JPH0356259B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF INDUSTRIAL APPLICATION This invention relates to new and improved compositions of thermoplastic polymers. More specifically, the present invention provides a thermoplastic polymer composition comprising a thermoplastic polyurethane and a modified block copolymer to which a dicarboxylic acid group or a derivative thereof has been added, and which has improved compatibility between the two and has excellent mechanical properties. It is about things. (Prior art) Conventionally, in applications such as fibers, films, sheets, molded products, etc. made of polymeric substances, there have been cases where using a single polymeric substance is insufficient for the purpose of the product. Many attempts have been made to provide sufficient strength, improve processability, and reduce the cost of products by creating compositions or laminates consisting of multiple components. However, when mixing polymeric substances to form a composition, there are not many combinations of different types of substances that have good compatibility. Mixed compositions of different types of polymeric substances with poor compatibility may suffer from heterogeneity due to poor miscibility.
In some cases, it was difficult to achieve modification by mixing due to separation between different phases. A styrene-butadiene block copolymer, a styrene-isoprene block copolymer, or a partially hydrogenated styrene-butadiene block copolymer, or a styrene-isoprene block copolymer, or a partially hydrogenated styrene-butadiene block copolymer, or a styrene-isoprene block copolymer, or a styrene-isoprene block copolymer may be used as a component for mixing polymeric substances to obtain a composition with excellent properties. It is well known that added block copolymers are used (for example, JP-A-50-119055, JP-A-50-148457).
Publication No. 75651, Japanese Patent Publication No. 1983-75651, Japanese Patent Application Publication No. 1983-
117940, Japanese Unexamined Patent Publication No. 150457/1983). (Problems to be Solved by the Invention) However, such block copolymers are limited to polar polymers such as polyamides, polyesters,
Since the compatibility with polyurethane and the like is extremely poor, it has not been possible to form a useful mixed composition. The present inventors have conducted intensive studies to obtain a thermoplastic polymer composition containing a polar polymer and a block copolymer, which has improved compatibility between the two and has excellent mechanical properties. Reached. (Means for Solving Problems) That is, the present invention comprises: (a) 2 to 98 parts by weight of thermoplastic polyurethane; (b) a vinyl aromatic compound polymer block A and an olefin compound polymer block having a degree of unsaturation not exceeding 20%; A block copolymer consisting of B and having a vinyl aromatic compound content of 10 to 90% by weight, and a molecular unit containing a dicarboxylic acid group or a derivative group thereof per 100 parts by weight of the block copolymer. The present invention relates to a thermoplastic polymer composition comprising 98 to 2 parts by weight of a modified block copolymer bound to 20 parts by weight. The present invention will be described in detail below. The modified block copolymer, which is one component of the present invention, is synthesized as follows. In other words, the degree of unsaturation in the conjugated diene portion of a block copolymer composed of a vinyl aromatic compound polymer block and a polymer block mainly composed of a conjugated diene compound does not exceed 20%. hydrogenated to
A block copolymer consisting of a vinyl aromatic compound polymer block A and an olefin compound polymer block B having a degree of unsaturation not exceeding 20% is then modified by an addition reaction with an unsaturated dicarboxylic acid or a derivative thereof. A block copolymer is obtained. The above block copolymer before hydrogenation contains at least one vinyl aromatic compound polymer block,
Preferably, it contains two or more polymer blocks, and at least one polymer block mainly composed of a conjugated diene compound. Here, the polymer block mainly composed of a conjugated diene is a polymer block having a composition in which the weight ratio of the vinyl aromatic compound and the conjugated diene compound is in the range of 0/100 to 50/50, preferably 0/100 to 40/60. It is a coalescing block, and the distribution of vinyl aromatic compounds in this block can be random, tapered (increasing or decreasing monomer content along the molecular chain),
It may be partially block-shaped or any combination thereof. In addition, in the block copolymer before hydrogenation in the present invention, a vinyl aromatic compound and a conjugated diene compound are contained in the transition region between the vinyl aromatic compound polymer block and the polymer block mainly composed of a conjugated diene compound. Although a copolymer portion may be present, such a polymer portion shall be included in the polymer block mainly composed of the conjugated diene compound. In the above block copolymer, the weight ratio of the vinyl aromatic compound content to the conjugated diene compound content is in the range of 10/90 to 90/10, and 20/80 to
A range of 85/15 is preferred. As the vinyl aromatic compound constituting the block copolymer before hydrogenation, one or more compounds are selected from styrene, α-methylstyrene, vinyltoluene, etc. Among them, styrene is particularly preferred. The conjugated diene compound may be one or more selected from butadiene, isoprene, 1,3-pentadiene, etc., and butadiene and/or isoprene are particularly preferred.
The above block copolymer has a number average molecular weight of 20,000.
500,000, and the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably in the range of 1.05 to 10. In addition, the molecular structure of the block copolymer is
It may be linear, branched, radial, or a combination thereof. Further, when butadiene is used as the conjugated diene compound in the block copolymer, the amount of 1,2 bonds in the microstructure of the butadiene portion is preferably in the range of 10 to 80%. When it is necessary for the modified block copolymer to have rubber elasticity, the amount of 1,2 bonds is particularly preferably in the range of 35 to 55%. When the above-mentioned block copolymer contains two or more blocks mainly composed of vinyl aromatic compound blocks or conjugated diene compounds, each block may have the same structure, and the monomer component content and their Each structure, such as the distribution in the molecular chain, the molecular weight of the block, and the microstructure, may be different. The above block copolymers usually contain benzene,
It is obtained by an anionic living polymerization method using an organic lithium compound such as butyllithium as a catalyst and a vinyl aromatic compound and a conjugated diene compound as monomers in an inert hydrocarbon solvent such as toluene, hexane, or cyclohexane. Furthermore, by reacting the block copolymer having a lithium active terminal obtained by the above method with a multifunctional coupling agent such as carbon tetrachloride, silicon tetrachloride, etc., a branched or radial block copolymer can be produced. It is also possible to do this. In the present invention, any polymer obtained by any polymerization method can be used as long as it falls within the above range. Furthermore, the block copolymers can be used not only as a single type but also as a mixture of two or more types. By hydrogenating the above block copolymer by a known method, for example, the method described in Japanese Patent Publication No. 42-8704, a portion not exceeding 20% of the aromatic double bonds of the vinyl aromatic compound block A can be obtained. and a partially hydrogenated block copolymer in which at least 80% of the aliphatic double bonds of the conjugated diene compound block B are hydrogenated is synthesized. The degree of unsaturation of block B in the present invention refers to the proportion of carbon-carbon double bonds contained in block B, and this refers to the proportion of carbon-carbon double bonds contained in block B, and this is determined by It is measured by instrumental analysis such as, chemical analysis such as iodometry. The partially hydrogenated block copolymer is then modified by addition reaction with an unsaturated dicarboxylic acid or derivative thereof. Examples of unsaturated dicarboxylic acids or derivatives thereof to be added to the partially hydrogenated block copolymer include maleic acid, maleic anhydride, fumaric acid, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid and its anhydride. substance, endo-cis-bicyclo[2,2,1]-5
Examples include -heptene-2,3-dicarboxylic acid, its anhydride, and maleimide, and among these, maleic anhydride is particularly preferred. The above-mentioned modified block copolymer, which is a component of the composition of the present invention, can be prepared by adding an unsaturated dicarboxylic acid or a derivative thereof to a partially hydrogenated block copolymer in a solution or melt state, using a radical initiator, or It can be obtained by adding it without using it. The method of producing these modified block copolymers is not particularly limited in the present invention, but the modified block copolymers obtained may contain undesirable components such as gels, or have a significantly increased melt viscosity and may be difficult to process. A manufacturing method that deteriorates properties is not preferred. A preferred method is, for example, a method in which an unmodified block copolymer is reacted with an unsaturated dicarboxylic acid or a derivative thereof in the presence of a radical initiator in an extruder. The amount of unsaturated dicarboxylic acid or its derivative added to the block copolymer is 100% of the block copolymer.
The amount is 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight. If the amount added is 0.05 parts by weight or less, when made into a composition, there is only a slight improvement compared to an unmodified conjugated diene polymer, and even if the amount added exceeds 20 parts by weight, there is no improvement compared to less than that. There is almost no increase in the effect of The unsaturated dicarboxylic acids or derivatives thereof used in the present invention can be used not only alone but also as a mixture of two or more. Next, the thermoplastic polyurethane, which is another component of the composition of the present invention, will be described. The thermoplastic polyurethane used in the present invention is
Depending on the synthesis conditions, it is classified into fully thermoplastic type and incompletely thermoplastic type, and these are determined by the molar ratio of the raw material bifunctional polyol, the OH group of the glycol, and the NCO group of the diisocyanate, approximately 0.95 <
Those synthesized with NCO/OH≦1 are completely thermoplastic, and those synthesized with approximately 1<NCO/OH<1.1 are incompletely plastic. As the above-mentioned thermoplastic polyurethane, for example, there is one in which a block of polyol (polyester or polyether) and diisocyanate is used as a soft segment, and a block of diisocyanate and glycol is used as a hard segment. Examples of the polyester diol used as the raw material include poly(1,4-butylene adipate), poly(1,6-hexane adipate), polycaprolactone, etc., and examples of the polyether diol include polyethylene glycol, polypropylene glycol, and polypropylene glycol. These include oxytetramethylene glycol. Furthermore, as glycols, ethylene glycol, 1,4-butanediol,
Examples of diisocyanates include aromatic, alicyclic, and aliphatic diisocyanates, such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone. Diisocyanates, etc. In addition to the thermoplastic polyurethane elastomers shown above, polyurethane polymers used for adhesives, foams, paints, etc. can also be used in a sufficient amount with the modified block copolymer, component (b) of the present invention. Those that are compatible can be used in the compositions of the present invention. As a thermoplastic polyurethane, the molecular weight is
5,000 to 500,000, preferably 10,000 to 300,000, can be used satisfactorily from the viewpoint of mechanical properties. Next, the characteristics of the thermoplastic polymer composition of the present invention will be described. The composition of the present invention can be obtained by using a modified block copolymer modified with an unsaturated dicarboxylic acid or a derivative thereof as a block copolymer component, or by using an unmodified block copolymer. It has the characteristics of a composition that has significantly improved compatibility with thermoplastic polyurethane compared to that of thermoplastic polyurethane. In other words, a composition of an unmodified block copolymer and a thermoplastic polyurethane has poor dispersibility due to poor compatibility between the two, and if the refractive index of the two is different, it becomes opaque. The composition of the modified block copolymer and thermoplastic polyurethane of the invention has good dispersibility and improved transparency. The mechanical properties of the composition of the present invention vary widely, from rubber-like or leather-like to resin-like, depending on the composition ratio of the modified block copolymer and thermoplastic polyurethane. For example, when the composition ratio is high in the modified block copolymer, the composition of the present invention has higher hardness, tensile strength, oil resistance, and heat resistance than conventional styrene-butadiene or styrene-olefin block copolymers. etc., resulting in an excellent rubber-like or leather-like polymer composition. As the thermoplastic polyurethane component increases, the composition changes into a tough resin-like state, and at a composition ratio with a large thermoplastic polyurethane component,
Shows significant improvements in impact resistance, adhesion, bending resistance, etc. Furthermore, the modified block copolymer used in the present invention is
Since the degree of unsaturation is limited to no more than 20%, it exhibits superior weather resistance compared to styrene-diene block copolymers with a high degree of unsaturation. In the thermoplastic polymer composition of the present invention, the composition ranges from 98 to 2 parts by weight of a modified block copolymer modified with an unsaturated dicarboxylic acid or a derivative thereof, and from 2 to 98 parts by weight of a thermoplastic polyurethane. Preferably, the amount is 5 to 95 parts by weight of the modified block copolymer. Outside the above range, no significant change in properties is observed compared to each polymer itself. Furthermore, a range of 98 to 50 parts by weight of the modified block copolymer and 2 to 50 parts by weight of the thermoplastic polyurethane is useful as a modified composition of the modified block copolymer; More than 50 parts by weight, more than 50 parts by weight of thermoplastic polyurethane
In a range of 98 parts by weight or less, it is useful for modifying thermoplastic polyurethane, particularly for improving impact resistance and adhesion. The scope of the present invention includes a graft copolymer composed of a modified block copolymer and a thermoplastic polyurethane, which is produced by a reaction between a reactive group contained in the modified block copolymer and a reactive group contained in the thermoplastic polyurethane. It also includes cases where the polymer is included as part of the composition of the invention. The composition of the present invention can be prepared using a conventional apparatus for mixing polymeric substances depending on the composition ratio of each component. Examples of the mixing device include an extruder, a mixing roll, a Banbury mixer, a kneader, etc. In the present invention, a melt mixing method using an extruder is particularly preferred. In addition, the thermoplastic polymer composition of the present invention may contain reinforcing agents or fillers such as calcium carbonate, silica, carbon black, glass fiber, clay, process oil, polyethylene glycol, etc., to the extent that its properties are not impaired. It is also possible to add plasticizers such as phthalate esters. In addition, other additives such as heat stabilizers, antioxidants, ultraviolet absorbers, colorants, pigments, etc. may be added, and a foaming agent may be further added to the composition of the present invention to form a foam. is also possible. (Effects of the Invention) The thermoplastic polymer composition of the present invention has excellent processability and can be molded by various conventional molding methods such as extrusion molding, injection molding, calendar molding, etc. It is a useful substance with excellent mechanical properties and a wide range of applications in various fields such as sheets, molded products, and rubber applications. (Example) Examples will be shown below, but these are intended to explain the present invention more specifically, and are not intended to limit the scope of the present invention. Examples 1 to 3 and Comparative Examples 1 to 6 (1) Preparation of hydrogenated block copolymer N-butyl lithium was used as a polymerization catalyst, and butadiene and tetrahydrofuran were used as a vinyl content regulator in n-hexane or cyclohexane solvent. The block copolymers shown in the table were synthesized by anionic block copolymerization with styrene.

[Table] The vinyl content of the butadiene moiety was measured by the Hampton method. Next, the block copolymers shown in Table 1 were mixed with n
- In a mixed solvent of hexane and cyclohexane, using cobalt naphthenate and triethylaluminum as catalysts, hydrogen pressure 7 Kg/cm ² and temperature 50°C.
After hydrogenation for 5 hours, about 90% of the double bonds in the butadiene block were hydrogenated, and the benzene rings in the styrene block remained almost unhydrogenated, resulting in a selectively hydrogenated block copolymer. Synthesized the union. The metal remaining on the catalyst was removed by washing with an aqueous hydrochloric acid solution and methanol. (2) Preparation of hydrogenated/modified block copolymer Hydrogenated block copolymer 100 synthesized in (1) above
2.5 parts by weight of maleic anhydride,
After uniformly mixing 0.1 part by weight of Perhexa 25B (manufactured by NOF Corporation), a screw type extruder (single screw, screw diameter 20 mm, L/D
=24, full flight type screw),
The maleation reaction was carried out at a cylinder temperature of 250°C. From the obtained modified block copolymer, unreacted maleic anhydride was removed under reduced pressure and 2,6-di-tert-butyl-4 was added as a stabilizer.
- Methylphenol was added in an amount of 0.5 parts by weight per 100 parts by weight of the polymer. When this modified block copolymer was analyzed, the results shown in Table 2-1 were obtained.

[Table] The amount of maleic anhydride added was measured using sodium methylate. (3) Preparation of non-hydrogenated/modified block copolymer To 100 parts by weight of the block copolymer shown in Table 1, 10.0 parts by weight of maleic anhydride and 0.3 parts by weight of 2,6-di-tertiary Butyl-4
- Add methylphenol (BHT) and 0.2 parts by weight of phenothiazine as a stabilizer, mix uniformly, and then use a screw extruder (single screw, screw diameter 20 mm, L/D = 24, full flight type) under a nitrogen atmosphere. The maleating reaction was carried out at a cylinder temperature of 210°C. Unreacted maleic anhydride was removed under reduced pressure from the obtained non-hydrogenated modified block copolymer at 120°C.
When this non-hydrogenated modified block copolymer was analyzed, the results shown in Table 2-2 were obtained.

[Table] (4) Preparation of composition Paraprene P- as thermoplastic polyurethane
Using 22SM (manufactured by Nippon Polyurethane), hydrogenated and
A composition of modified block copolymer M(), hydrogenated non-modified block copolymer () and non-hydrogenated modified block copolymer M()-C was heated at 180°C using a Brabender plastograph. It was obtained by mixing. These compositions are combined with polyvinyl chloride sheets and high-density polyethylene sheets.
Pressure bonding was performed at 180°C, and the adhesive peel strength was measured.
The results are shown in Table 3. As is clear from the results in Table 3, the composition of the present invention has excellent adhesion to polyvinyl chloride and polyethylene sheets over a wide composition range. On the other hand, the adhesion of the composition of the comparative example is inferior to the results of the corresponding example.

【table】

Claims (1)

[Scope of Claims] 1 (a) Thermoplastic polyurethane 2 to 98 parts by weight (b) Consisting of a vinyl aromatic compound polymer block A and an olefin compound polymer block B having a degree of unsaturation not exceeding 20%, Modification in which 0.05 to 20 parts by weight of a molecular unit containing a dicarboxylic acid group or its derivative group is bonded to a block copolymer having an aromatic compound content of 10 to 90 parts by weight per 100 parts by weight of the block copolymer. A thermoplastic polymer composition comprising 98 to 2 parts by weight of a block copolymer.