modified block copolymers M-1 b and M-9a and polyvinyl chloride as shown in Table 24, using a mix ing roll heated at 175"C. These compositions were admixed with a stabilizer for vinyl chloride in an amount of2 parts by weight with respect to the total amount. Forthe purpose of comparison, composi tions were prepared in the same manner by using the unmodified block copolymers SB-1 and SB-9 (Comparative Examples 19-1 to 19-3). Izod impact strength and transparency (sheet of a thickness of 0.3 mm) of the compression molded products of these compositions were measured.The results were as shown in Table 24. Table 24 also shows the measured results of the polyvinyl chloride as the Reference Example.

All of the compositions of Examples 19-1 to 194 exhibited improved compatibility with respect to polyvinyl chloride, as well as good transparency and improved impact resistance as compared with the compositions of the corresponding Comparative Examples 19-1 to 193. It is, therefore, obvious that the compositions of the present invention employing modified blockcopolymers are very useful.

Table 24 Example No.

Item Comparative Comparative Comparative Reference Example 19-1 Example 19-2 Example 19-3 Example 19-4 Example 19-1 Example 19-2 Example 19-3 Example Blending Ratio of Compositions: Component A:Specimen No. M-1b M-1b M-9a M-1d SB-1 SB-1 SB-1 (type) (modified) (modified) (modified) (ionically (unmodified) (unmodified) (unmodified) crosslinked) (Note 2) Amount 20 15 30 10 20 15 30 (partabyweight) Component B: Polyvinyl chloride (Note t), Amount 50 60 70 90 60 60 70 100 (parts by weight) Additive:Type - dioctyl - - - dioctyl phthalate phthalate Amount - 25 - - - 25 - (parts by weight) Phisical Properties: Izod impact strength 8.4 10.5 5.7 10.3 6.5 9.6 4.9 4.6 (kg.cmlcm. with notch) Transparency, Haze (%) 14.6 8.9 15.3 17.1 43.0 38.2 41.3 2.5 Note 1: Polyvinyl chloride... Nippolit SL (a product of Chisso Co.. average polymerization degree 1030).

Note 2: M-ld (lonicallycrosslinked product) . . . Specimen P was lonicelly crosslinked by the addition of NaOH in an amount of 1/3 molewith respect to acid anhydride groups.

Examples 20-1, 20-2 and Comparative Examples 20- 1, 20-2 The compositions of Table 25 were prepared employing the modified block copolymer M-1 b in large amounts, using a mixing roll heated at 175 C (Examples 20-1 and 20-2). Compositions were also prepared in the same manner but using the unmodified blockcopolymerSB-1 instead of the modified block copolymer M-1 b (Comparative Examples 20-1 and 20-2). The physical properties of these compositions and of the unmodified block copolymer SB-1 of the Reference Example are shown in Table 25.

As will be obvious from the transparency (measured using a sheet of a thickness of 0.3 mm ) and oil resistance shown in Table 25, the compositions employing the modified block copolymer of Examples 20-1 and 20-2, exhibited improved compatibility with respect to two phases, good transparency and increased oil resistance, as compared with the compositions of the corresponding Comparative Examples 20-1 and 20-2 employing the unmodified block copolymer.

Table 25 Exam pie No.

Item Comparative Comparative Reference Example 20-1 Example20-2 Example 20-1 Example 20-2 Example Blending Ratio of Compositions: Component A:Specimen No. M-1b M-1b SB-1 SB-1 SB-1 (type) (modified) (modified) (unmodified) (unmodified) (unmodified) Amount (parts by weight) 75 80 75 80 100 Component B: Type Polyvinyl chloride Vinyl chloride- Polyvinyl chloride Vinyl chloride- vinyl acetate vinyl acetate copolymer (Note 1) copolymer (Note 1) Amount (parts by weight) 15 20 15 20 Additive: Type Dibutyl phthalate - Dibutyl phthalate Amount(partsbyweight) 10 - 10 Physical Properties:: Transparency, Haze (%) 7.2 9.8 25.4 21.2 2.6 Oil resistance (Note 2) 41 44 66 61 74 (rate ofweight increase) (%) (Note 1) Vinyl chloride-vinyl acetate copolymer: Nippolit MR (a product of Chisso Co., average polymerization degree 800).

(Note 2) Immersed in an oil of JIS No. 3 at 25 C for 24 hours.

Example 21-1 and Comparative Example 21-1 Composition of the modified block copolymer M-1 b (Example 21-1) or the unmodified block copolymer SB-1 (Comparative Example 21-1) and the chlorinated polyethylene ELASLEN manufactured from Showa Denko Co.) listed in Table 26 below was prepared by blending in a Brabender Plastograph at 200 C.

The results of the oil resistance test of these compositions are shown in Table 26 below. As will be obvious from the results in Table 26, the oil resistance of the composition of Example 21-1 containing the modified block copolymer is improved, as compared with that of the composition of Comparative Example 21-1.

Table 26 Example No.

Item Comparative Example2l-l Example 21-i Component A: Modified block copolymer (M-1b) 77 (parts by weight) Unmodified block copolymer (SB-I) - 75 (parts by weight) Component B: Chlorinated polyethylene 25 (parts by weight) OilResistancee 33 56 (rate of weight increase) (%) Immersed in an oil of JIS No.3 for 24 hours Example 22-1 to 22-10 and Comparative Example 22-1 to 22-6 100 parts by weight of each thermoplastic polymer listed in Table 27, 10 parts by weight of the modified block copolymer M-5b (Example) or the unmodified block copolymerSB-5 (Comparative Example), 1 part by weight of 2,6 - di -tert. - butyl -4 - methyl phenol and 1 part by weight of tris - nonylphenyl phosphite, as stabilizers, were mixed by using a Henschel mixer and, then, the mixture was pelletized by using a 40 mm extruder. The pellets thus obtained were injec tion molded to form flat plates having a size of 120 x 1203 mm.

After degreasing the flat plates with methyl alcohol, a commercially available acryl resin type coating composition was sprayed onto the surfaces of the plates and air dryed . In the case of the plates obtained from the compositions containing, as the thermoplastic polymer polyoxymethylene and nit rile resin, the degreasing with methyl alcohol was replaced with the immersion in hydrochloric acid for 30 minutes followed by washing with water spray ing.

The results of adhesion test coating of the plates are shown in Table 28 below. As will be clear from the results shown in Table 28,the adhesion of coating in the present polymer compositions is remark ably superior to that of the comparative composi tions.

Table 27 Thermoplastic Polymer Used in Examples 22 to 29 \Abbreviation Thermoplastic Polymer Manufacturer Trade Name PO Polyoxymethylene Polyoxymethylene diacetate having MI of approximately 10 g/10 min, (210 C, 2.16 kg) PC Polycarbonate Teijin Kasei Co. PANLITEL-1225 PS Polysulfone I.C.I. POLYETHERSULFONE 200P NR Nitrile regin Acrylonitrile/Styrene (90/10) Copolymer having a MI of approximately a g710 min. 8190 C, 12.5 kg) PPE Polyphenylene ether GE NORYL 701 GPPE Styrene-grafted Asahi Dow Co. XYLON 500H Polyphenylene ether PPS Polyphenylene sulfide Phillips Petroleum Co. Ryton R-6 PBT Polybutylen terephthalate Toray Co. PBT 1041 TIPET Thermoplastic Polyester Toyoboseld Co. PELPRN P150B PA Polyamide Toray Co. AMILAN CM-1017 ABS Acrylonitrilessutadiene Asahi Dow Co. STYLAC 181 Styrene Copolymer HIBS Rubber-Modified High Asahi Dow Co. STYLON 492 Impact Polystyrene Table 28 Item Example 22 Comparative Example 22 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 Type of Block Modified Block Copolymer M-5b Unmodified Block Copolymer Copolymer SB-5 Type of Thermoplastic *2 *3 *4 Polymer*1 PO PC PS NR PPE GPPE PPS PC PS PO PO PC PS NR PPE PPS + + + PET PA TPET Adhesion of + ++ ++ + ++ ++ ++ + + + -- - - -- + Coating (Remarks) * 1 Please refer to Table 27.

* 2 Blend of PC and PET (blending ratio = 2:1) * 3 Blend of PS and PA (blending ratio = 2 :1) *4 Blend of PO and TPET (blending ratio = 4:1) * 5 A hundred of small portions each having a size of 1 mmx 1 mm were prepared on the coated surface of each plate by cutting the surface with a knife, and a pressure-sensitive adhesive tape was applied onto the coated surface. After that, the tape was peeled off from the surface at a right angle. The number of the small portions which were peeled together with the tape was counted and the adhesion of coating was evaluated according to the following standard.

Rating Number of the small portions which was peeled-off ++ ..... lOorless + ..... 11 through 20 - ..... 1 through 40 - - .... 41 or more Examples 23-1,23-2 and Comparative Examples 23-1,23-2 100 parts by weight of PO or NR was mixed with 25 parts by weight of the modified block copolymer M-1 1a (Example) or 25 parts by weight of the unmodified block copolymer SB-11 (Comparative Example), 0.5 part by weight of 2,6 - di -tert. - butyl 4 - methylphenol and 0.5 part by weight of tris nonylphenyl phosphite by using a Henschel mixer and the mixture was pelletized in an extruder. The pellets thus obtained was injection molded to form flat plates. The Dart impact strength of the plates was determined.The results are shown in Table 29 below. As will be clear from the results in Table 29, it is observed that the present compositions are superior, in the impact resistance, to the comparative compositions and that the denseness of the present compositions is superior to that of the comparative compositions.

Table 29 Item Example 23 Comparative Example 23 1 2 1 2 Type of Block Copolymer Modified Block Copolymer Unmodified Block Co polymer (M-11a) (SB-11) Type of Thermoplastic Polymer*1 PO NR PO R Dart Impact Strength (kg.cm)* 2 220 150 Determination could not be effected due to the serious interfacial peeling.

* 1 Please refer to Table 27.

* 2 Various weights were dropped onto the fixed plates at a height of 1 m and the energy by which 50% of the plates were broken was determined.

Examples 24-1 to 24-4 and Comparative Examples 24- 1 to 24-4 The pellets were obtained in a manner as described in Example 23, except that the thermoplastic polymers were replaced with those listed in Table 30 below. By using these pellets, test pieces were prepared by an injection molding and the impact strength test and the surface glossiness test were carried out.

The results are shown in Table 30. In Table 30, the surface gloss test results obtained from the compositions in which the ionically crosslinked modified block copolymer M-1 1 b was used in lieu of M-1 1 a are also shown. As will be clear from these result, it is quite unexpected that the use of the ionically crosslinked product M-1 1 b further improve the surface gloss, as compared with the modified block copolymer M-1 1 a. The ionically crosslinked product M-1 1 b was obtained by reacting 0.6 parts by weight of sodium methylate in the form of a toluenemethanol mixed solvent solution with 100 parts by weight of M-1 1 a in the form of a 20% toluene sotu- tion at a room temperature, followed by the removal of the solvent.

As will be clear from the results in Table 30, the impact strength is improved by the use of the modified blocicopolymer.

Table 30 Example 24 Comparative Example 24 1 2 3 4 # 2 3 4 Type of Block Copolymer Modified Block Copolymer Unmodified Block Copolymer (M-11a) (SB-11) Type of Thermoplastic Polymer PC PS GPPE PPS PC PS GPPE PPS Izod Impact Strength 31.3 8.2 26.5 3.0 26.6 5j 22.3 23 (kglcm.cm, with notch) Gloss(%)*1 71 63 73 64 66 58 69 60 *2 76 78 71 - - - +1 M-11a was used *2 M-11b was used.

Examples 25-1 to 25-4 The pellets were prepared in a manner as described in Example 23 by using the modified block copolymer M-12a, as listed in Table 31 below. The pellets were injection molded to form test pieces and the impact strength thereof were tested. The results are shown in Table 31.As will be clear from the results in Table 31 the compositions of the present invention have extremely high impact strengths.

Table 31 Example 25 1 2 3 4 Component A: Type Modified Block Copolymer Amount (parts by weight) 10 20 20 10 Component B: Type PC PS GPPE Amount (parts by weight) 70 60 65 70 Component C: Type ABS HIPS Poly- HIPS styrene Amount (parts by weight) 20 20 15 20 Izod Impact Strength 45.3 18.5 34.1 t5.7 (kg.cmlcm, with notch) Example 26-1, 26-2 The compositions containing glass fibers together with the modified block copolymers and the thermoplastic polymers in the blending ratios listed in Table 32 below were pelletized. The pellets thus obtained were injection molded to form test pieces and the impact strength tests were carried out by using these test pieces. The results are shown in Table 32 below.

Table 32 Item Example 26-1 Example 26-2 ComponentA M-iia M-5b (parts by weight) 20 10 Component B PS PPE (parts by weight) 40 70 Glass Fibers* 40 20 (parts by weight) Izod Impact Strength 9.1 21.5 (kg - cm/cm, with notch) * 1 CS 69A401 available from Nitto Boseki Co.

Examples 27-1 to 27-8 and Comparative Examples 27-1 to 27-7 The compositions were prepared according to the following formulation.

(1) Blending Ratios of Composition Parts by weight (a) Modified Block Copolymer M-5b (Examples) 100 or Unmodified Block Copolymer SB-5 (Comparative Example) (b) Thermoplastic Polymer listed in Table 33*' 50 (c) Naphthenic Process Oil 50 (d) Titanium Dioxide 1 (e) Stabilizer*2 0.7 * 1 Each thermoplastic polymer in the forming pellets was refrigera tion ground to form powders having a size of approximately 50 mesh.

* 2 2,2'-methylene bis(4-methyl64ert.-butylphenol) was used.

(2) Extrusion Blending Condition (a) Extruder : Extruder used in the above mentioned Reference Examples (b) CylinderTemperature : 130through 1700C The test pieces were prepared from each composition and the tensile strength, the abrasion resistance and the compression set were determined. The results are shown in Table 33 below.

As will be clear from the results shown inTable33, the present compositions are superior, in tensile strength, abrasion resistance and compression set resistance, to the comparative compositions containing the unmodified block copolymer. In addition, the heat resistance of the present compositions includ ing the ionically crosslinked products of the modified block copolymer is improved.

Table 33 Example 27 Comparative Example 27 1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 Type of Block Modified Block Copolymer (M - 5b) Unmodified Block Copolymer (SB - 5) Copolymer *6 *7 Type of Thermoplastic PO PC NR PPE PPS PC PS PO PC PS NR PPE PPE Polystyrene Polymer* + + PBT PA Tensil Strength* 123 138 130 120 136 133 129 125 93 102 97 90 100 98 120 (kglcm2) Abrasion Resistance* (Picco Abrasion) 130 150 140 130 160 140 130 130 80 100 90 70 100 90 100 (Index) Compression Setu 1% 20 C 21 19 17 20 18 19 19 20 36 30 34 38 32 34 27 60 C 35 31 25 32 29 28 3235 58 53 47 51 54 51 63 20 C*5 13 11 10 11 12 11 11 13 - - - - - - 60 C*5 23 20 13 21 21 18 21 22 - - - - - - * 1 Please refer to Table 27.

*2 JISK6301 *3 ASTM 0 2228, the wearing amount of polystyrene in Comparative Example 27-7 was expressed as 100 and the other results were relatively determined as compared with the resuit of polystyrene. The higher the result in terms of index, the better is the wear resistance.

*4 JIS K 6301 (250/ocompression rate, 22 hours) * 5 The oniCally crosslinked product of M-5b, which was obtained by further blending 0.5 parts by weight of zinc stearate, based on 100 parts by weight of M-5b was used in lieu of M-5b in the composition.

Examples 28-1 to 28-8 100 parts by weight of the modified block copolymer M-1 1 a, the ionically crosslinked product M-1 1 c of the modified block copolymer M-1 1 a or the unmodified block copolymer SB-11 was completely mixed with 50 parts by weight of the thermoplastic polymer powders listed in Table 34,0.5 parts by weight of 2,6 - di -tert. - butyl - 4 - methyl - phenol and 0.5 parts by weight of tris - nonylphenyl phos phite in a Henschel mixer, and the mixture was pel letized by using the extruder used in the above mentioned Modified Block Copolymer Production Examples (the cylinder temperature of 150 to 2000C).

The pellets thus obtained were injection molded to form test pieces and the heat resistance and the surface peeling properties were examined.

The ratios of the tensile strength (at 70 C), of the present compositions to that of the composition con taining the unmodified block copolymer are shown in Table 34 below. As will be clear from the results shown in Table 34, the heat resistance of the present compositions is remarkably improved over that of the comparative composition.

Furthermore, the molded articles of the present compositions containing the modified block copolymer M-l 1a orthe ionically crosslinked product M-1 lc did not exhibit any surface peeling, whereas, in the molded articles of the comparative compositions containing the unmodified block copolymer SB-11 and PO, NR, the blend of PC and PET or the blend of PS and PA as the thermoplastic polymer, remarkable surface peeling was observed.

The ionically crosslinked product was obtained by adding a mixture solvent solution of toluene and methanol of sodium methylate to a 20%toluene solution of M-1 1 a at a room temperature in such an amount that the amount of sodium methylate was 0.2 parts by weight, based on 100 parts by weight of M-11a.

Table 34 Example 28 7 2 3 4 5 6 7 8 PC PS Type of Thermoplastic Polymer PO PC PS NR PPE PPS + + PBT PA Ratio of Tensile Strength at 70 C of the Present Composition containing M-i 1 a to the Comparative Composition containing SB-11 1.30 1.20 1.20 1.30 1.20 1.20 1.25 1.25 Ratio of Tensile Strength at 70"C of the Present Composition containing M-i to the Comparative Composition containing SB-11 1.45 1.35 1.35 1.45 1.35 1.35 1.40 1.40 (Remarks) The determination of tensile strength was carried out according to a method set forth in JIS K-6872 at 70 C.

Examples 29-1 to 29-4 and Comparative Examples 29- 1 to 29-4 The polymer compositions of these Examples and Comparative Examples were prepared by using the modified block copolymer M-12a (Examples) and the unmodified block copolymer SB-12 (Comparative Examples) according to the following formulation.

Blending Ratio Parts by Weight (a) Modified or Unmodified Block 100 Copolymer (b) Thermoplastic Polymer listed 60 in Table 35 below (c) Naphthenic Process Oil 90 (d) Light Calcium Carbonate 55 (e) Titanium Dioxide 10 (f) Stabilizer 0.5 The extrusion blending ofthe compositions and the tests of the physical properties thereof were carried out in a manner as described in Example 27. The results are shown in Table 35 below.

As will be clear from the results shown in Table 35.

The abrasion resistance and the compression set resistance at an elevated temperature of the present compositions are superiorto those of the compositions containing the unmodified block copolymer.

Table 35 Example 29 Comparative Example 29 Reference 1 2 3 4 1 2 3 4 Example Component A Modified Block Copolymer (M-12a) Unmodified Block Copolymer (SB-12) Component Bf' PC/ PSI GPPE/ PPS/ PC/ PSI GPPE/ PPS/ component C Poiy- Poly- Poly- Poly- Poly- Poly- Poly- Poly- Polystyrene (Blending Ratios styrene styrene styrene styrene styrene styrene styrene styrene by weight) (411) (411) (411) (411) (4/1) (4/1) (4/1) (4/1) Abrasion Resistance*2 140 130 150 130 100 90 100 90 100 (Picco Abrasion) (Index) Compression*2 23 19 24 20 33 30 38 35 45 set (%) at 60"C * 1 Please referto Table 27 *2 Please refer to Rema rks of Table 33 Examples 30-1 to 30-3 and Comparative Examples 30-1 to 30-3 The compositions containing the modified block copolymer M-7a or M-3a (Examples) on the unmodified block copolymer SB-7 or SB-3 as com ponent A and Surlyn A (i.e. ionomer) as component B, listed in Table 36 below, were prepared by mixing in a mixing roll at 180"C. The phisical properties of the compression-molded articles obtained from these compositions are shown in Table 36.

As will be clear from the results shown in Table 36, the tensile stressing of the present compositions containing the modified block copolymers is improved and the oil resistance of the block copolymer is remarkably improved by the addition of the ionomer.

Furthermore, it was confirmed by analysis with an IR spectrophotometer that the acid anhydride groups in the modified block copolymers were ionically crosslinked.

Table 36 Comparative Reference Example 30 Example 30 Example 7 2 3 1 2 3 Kind of Component A M-7a M-7a M-3a SB-7 SB-7 SB-3 M-3a SB-3 Amount (parts by weight) 80 70 90 80 70 90 100 100 Amount of Component B (lonomer) (parts by weight) 20 30 10 20 30 10 - Hardness (HS) (JIS) 90 92 86 88 90 85 84 21 300% Modulus (Kglcm2) 67 73 50 37 43 30 24 21 Tensile Strength (Kg/cm2) 143 150 170 83 76 100 163 143 Elongation at break (%) 720 630 700 850 760 740 1010 1050 Oil Resistance (%)* (Rate of Weight Increase) 21 15 33 64 59 68 56 - 74 * Immersed in an oil of JIS No.3 at a room temperature for 24 hours.

Examples 31-1 to 31hand Comparative Examples 31-1 to 31-4 The compositions, listed in Table 37 below, containing the modified block copolymer M-7a, M-lOa or the ionically crosslinked product M-7e of M-7a (Example) or the unmodified block copolymer SB-7 or SB-10 (Comparative Example) as component A, COPOLENE QD400 (ionomer available from Asahi Dow Co.) as component C were prepared by blending the components in a mixing roll at 1800C. The physical properties of the composition thus obtained were examined and the results are shown in Table 37 below.

As will be clear from the results in Table 37, the adhesion properties and the water resistance of the adhesion strength of the present compositions of Examples 31-1 to 314 to nylon (non-stretch sheet of nylon-6) are superior to those of the compositions of Comparative Examples 31-1 to 314. In addition, the tensile strength of the present compositions of Examples 31-1 to 314 are higherthan those of the corresponding comparative compositions of comparative Examples 31-1 to 314. Furthermore, in Example 31-5, the ionically crosslinked product M-7e of the modified block copolymer M-7a was used as component A in the composition. The ionically crosslinked product M-7ewas prepared by ionically crosslinking the modified block copolymer M-7a with sodium methylate (CH3ONa/acid anhydride group = 0.4).The tensile strength of the composition of Example 31-5 containing the ionically crosslinked product M-7e is improved over the composition containing the modified block copolymer M-7a and the water resistance of the adhesion strength thereof is also good.

Table 37 Example 31 Comparative Example Reference Example Item 1 2 3 4 1 2 3 4 Example 31-5 COMPOSITION Type of Component A M-7a M-10a M-7a M-7a SB-7 SB-10 SB-7 SB-7 - M-7e Amount of Component A (parts by weight) 20 30 40 30 20 30 40 30 - 20 Amount of lonomer (component B) (partsbyweight) 80 70 60 50 80 70 60 50 100 80 Amount of Low-dencity Polyethylene (Component C) (parts by weight) - - - 20 - - - 20 PHYSICAL PROPERTY Tensile Strength (Kglcma) 256 230 206 215 232 233 191 198 323 271 Elongation at break (%) 380 310 370 330 390 290 360 330 440 370 Adhesion Peel Before 3.5 3.3 5.3 3.1 1.1 0.9 1.0 0.5 1.2 3.4 Strength to immersion Nylon After 2.8 3.1 4.4 2.7 0.2 0.1 0.1 0.1 0.2 3.0 (Kgl25 mm)* immersion*2 * 1 According to a method of JIS-K-6854 * 2 The determination was made after the test pieces were immersed in water at 609C for 24 hours.

Example 32 and Comparative Example 32 A polymer composition containing 100 parts by weight of the modified block copolymer M-7b as component A and 15 parts by weight of polyethylene glycol nonylphenyl ether, as component B, which was an oligomer containing hydroxyl group and which was available from Nippon Oil and Fat Co, as NON ION NS-220 (polymerization degree of polyethylene glycol = 20 and number-average molecular weight = 1100)was prepared as follows.

100 parts by weight of the component A were fed to a Brabender Plastograph at a temperature of 170"C.

After the component A was melted in the Brabender Plastograph, 15 parts of the component B were fed to the Brabender Plastograph in small portions over 20 minutes and were mixed for further 10 minutes.

The resultant composition (Example 32) was clear and it was observed by IR spectrophotometer analysis that the absorption band of the dicarboxylic anhydride group of the modified block copolymer disappeared at approximately 1785 cm-' and a new absorption band appeared at approximately 1730 cm-1.The appearance of the absorption band at approximately 1730 cm-1 corresponding to the ester group shows that the acid anhydride groups of the component A were reacted with the terminal hydroxyl groups to form graft copolymers in the composition. It was also observed by a solvent extraction that approximately 10% of the component B remained in the composition without causing the reaction.

As a comparative example, although 100 parts by weight of the unmodified block copolymer SB-7 was blended with 15 parts by weight of the component B employed in Example 32 in manner as described in Example 32, only a small'amount of the component B could be fed to the Brabender Plastograph, since the compatibility or miscibility of the components A and B was not good. The resultant composition was not clean The physical properties of the compositions of Example 32 and Comparative Example 32, as well as the unmodified blook copolymer SB-7, are shown in Table 38 below.As will be clear from the results in Table 38, the oil resistance of the composition of Example 32 was improved, compared to the unmodified block copolymer SB-7, while other properties, including the mechanical properties, such as the tensile strength and the hardness, and the rub beriness and the flowability of the present composition were substantially maintained at the levels of those of the unmodified block copolymer SB-7. In addition, although the blending ratio of the component B was small (i.e. the ratio of component B/component A = 7/100), the properties, such as the tensile strength, of the composition of the Comparative Example 32 were remarkably decreased, compared with the present composition and the unmodified block copolymer.

Table 38 Comparative Reference Example 32 Example 32 Example M7b + SB-7 + SB-7 Type of Composition or Polymer OH Oligomer OH Oligomer Hardness (JIS) 79 77 80 300% Modulus (Kg/cm2) 20 14 21 Tensile Strength (Kglcm2) 138 80 143 Elongation at break (%) 1100 800 1050 Resilience (Dunlop) (%) 47 - 45 Melt Index (gllOmin) 8.0 22.3 11.0 Oil Resistance*1 (Weight Increase %) 46 - 74 * 1 Immersed in an oil of JIS No.3 at 25"C for 24 hours.

Examples 33-1 to 33-4 and Comparative Examples 33-1 to 33-4 Various compositions containing the modified block copolymer M-7b (Example) or the unmodified block copolymer SB-7 (Comparative Example) as component A and the various polar oligomers listed in Table 39 below as component B were prepared in a blending ratio listed in Table 39 in a manner as described in the preceding Example. The physical properties of these compositions are shown in Table 39 below.

As will be clear from the results shown in Table 39, the properties of the present compositions of Examples 33-1 to 334 are improved over those of the corresponding comparative compositions of Comparative Examples 33-1 to 334 and the use of the polar oligomers are effective in the improvement of the polar oligomers.

Table 39 Compara- Compara- Compara- Compara tive tive tive tive Example Example Example Example Example Example Example Example 33-1 33-1 33-2 33-2 33-3 33-3 33-4 334 COMPOSITION Amount of Modified Block Copolymer M-7b 100 - 100 - 100 - 100 (parts by weight) Amount of Unmodified Block Copolymer SB-7 - 100 - 100 - 100 - 100 (parts by weight) Amino-terminated Epoxyidized Styrene-MMA-GMA Isocyanated Type of Liquid NBR Polybutadiene Copolymer Polybutadiene PolarOligmer (Ube Industries Ltd., (Adeka Argus Co., (GMA: 3% by weight. (NISSO-PB-TP-1000, (Component B) HYCAR ATBN BF-1000, MW = 3500) MW = 1000) MW = 5000) NCO = 3.8%) Addition Amount 15 40 20 10 (parts by weight) PHYSICAL PROPERTY Tensile Strength 141 80 130 100 175 120 155 108 (parts by weight) Oil Resistance 51 68 55 71 43 66 53 76 (increased weight %)

Claims (46)

1. A thermoplastic polymer composition comprising: (a) 1 through 99 parts by weight of a component A consisting essentially of at least one member selected from the group consisting of modified block copolymers and the ionically crosslinked products of at least one said modified block copolymerwith at least one univalent, bivalent or trivalent metal ion, said modified blockcopolymercomprising a block copolymer of at least one aromatic vinyl compound and at least one conjugated diene compound onto which at least one molecular unit containing at least one dicarboxylic acid group or the derivative thereof is grafted; and (b) 99 through 1 parts by weight of a component B consisting essentially of at least one thermoplastic polymer having polar groups.

2. A composition as claimed in claim 1, wherein said thermoplastic polymer containing polar groups is selected from the group consisting of polyamides, thermoplastic polyesters, polyurethanes, vinylal cohol polymers, polyacrylates, polymethacrylates, chlorinated hydrocarbon polymers, polyox ymethylene polymers, polycarbonates, polyarylene ethers, polyarylene sulfides, unsaturated nitrile polymers, polysulfones, ionomers and oligomers other than the above-mentioned polymers, said oligomers having at least one polar group which is reactive to the dicarboxylic acid or the derivative thereof and having a number-average molecular weight of 100 through 10,000.

3. A composition as claimed in claim 2, wherein the content of the molecular unit containing the dicarboxylic acid group or the derivative thereof in the modified block copolymer of the component A is 0.05 through 20 parts by weight, based on 100 parts by weight of the modified block copolymer.

4. A composition as claimed in claim 3, wherein the derivative of the dicarboxylic acid group of the component A is a dicarboxylic anhydride group.

5. A composition as claimed in claim 2, wherein the content of the aromatic vinyl compound in the block copolymer of the aromatic vinyl compound and the conjugated diene compound of the compo nent A is 5 through 70% by weight, based on the weight of the block copolymer.

6. A composition as claimed in claim 2, wherein the content of the aromatic vinyl compound in the block copolymer of the aromatic vinyl compound and the conjugated diene compound of the compo nent A is more than 70% by weight through 95% by weight, based on the weight of the block copolymer.

7. A composition as claimed in claim 2, wherein the ionically crosslinked modified block copolymer is derived from the reaction of the modified block copolymer with at least one metallic compound selected from the group consisting of the com pounds of univalent, bivalent and trivalent metal ions.

8. A composition as claimed in claim 7, wherein the molar ratio of the metal component of the metallic compound to the dicarboxylic acid or the derivative thereof contained in the modified block copolymer of the component A is 0.1 through 3.0.

9. A composition as claimed in claim 2, wherein the modified block copolymer of the component A is derived from the reaction of the block copolymer of the aromatic vinyl compound and the conjugated diene compound with an unsaturated dicarboxylic acid orthe derivative thereof.

10. A composition as claimed in claim 9, wherein the modified block copolymer of the component A is derived from the reaction of the block copolymer with an unsaturated dicarboxylic acid or the deriva tive thereof in a molten state in the absence of a free-radical initiator.

11. Acomposition as claimed in claim 10, wherein the unsaturated dicarboxylic acid or the derivative thereof is at least one member selected from the group consisting of maleic acid, fumaric acid and maleic anhydride.

12. A composition as claimed in claim 2, wherein the polyamide of the component B is at least one member selected from the group consisting of ring opening polymers of cyclic lactums, polycondensates of a-amino carbonic acids, polycondensates of dicarboxylic acids and diamines and copolymers of these monomers.

13. Acomposition as claimed in claim 12, wherein the polyamide of the component B is selected from the group consisting of nylon-6, nylon-6,6 and copolymers of nylon-6 and nylon-6,6.

14. Acomposition as claimed in claim 2, wherein the thermoplastic polyester of the component B is at least one member selected from the group consisting of polycondensates of glycols and dicarboxylic acids and polylactones.

15. Acomposition as claimed in claim 14, wherein the thermoplastic polyester is selected from poly(ethylene terephthalate) and poly(butyrene terephthalate).

16. Acomposition as claimed in claim 14, wherein the thermoplastic polyester is a thermoplastic copolyester consisting essentially of at least one alkylene glycol having 2to 10 carbon atoms, as a glycol component, and at least two dicarboxylic acids selected from (i)terephthalic acid, (ii) isophthalic acid and (iii) aliphatic dicarboxylic acids having 4 to 20 carbon atoms, as a dicarboxylic acid component.

17. A composition as claimed in claim 2, wherein the polyurethane of the component B is at least one thermoplastic elastomer.

18. Acomposition as claimed in claim 17, wherein the polyurethane is a complete thermoplastic type polyurethane derived from a diisocyanate compound and a dihydroxy compound, the molar ratio (NCO/OH ) of the diisocyanate compound and the dihydroxy compound being more than 0.95 through 1.

19. Acomposition as claimed in claim 17, wherein the polyurethane is an incomplete thermoplastic type polyurethane derived from a diisocyanate compound and a dihydroxy compound, the molar ratio (NCO/OH) of the diisocyanate compound and the dihydroxy compound being more than 1 and less than 1.1.

20. A composition as claimed in claim 2, wherein the polyvinyl alcohols of the component B are saponified ethylene-vinyl acetate copolymers.

21. A composition as claimed in claim 20, wherein the vinyl acetate content of the ethylenevinyl acetate copolymers is 0.5 through 80 mol %.

22. Acomposition as claimed in claim 21, wherein the saponification degree of the vinyl acetate is 10through 1û0 mol /O.

23. A composition as claimed in claim 2, wherein the polyacrylates or polymethacrylates of the component B are those which contain more than 50% by weight of alkyl esters of acrylic or methacrylic acid having an alkyl group of 1 through 12 carbon atoms.

24. A composition as claimed in claim 23, wherein the polymethacrylate is selected from the group consisting of poly(methyl methacrylate) and copolymers of methyl methacrylate and other comonomers copolymerizable therewith.

25. A composition as claimed in claim 2, wherein the chlorinated hydrocarbon polymer of the component B is at least one member selected from the group consisting of polyvinyl chloride and copolymers of vinyl chloride and other comonomers copolymerizable therewith.

26. A composition as claimed in claim 2, wherein the chlorinated hydrocarbon polymers are chlorinated polyolefins.

27. Acomposition as claimed in claim 2, wherein the polyoxymethylene polymers of the component B are homopolymers of formaldehyde ortrioxane and copolyners containing, as a main constituent, formaldehyde ortrioxane.

28. A composition as claimed in claim 2, wherein the polycarbonates of the component B are aromatic polycarbonates having a structural unit,

wherein Ar' is a phenylene group or a phenylene group substituted with an alkyl group, a substituted alkyl group, an alkoxy group, a halogen atom or a nitro group, and A is an alkylene group, an alkylidene group, a cycloalkylene group, a cycloalkylidene group, sulfur, oxygen, sulfoxide or sulfone group.

29. A composition as claimed in claim 2, wherein the polyarylene ethers of the component B are polyphenylene ethers having a structural unit,

wherein R1 and R2 are, independently, alkyl groups having 1 to 4 carbon atoms, substituted alkyl groups or halogen atoms.

30. A composition as claimed in claim 2, wherein the polyarylene ethers of the component B are grafted polyphenylene ethers derived from the graft polymerization of aromatic vinyl compounds onto polyphenylene ethers having a structural unit,

wherein R' and R2 are, independently, alkyl groups having 1 to 4 carbon atoms, substituted alkyl groups or halogen atoms.

31. A composition as claimed in claim 2, wherein the polyarylene sulfides of the component B are polyarylene sulfides having a structural unit, tAr2-S.p wherein Ar2 is a phenylene group or a phenylene group substituted with at least one group selected from alkyl groups and substituted alkyl groups.

32. A composition as claimed in claim 2, wherein the unsaturated nitrile polymers are homopolymers of a,ss-unsaturated mononitriles or copolymers of a,P-unsaturated mononitriles and other monomers copolymerizable therewith.

33. A composition as claimed in claim 2, wherein the polysulfones are aromatic polysulfones having a structural unit, t Ar3 - B - Ar3 - S02 = or < Ar3 - SOlt wherein Ar3 is a phenylene group or a phenylene group substituted with at least one group selected from alkyl groups and substituted alkyl groups, B is sulfur, oxygen or a residual group of aromatic diol.

34. Acomposition as claimed in claim 2, wherein the ionomers of the component B are ionically crosslinked products of base copolymers of a,ss - unsaturated carboxylic acids and other monomers copolymerizable therewith in which basic copolymers are ionically crosslinked with at least one metallic ion selected from the group consisting of univalent, bivalent and trivalent metallic ions.

35. Acomposition as claimed in claim 34, wherein the base copolymers of the monomers are olefin - a,ss - unsaturated monocarboxylic acid copolymers.

36. Acomposition as claimed in claim 35, wherein the olefin - a,p - unsaturated monocarboxylic acid copolymer is ethylene-acrylic acid copolymer or ethylene-methacrylic acid copolymer.

37. A composition as claimed in claim 34, wherein the content of the a,p-unsaturated carboxylic acid in the base copolymer is 0.2 through 25 mol %

38. A composition as claimed in claim 2, wherein the polar group of the oligomer of the component B is at least one selected from the group consisting of an amino group, a hydroxyl group, an epoxy group and an isocyanate group.

39. Acomposition as claimed in claim 2 or 38, wherein the composition contains the reaction product of the components A and B.

40. A composition as claimed in claim 39, wherein the reaction product of the components A and B is a graft copolymer comprising the component A, as a backbone component, and the component B, as a superstrate component, grafted onto the component A.

41. A composition as claimed in claim 2, wherein the composition comprises 1% by weight through less than 50% by weight of the component A and more than 50% by weight through 99% by weight of the component B.

42. A composition as claimed in claim 2, wherein the composition comprises 50 through 99% by weight of the component A and 1 through 50% by weight of the component B.

43. A composition as claimed in claim 2, wherein the composition further contains a component C consisting essentially of at least one member selected from the group consisting of styrene polymers and polyolefins, the content of the component C being 1 through 100 parts by weight based on 100 parts of the total amount of the components A and B.

44. A composition as claimed in claim 2, wherein the composition is an adhesive composition.

45. A composition as claimed in claim 1 substantially as described in any one of the Examples.

46. A thermoplastic composition corn prising: (a) 1 to 990/0 by weight of a component A which is, or consists essentially of, at least one modified block copolymer or the onically crosslinked product of at least one said modified block copolymer with at least one univalent, bivalent or trivalent metal ion, said modified block copolymer comprising a block copolymer of at least one aromatic vinyl or vinylidene compound and at least one conjugated diene compound onto which at least one molecular unit containing at least one dicarboxylic acid group or a derivative thereof is grafted; ; (b) 99to 1% by weight of a component B which is, or consists essentially of, at least one thermoplastic polymer having polar groups, the individual % by weight of components A and B being based on the combined weight of components A and B; and optionally (c) 0 to 100% by weight of component C which is, or consists essentially of, a styrene polymer or an olefin polymer; the % by weight of component C being based on the combined weight of components A and B.