JPS63254119A - Modified block copolymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a modified block copolymer c'- to which a dicarboxylic acid group or derivative thereof is added.

The modified block copolymer according to the present invention has improved compatibility with a polar thermoplastic superpolymer having a polar functional group, and by utilizing the present invention, a thermoplastic polymer composition with excellent mechanical properties can be obtained. things are provided.

(Prior art) Traditionally, fibers, films,
Uses of sheets, molded products, etc. (1) In cases where using a single polymeric substance is insufficient for the purpose of the product, it may be necessary to use a composition consisting of multiple components or a laminate. Many attempts have been made to increase the strength of the product, improve processability, and reduce the cost of the product. In this case, there are not many combinations of different types with good [1fd properties].

In addition, in a mixed composition of different types of molecular substances with poor compatibility, it may be difficult to realize page breaks due to poor mixability, resulting in non-uniformity, and confusion between different types of substances. Ta.

As one component for obtaining Saga's excellent composition by mixing polymeric substances, a 1F styrene-butadiene block copolymer, a styrene-isoprene block copolymer, or a portion of the above block copolymer is used. It is well known that hydrogenated block copolymers are used (for example, in Japanese Patent Application Laid-Open No. 2003-110001,
Unexamined Japanese Patent Publication Shojθ-/G♂Guj7 Publication, Unexamined Japanese Patent Publication Shojθ-'7!
;1,3/ publication, JP-A-3.2-//7 tag θ publication, JP-A-3.2-7! fθ gu j7 publication).

(Problems to be Solved by the Invention) However, such block copolymers have extremely poor compatibility with polar polymers such as polyamides, polyesters, polyurethanes, etc., and therefore cannot be used as a useful mixed composition. It didn't come out.

The present inventors can provide a thermal II plastic aggregate composition with improved compatibility with a polar polymer and excellent mechanical properties.
We conducted intensive studies to obtain a modified block copolymer.

(Means for solving the problem) As a result, a new modified block copolymer is created in which a molecular unit containing a dicarboxylic acid group or its derivative group is bonded to a specific block copolymer, and this is utilized. The inventors have discovered that the object can be achieved by doing so, and have arrived at the present invention.

That is, the present invention provides at least two vinyl aromatic compound polymer blocks A
and at least seven olefin compound polymer blocks B whose degree of unsaturation does not exceed λθ and force X, and the content of vinyl aromatic compounds is 7θ~? θ weight, a block copolymer having a number average molecular weight of 20,000 to 500,000, and a molecular unit containing a dicarbonate group or its derivative group being 0.05 per part of the block copolymer/θθby.
A modified block copolymer having ~20M fm moieties bonded is provided.

Hereinafter, the present invention will be described in detail.

The modified block copolymer of the present invention is, for example, synthesized as follows (two-C synthesis; that is, it is composed of a vinyl aromatic compound polymer block and a polymer block mainly composed of a conjugated diene compound). selectively swims to the extent that the degree of unsaturation of the conjugated diene moiety of the block copolymer does not exceed the λθ coefficient, and the vinyl aromatic compound polymer block A,
A block copolymer consisting of an olefin compound polymer block B having an unsaturation degree not exceeding the λθ coefficient is obtained, and then a modified block copolymer is obtained by an addition reaction with an unsaturated dicarboxylic acid or a derivative thereof.

The above block copolymer before hydrogenation contains at least two vinyl aromatic compound polymer blocks and at least seven polymer blocks mainly composed of a conjugated diene compound. Here, in the polymer block mainly composed of a conjugated diene, the weighting ratio of the vinyl aromatic compound and the conjugated diene compound is θ//θθ to θ/jθ, preferably θ//θ
It is a polymer block consisting of a composition range of θ to θ/Otsu0, and the distribution of the vinyl aromatic compound in this block is random, tapered (the monomer component increases or decreases along the molecular chain), It may be partly block-like or any combination thereof.In addition, the block copolymer before hydrogenation in the present invention mainly contains a vinyl aromatic compound polymer block and a conjugated gene compound. There may be a copolymer portion of a vinyl aromatic compound and a conjugated diene compound in which the Cnivinyl aromatic compound exceeds jθ, such as a transition portion with a 1-lock, but such a polymer The part is a polymer block mainly composed of the above-mentioned conjugated diene compound (
= shall be included.

- In the h block copolymer, the content value of the vinyl aromatic compound and the content value of the conjugated diene compound are expressed as /θ
/9θ to riθ//θ, and koθ/♂θ to ♂s/
A range of is is preferred.

As the vinyl aromatic compound constituting the block copolymer before hydrogenation, one or more species are selected from styrene, α-methylstyrene, vinyltoluene, etc.,
Among them, styrene is particularly preferred. Further, as the conjugated diene compound, seven or two or more types are selected from butadiene, isoprene, and/or 3-pentadiene, among which butadiene and/or isoprene are particularly preferred.

The above block copolymer has a number average molecular weight of θ, θOθ
~ evening θθ, θθθ range. The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably in the range of /, θ - - /θ. The molecular structure of the block copolymer may be straight, branched, radial, or a combination thereof. Furthermore, when butadiene is used as a conjugated diene compound in a block copolymer, the 7,2 bond in the microstructure of the butadiene moiety is 7θ~
A range of ♂θ ratio is preferable. If the modified block copolymer needs to have rubber elasticity, the amount of /,2 bonds is 3! The range of ~jjt4 is particularly preferred.

In the case where the above 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 content of the heptamer component, Their structures such as distribution in molecular chains, molecular weights of blocks, and microstructures may be different.

The above block copolymer is usually produced by combining a vinyl aromatic compound and a conjugated diene compound in an inert hydrocarbon solvent such as benzene, toluene, hexane, or cyclohexane using an organic lithium compound such as butyllithium as a catalyst.
It can be obtained by anionic living polymerizable C2. Furthermore, by reacting the block copolymer having lithium active terminals obtained by the above method with a polyfunctional coupling agent, such as carbon tetrachloride, butylene tetrachloride, etc., branched or radial In the present invention, any polymer obtained by any polymerization method can be used as long as it is within the above range. There are not only 7 types of polymers but also 2 types.
It is also possible to use it as a mixture of ridges and above.

By flowing the above block copolymer with water using a known method, for example, the method described in Japanese Patent Publication No. 7-6, the 1-theta chain of the aromatic double bond of the vinyl aromatized metal block A is removed. Invisible part and conjugated diene compound block B
A partially hydrogenated block copolymer is synthesized in which at least lθ of the divalent aliphatic bonds are hydrogenated.

The degree of unsaturation of block B in the present invention refers to the proportion of carbon-carbon divalent bonds contained in block B, and this is determined by nuclear magnetic resonance absorption spectrum (NMR), infrared absorption spectrum (IR). 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, and cis-gucyclohexene. ．． 2-dicarboxylic acid and its anhydride, endo-cis-bicyclo[λ, ,;z,i]-
Among these, maleic anhydride is particularly preferred.

The above-mentioned modified block copolymers of the present invention include - for example, a partially hydrogenated block copolymer with an unsaturated dicarboxylic acid or
2 The derivative is placed in a solution state or a molten state (:
It can be obtained by addition with or without the use of a radical initiator.

-T- The method for producing these modified block copolymers is not particularly limited in the present invention, but the modified block copolymers obtained may contain undesirable components such as gel,
A manufacturing method in which the melt viscosity significantly increases and processability deteriorates 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 its Mg form in an extruder in the presence of a radical initiator.

Addition of an unsaturated dicarboxylic acid or its derivative to a block copolymer is θ, 0.3--KθE1 is 0.7 to 10% by weight per part of block copolymer/θθ part is preferred. When the addition is more than 1 part by weight of O6θj, the improvement is slight compared to an unfriendly conjugated diene polymer, and even if the addition exceeds 20 parts by weight, Thereafter, there is almost no increase in the improvement effect compared to F. The unsaturated dicarboxylic acids or derivatives thereof used in the present invention may be used alone or in combination of two or more.

The female block copolymer of the present invention has four functions:
Since it has improved compatibility with polar thermoplastic polymers having θ − groups, compositions using the present invention obtained in combination with the polar thermoplastic polymers have extremely excellent mechanical properties, processability, etc. has.

Examples of polar thermoplastic polymers that can provide such compositions are discussed in detail below.

The polar functional group here refers to a functional group that chemically bonds or exhibits strong interaction with the unsaturated dicarboxylic acid or its derivative added to the modified block copolymer. The above-mentioned functional groups (urethane groups, ester groups, amide groups, ammonium bases, etc.) can be easily opened by means of amino groups, hydroxyl groups, isocyanate groups, thiol groups, heating, etc.

Examples of the polar thermoplastic polymer having a polar functional group include polyamide, thermoplastic polyester, thermoplastic polyurethane, vinyl alcohol spinning wheel combination, vinyl ester spinning wheel combination, and the like. The functional group may be bonded to the terminal or side chain of these polymers.

Examples of polyamides include heavy silk compounds of dicarboxylic acids and diamines, terminating compounds of α-aminocarboxylic acids, and ring-opening compounds of cyclic lactams.Specifically, nylon-Otsu, nylon-6 Otsu, nylon-Otsu/θ, nylon-//, nylon-762, etc., and their copolymers, ie, nylon-6-nylon-66 co-east combination, nylon-6-nylon-7,2 military combination, etc. Can be mentioned. The number average molecule of these polyamides;
If better processability is desired, the melting point of the number-average molecules below θ, θ0θ is preferably 22θ°C or below.

Polyamides can be used not only in part but also as a mixture of two or more types.

The polyester polymer is a hot-mouth plastic type. Polyester polymers contain ester bonds in their molecules, and typical polyesters have a structure in which dicarboxylic acid and glycol are combined, and these include dicarboxylic acid, its lower ester, its acid halide, or This combination of acid anhydride and glycol (= thus obtained. This is the raw material for this polyester.
Aromatic or aliphatic dicarboxylic acids include oxalic acid,
Malonic acid, succinic acid, glutaric acid, pimelic acid, speric acid, adipic acid, cepacic acid, azelaic acid, /, 9
-nonanedicarboxylic acid, /, /θ-decanedicarboxylic acid, /, /O-hequinadecanedicarboxylic acid, terephthalic acid, isophthalic acid, p, p'-dicarboxydiphenyl,
Examples include p-carboquinphenoxyacetic acid, co-naphthalene dicarboxylic acid, and the like, and they can also be used in any desired combination. Among these, terephthalic acid and isophthalic acid are particularly preferred.

Glycols (or diols), which are another important raw material for the above polyester, can be aliphatic or aromatic, examples of which include ethylene glycol,
3-propanediol, 7.2-propanediol, /
, goobutadiol, hexanediol, /, cyclohexanediol, /, /θ-decanediol, neopentyl glycol, p-xylene glycol, etc., and these can be used alone or in any combination. Can be done. Among these, the number of carbon atoms is 2~/
Preferred are alkylene glycols of θ, and particularly preferred are C-niethylene glycol and terbutadiol. Among the above polyesters consisting of dicarboxylic acid units and glycol units, useful ones include polyethylene phthalate,
Polybutylene phthalate and a part of these seven units are substituted with other seven units (disubstituted).

The molecular weight of these polyesters is jθθ~/θθ, θθO
3,0θθ to Oθ, θθ0 is preferred.

There are no particular restrictions on the polymerization method for polyester, and Togane can carry out the process using conventional method C2. There is a method in which one or more glycols are simultaneously or stepwise directly esterified or transesterified or transesterified and then polymerized.In this case, any of the commonly used catalysts, stabilizers, and Agents and additives may also be used.

Other useful polyesters include cyclic lactones,
Examples include polylactones obtained by ring-opening polymerization such as pivalolactone, I-propiolactone, and ε-caprolactone.

The molecular terminals of these polyester polymers are hydroxy groups or carboxyl groups, and these terminals are further reacted with monofunctional alcohols or -functional carboxylic acids to convert the functional groups into inert C2 groups. There are some things.

In the present invention, the polyester polymer preferably has a functional group that reacts with a functional group of the modified block copolymer at part or all of its molecular terminal.

A portion of such functional group-containing polyester reacts with the modified block copolymer, thereby significantly improving the compatibility of the composition.

The above-mentioned polyester-based polymers can be used not only in / but also in combination of two or more.

Thermoplastic polyester polymers include fibers, films, resins, etc. such as polyethylene terephthalate (in addition to the polyesters used, low-crystalline polyesters with lower melting points, hard segments and soft segments) Also included are polyetherester block polymers contained within the same molecule.

Plastic polyurethane is classified into fully thermoplastic type and incompletely thermoplastic type depending on the synthesis conditions. determined by the molar ratio of
About θ,? The one synthesized with t < NC010f (≦/ is a completely thermoplastic type, and the one synthesized with about / NC010H</, / is an incompletely processed type. For example, as the above thermoplastic polyurethane, Some have polyol (polynisder or polyether) and diisocyanate blocks as soft segments, and diisocyanate and glycol blocks as all hard segments.

As the polyester diol of the above raw material, Bo! I
(/, y-butylene adipate), poly(i, t-hexane adipate), polycaprolactone, etc., and polyether diols include polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, etc. Further, glycols include ethylene glycol, /, couptanediol, /, and hexanediol, and diisocyanates include aromatic, alicyclic, and aliphatic types, such as tolylene diisocyanate and diisocyanate. ,the law of nature'
- Diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc.

In addition to the water-treated thermoplastic polyurethane elastomer,
Even if it is a polyurethane polymer used for adhesives, foams, hardwoods, etc., those having sufficient compatibility with the modified block copolymer of the present invention can be used for the modified block copolymer of the present invention. It can be suitably used in combination with this.

As a thermoplastic polyurethane, the molecular weight is
~500,000, preferably /θ, θθθ ~ 3θθ,
θθθ can be used because it has good mechanical properties.

Examples of vinyl ester polymers include vinyl ester skewers, olefin-vinyl ester copolymers, polyvinyl acetate, ethylene-vinyl acetate copolymers,
It is a polymer consisting of propylene-vinyl acetate core units or a copolymer containing vinyl alcohol units, and it is a polymer obtained by partially saponifying or completely saponifying a vinyl ester polymer using an alkali. Ethylene-vinyl alcohol military support uses the corresponding ethylene-vinyl acetate copolymer as a starting material,
The ethylene-vinyl acetate copolymer generally has a vinyl acetate content of θ, 5 to ♂θ mol. The above polymer has vinyl acetate units of /θ to /θθ
The molar ratio is saponified to form an ethylene-vinyl alcohol copolymer. In the present invention, various polyvinyl alcohols or olefin-vinyl alcohol copolymers can be used, but ethylene-vinyl alcohol copolymers are preferred from the viewpoint of processability and mechanical properties.

Next, the characteristics of the thermoplastic polymer composition containing the modified block copolymer of the present invention will be described.

A composition containing the modified block copolymer of the present invention uses, as a block copolymer component, an olefin whose degree of unsaturation does not exceed the 2θ coefficient, which has been modified with the unsaturated dicarboxylic acid or derivative thereof of the present invention C. By using a modified block copolymer having a compound polymer as one of its constituent elements, polar thermal iTg with polar functional groups can be improved compared to the case of using an unmodified swimming block copolymer.
It is characterized by a composition that has significantly improved compatibility with the Ji-based polymer.

In other words, a composition of an unmodified water-side block copolymer and a polar thermoplastic polymer having a polar di-functional group has poor compatibility with the two (2) poor dispersibility and low refractive index of both. In contrast, the composition of the modified block copolymer of the present invention and a polar thermoplastic polymer having a polar functional group has good dispersibility and improved brightness. ing.

The composition containing the modified block copolymer of the present invention has mechanical properties ranging from rubber-like or leather-like to resin-like, depending on the composition ratio of the modified block copolymer and the polar thermoplastic polymer. The axis varies widely up to the shape of the shape. For example, when the composition ratio is high in the modified block copolymer, the composition containing the modified block copolymer of the present invention is
The result is a rubber-like or leather-like polymer 4J↓ composition that has superior hardness, tensile strength, oil resistance, heat resistance, etc., as compared to butadiene or styrene-olefin block copolymers. Then, as the four components are added, the composition changes into a strong resinous state, and when the composition ratio is high in polar thermoplastic resin components, it depends on the type of polar thermoplastic resin used. Although the degree is different, it has a remarkable educational effect on impact resistance, material contact, bending resistance, etc.

Furthermore, the modified block copolymer of the present invention has a degree of non-separation that is limited to not exceed 10%, compared to the nutylene-diene block copolymer having a high degree of unsaturation. Shows excellent weather resistance.

In the thermoplastic polymer composition containing the modified block copolymer of the present invention, the composition includes 9♂ to 2 parts by weight of a modified block copolymer modified with an unsaturated dicarboxylic acid or a derivative thereof, a polar functional group 1 to 9 parts by weight of the polar thermoplastic polymer, preferably 1 to 9 parts by weight of the polar thermoplastic polymer. Outside the above range, no significant change in properties is observed compared to each polymer itself.

Further, the range of modified block copolymer 9 to Sθ and polar thermoplastic polymer 2 to Sθ is useful as a modified composition of the modified block copolymer. 2 to 50 parts by weight of copolymer, polar thermoplastic polymer
~! In the range of the θ east hook part, it is useful as a modified polar thermoplastic polymer with improved impact resistance and adhesion.

Furthermore, contained in the modified block copolymer -,,
2/- A graft copolymer composed of a modified block copolymer and a polar thermoplastic polymer, which is produced by a reaction between a reactive group and a reactive group contained in a polar thermoplastic polymer, is added to one part of the composition. Even when it is contained as part of the modified block copolymer of the present invention, it is included within the scope of the composition containing the modified block copolymer of the present invention.

The composition containing the modified block copolymer of the present invention can be prepared in accordance with the composition ratio of each component using equipment commonly used for mixing commercial molecular substances.

Examples of such mixing devices include an extruder, a mixing roll, a Banbury mixer, and a kneader.
Particularly (2) In the present invention, a melt mixing method using an extruder is preferred.

In addition, the thermoplastic polymer composition containing the modified block copolymer of the present invention may contain reinforcing agents such as calcium carbonate, silica, carbon black, glass fiber, and clay to the extent that its properties are not impaired. Alternatively, it is also possible to add fillers, process oils, polyethylene glycols, plasticizers such as phthalate esters, and the like. In addition, other additives such as heat stabilizers, antioxidants, ultraviolet absorbers, colorants, pigments, etc. may be added, and the composition of the present invention (1) may be added with a blowing agent to form a foam. It is also possible to do this.

(Effects of the Invention) The modified block copolymer of the present invention or a thermoplastic polymer composition containing the same, that is, a composition utilizing the present invention,
It has excellent processability and can be molded by various conventional molding methods such as extrusion molding, injection molding, and pre-calender molding, and has excellent mechanical properties in various fields such as films, sheets, molded products, and rubber tubes. It has a wide range of uses and is a useful substance.

(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 /, λ and Comparative Examples /, - (1) Preparation of hydrogenated block copolymer Using n-butyllithium as a bundling catalyst, 1-trahydrofuran was mixed with vinyl-containing polymer in n-hexane or cyclohexane solvent. Block copolymers shown in Table 7 were synthesized by anionic block copolymerization of butadiene and styrene as a blocking agent.

Table 1 The vinyl content of the butadiene portion of the styrene-butadiene block copolymer was determined by the Hampton method.

Next, the block copolymer shown in Table 1 was prepared in a mixed solvent of n-hexane and cyclohexane using cobalt naphthenate and triethylaluminum as catalysts under hydrogen pressure of 7.
(Approximately 90 bonds of the double bond in the butadiene block portion were added with hydrogen by performing slow addition in an aqueous system for j hours at a temperature of jθ°C,
A selectively hydrogenated block copolymer was synthesized in which the benzene ring of the styrene block remained almost unswimmed. The metal remaining on the catalyst was removed by washing with an aqueous hydrochloric acid solution and methanol.

(2) Preparation of modified block copolymer Swimming block metal body synthesized in the above (1) / θθ parts by weight (2 parts by weight, 2 parts by weight of maleic anhydride, 0.7 parts by weight of 2 parts by weight) After uniformly mixing B (manufactured by Nippon Menkaisha), it was supplied to a screw type extruder (axle, screw diameter 2θ throat, L/D-2g, full flight type screw) under a nitrogen atmosphere, and the cylinder was A maleation reaction was carried out at a temperature of 2jθ°C. Unterminated maleic anhydride was removed under heat and pressure from the obtained modified block copolymer, and λ, Otsu-Terchary-Petit Rougou methylphenol was added as a stabilizer. was added in an amount of θ, j parts per polymer/θO = amount S. When this modified block copolymer was analyzed,
Hs results were obtained.

Table 2 Modified block copolymer □ -, 21-jilu water The amount of maleic acid added was measured by titration with sodium methylate (secondary method).

(3) Preparation of composition A polar thermoplastic polymer layer is added to nylon (number average molecular weight/Z, θ0θ), 0 parts by weight and M (B or M
Il)! θ weight part and 3θ throat extrusion m (L/II)-2
A composition was obtained by blending the mixture at 22θ° C. in a ♂ and further forming into pellets.

For comparison (2. Instead of the above Mfll, M fl) (
A composition was obtained in the same manner except that (1) or (n) in Table 7, which is an unmodified block copolymer, was used. The above composition was injection molded and the mechanical saga was measured. The results are shown in Table 3. For reference, Table 3 shows examples/
The physical property values of the injection-molded nylon sample used in the comparison example/certification are also shown.

(hereinafter referred to as Eihaku) - Table 3 As shown in Table 3, the composition containing the modified block copolymer of the present invention has a lower temperature than the composition containing the unmodified block copolymer of the comparative example. Excellent compatibility and resistance (11
'74 provides a significantly improved Chiron composition.

Example 3, Comparative Example 3 Nylon-O (number average molecular weight/♂, θθθ) was used as a polar thermoplastic polymer in 3θ parts by weight, and M fil in Table 2 of Example/, as a modified block copolymer was used as a 7θ wheel. Both were kneaded in a room atmosphere at a temperature of 22θ°C for 10 minutes using a Brabender plastograph. The obtained composition was subjected to pressure molding and its mechanical properties were measured. For comparison, parts by weight of unmodified sample (1) 7θ in Table 1 and parts by weight of the above-mentioned nylon-Otsu and 3θN were mixed in the same manner and the same measurements were performed. Display the results (shown below).

(The following is a blank space.) As is clear from the results in Table 9, the composition of the modified block copolymer of the present invention and nylon-B is different from the composition containing the unmodified block copolymer of the comparative example (the second comparative example). The compatibility is significantly improved as indicated by the transparency values, the tensile strength and modulus are also higher, and the heat resistance as indicated by the tensile strength at elevated temperatures is improved. Further, remarkable improvement in weather resistance is a major feature of the composition containing the modified block copolymer of the present invention.

Example! and Comparative Example G, j Except for using nylon-66 (number average molecular weight 2θ, θθθ) in place of nylon-B and blending at 2≦θ°C, Example/, λ and H Comparative Example/, A composition was obtained in the same manner as in Example 2. Table 5 shows the results of measuring the mechanical properties of this composition. For comparison, the physical property values of an injection molded sample of Nylon-6 Otsu are also shown.

(Leaving space below) -3θ - Table j Example B, 7 Ratios Example 6.7 Polybutylene terephthalate (PBT/θg/, made by Toshi) was used as a polar thermoplastic polymer. M(1) or Mfl in Table λ as a modified block copolymer
0 parts by weight of L+ was used, and a 3θ■ twin screw extruder (L/D=
, 2 g) at a temperature of 2 g θ to λ θ °C,
The mixture was further pelletized to obtain a composition. The obtained composition was injection molded at 2'lθC, and the physical properties of the molded product were measured.

The results are shown in Table (2).For comparison, (2, Table/
The results of measuring the mechanical properties of the composition of the unmodified block copolymer and polybutylene terephthalate and of polybutylene terephthalate alone are also shown.

(Remaining days below) Table 2 As is clear from the results in Table 2, the compositions of Examples 2 and 2 using the modified block copolymer sample IVi (11 or M(It)) Copolymer sample +1
1, = 33-fil) and the composition of Comparative Example B, 2 and P B'
Compared to 1' alone, the impact resistance is improved.

Example ♂, 9 and comparative example? Using sample M (1) of a modified block copolymer and sample (1) of an unmodified block copolymer as a comparison, softening was performed using these and ethylene glycol as a diol component and terephthalic acid and isophthalic acid as dicarboxylic components. Points/93
C, intrinsic viscosity (3.jt in orthochlorophenol solution)
(measured at °C) 0.73 polyester (hereinafter referred to as sample P-7)
) was prepared by the method shown in F below.

The pellet size of sample Mil+ or sample (1) is 1 part and the pellet size of sample P-/ is 20 parts by 3θ11111.
1 extrusion bar, mixed at a temperature of θθ to 210C, and further pelletized to obtain a composition. This composition is λθ0
Compression molding was performed using C, and the physical properties of the molded product were measured.

These results are shown in Table 2 together with the results for sample M(1) alone.

-3g - Table 7 From the results in Table 2, it can be seen that the composition of the modified block copolymer and polyester of Example ♂ is different from the composition of the unmodified block copolymer and polyester of Comparative Example ♂ (- compared to The modified block copolymer of the present invention has improved mechanical properties such as tensile strength, 3θθ tensile stress, oil resistance, and heat resistance as indicated by tensile strength retention at 2θ°C. This indicates that the composition contained therein is a useful material.

Examples /θ to /2 and Comparative Examples /θ As the vinyl alcohol polymer, EVAL, EP-g (manufactured by Kuraray) of ethylene-vinyl alcohol copolymer which is a saponified product of ethylene-vinyl acetate copolymer Using 1(I) or M(n) in Table 2 as a modified block copolymer, with the composition shown in Table ♂ (1),
A composition was obtained by kneading using a mixing roll at ℃. For comparison, compositions were obtained in the same manner using the unmodified block copolymer t1+ or (It) in Table 7. Compression molded products of these compositions (molded at /♂θ°C)
Table ♂ shows the measured values of mechanical properties and tangentiality with simple density polyethylene.

(Left below) As is clear from the results in Table ♂, the composition of Example/θ to which the modified block copolymer was added had a higher notch concentration than Comparative Example 9 to which the corresponding unmodified block copolymer was added. The Izoll impact strength was surprisingly improved, and the tensile yield strength was almost the same as that of the comparative example. Note that the notched eye knot uniformity strength of ethylene-vinyl alcohol alone is even lower.

As a result of observing the samples of Example 10 and Comparative Example 9 using a phase contrast microscope, it was found that the sample of Example/θ has a modified block copolymer in the matrix of the ethylene-vinyl alcohol copolymer at approximately θ, In contrast, the sample of Comparative Example 9 has unmodified block copolymer particles of approximately t~/θμ or more dispersed, indicating that the compatibility between the two is uniform. The difference is obvious.

Additionally, compositions containing the modified block copolymers of the present invention had improved adhesion to polyethylene.

Example/3, /g and Comparative Example//, 72 A composition mainly composed of a modified block copolymer having the composition shown in Table 9 was
It was prepared using a mixing roll at 0°C. Table 9 shows the measurement results of physical properties, oil resistance, and adhesion of compression molded products (molded at /J'θ°C) of these compositions.

(Additional margin) As is clear from the results shown in Table 9, the composition containing the modified block copolymer of the present invention has improved tensile stress while maintaining sufficient negotiating θ − properties. Furthermore, oil resistance was greatly improved by adding a small amount of ethylene-vinyl alcohol copolymer. Furthermore, both the modified block copolymer of the present invention and the composition containing the copolymer have improved adhesion to polyethylene.

Example/Evening/7 and Comparative Example 73-/Taraprene P-,2,2siv (manufactured by H Honpolyurethane) was used as the thermoplastic polyurethane, and modified block copolymer M (1)
using a Brabender blast graph/
Obtained by heating at ♂θ°C. These compositions were pressure bonded to a polyvinyl chloride sheet and a polyethylene sheet with a high sieving density at /♂θ°C, and the adhesive peel strength was measured. , the results are shown in Table/θ.

(Hereinafter F margin) - As is clear from the results in Table/θ, the composition containing the modified block copolymer of the present invention is excellent against polyvinyl chloride and polyethylene sheets over a wide composition range. It has good adhesive properties. In contrast, the implantability of the composition containing the unmodified block coaggregate of the comparative example is inferior to the results of the corresponding example.

Claims (1)

[Claims] at least two vinyl aromatic compound polymer blocks A
and at least one olefin compound polymer block B with a degree of unsaturation not exceeding 20%, with a vinyl aromatic compound content of 10 to 90% by weight and a number average molecular weight of 2.
0,000 to 500,000 molecular units containing dicarboxylic acid groups or derivative groups thereof per 100 parts by weight of the block copolymer.
A modified block copolymer formed by combining 20 parts by weight.