JPH0762126A - Thermoplastic norbornene resin molding - Google Patents

Abstract

PURPOSE:To obtain the title molding improved in adhesion to a hard-coating layer or a metal compound layer by forming layer made of an unsaturated- carboxylic-acid-modified vinylaromatic/conjugated diene copolymer on the surface of a thermoplastic norbornene resin molding. CONSTITUTION:The surface of a thermoplastic norbornene resin molding is subjected to e.g. corona discharge treatment to obtain a modified molding having a surface tension of 50dyn/cm or above. 1-15wt.%, based on the copolymer, unsaturated carboxylic acid is grafted onto a vinylaromatic/conjugated diene block copolymer having a melt index of 0.1-60g/10min as measured at 200 deg.C under a load of 5kg, a vinylaromatic compound content of 10-80wt.% and a degree of hydrogenation of double bonds of 70% to obtain a grafted copolymer. The grafted copolymer is dissolved in a solvent to form a solution of a concentration of 1-20wt.%, and this solution is applied to the surface of the modified molding to form a primary primer layer of a thickness of 1-20mum. If required, a secondary primer layer is formed thereon, and a hard-coating layer, a metal compound layer or an adhesive layer or the like is formed on the molding through the primary or secondary primer layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic norbornene-based resin molded product having excellent adhesion to a hard coat layer, a metal compound layer and the like.

[0002]

2. Description of the Related Art Thermoplastic norbornene resins are known as resins excellent in heat resistance, moisture resistance, water resistance, chemical resistance, solvent resistance, transparency, low birefringence and the like. But,
When forming a hard coat layer or when evaporating a metal or a metal compound, the adhesiveness or adhesion may be insufficient, and the thermoplastic resin having a polar group exhibits relatively good adhesion / adhesion. Even with the norbornene-based resin, the adhesive surface may be peeled off under high temperature and high humidity conditions or in an environment where the temperature changes drastically.

In order to solve this problem, it has been attempted to improve the adhesiveness of the surface by a primer layer forming treatment, a surface treatment such as a plasma treatment or a corona discharge treatment, or a combination thereof. Among the surface modification treatments and the like, there is a demand for improvement in adhesiveness / adhesion by a primer layer forming treatment because no special facility or equipment is required. However, even if a primer layer forming treatment is performed using a conventionally known primer, sufficient adhesiveness and adhesion are not always obtained.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have made diligent efforts to improve the adhesiveness and adhesion of the surface of a thermoplastic norbornene-based resin molded product. As a result, the surface of the thermoplastic norbornene-based resin molded product has been improved. It was found that by forming a layer composed of an unsaturated carboxylic acid-modified vinyl aromatic / conjugated diene copolymer, it can be firmly bonded to a hard coat layer or a metal compound layer, and the present invention has been completed.

[0005]

Thus, according to the present invention, a polar group is introduced into a copolymer of a vinyl aromatic compound and a conjugated diene or a hydrogenated product thereof on the surface of a substrate composed of a thermoplastic norbornene resin. There is provided a molded article forming a layer comprising the modified product.

(Thermoplastic Norbornene Resin) The thermoplastic norbornene resin is disclosed in JP-A-51-80400, JP-A-60-26024 and JP-A-1-168.
725, JP-A-1-190726, JP-A-3-14882, JP-A-3-122137, JP-A-4-63807, and the like, and specifically, norbornene-based resins. Ring-opening polymer of monomer,
Examples thereof include hydrogenated products, norbornene-based monomer addition-type polymers, and norbornene-based monomer-olefin addition-type polymers.

Norbornene-based monomers are also known monomers in the above-mentioned publications, JP-A-2-227424 and JP-A-2-276842, and examples thereof include norbornene, its alkyl, alkylidene and aromatic. Substituted derivatives and halogens of these substituted or unsubstituted olefins,
Polar group substituents such as hydroxyl group, ester group, alkoxy group, cyano group, amide group, imide group, silyl group, for example, 2
-Norbornene, 5-methyl-2-norbornene, 5,
5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methoxycarbonyl-
2-norbornene, 5-cyano-2-norbornene, 5
-Methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5-phenyl-
5-methyl-2-norbornene, 5-hexyl-2-norboernene, 5-octyl-2-norbornene, 5-
Octadecyl-2-norbornene, etc .; Monomers obtained by adding one or more cyclopentadiene to norbornene, derivatives or substitution products similar to the above, for example, 1,4: 5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-
2,3-cyclopentadienooctahydronaphthalene,
6-methyl-1,4: 5,8-dimethano-1,4,4
a, 5,6,7,8,8a-octahydronaphthalene,
1,4: 5,10: 6,9-trimethano-1,2,3,3
4,4a, 5,5a, 6,9,9a, 10,10a-dodecahydro-2,3-cyclopentadienoanthracene, etc .; a polycyclic monomer which is a multimer of cyclopentadiene, similar to the above Derivatives and substitution products, for example, dicyclopentadiene, 2,3-dihydrodicyclopentadiene, etc .; Addition products of cyclopentadiene and tetrahydroindene, etc., derivatives and substitution products similar to the above, for example, 1,4-methano- 1, 4, 4a, 4b, 5, 8, 8
a, 9a-octahydrofluorene, 5,8-methano-
1,2,3,4,4a, 5,8,8a-octahydro-
2,3-cyclopentadienonaphthalene and the like; and the like.

The norbornene-based monomer may be polymerized by a known method, and if necessary, it may be a thermoplastic saturated norbornene-based resin by copolymerizing with another copolymerizable monomer or by hydrogenation. It can be a thermoplastic norbornene-based polymer hydrogenated product. Further, a polymer or a polymer hydrogenated product is subjected to a method known in JP-A-3-95235 or the like to obtain an α, β-unsaturated carboxylic acid and / or a derivative thereof, a styrene-based hydrocarbon, an olefin-based unsaturated bond and a hydrate. It may be modified by using an organosilicon compound having a decomposable group or an unsaturated epoxy monomer. In addition, in order to obtain a resin excellent in moisture resistance and chemical resistance, a thermoplastic norbornene-based resin containing no polar group is preferable. In addition, those containing no polar group have a modified product layer in which a polar group is introduced into a copolymer (hydrogenated product) of a vinyl aromatic compound and a conjugated diene, as compared with one containing a polar group. The degree of improvement in the adhesion to the metal compound layer and the like due to the provision is great.

In the present invention, the number average molecular weight of the thermoplastic norbornene-based resin is GPC with a toluene solvent.
The polystyrene conversion value measured by the (gel permeation chromatography) method is 10,000 to 200,
000, preferably 15,000 to 100,000, more preferably 20,000 to 50,000. When the thermoplastic norbornene-based resin has an unsaturated bond in the molecular structure, it can be made into a thermoplastic saturated norbornene-based resin by hydrogenation. In the case of hydrogenation, the hydrogenation rate is 90% or more, preferably 95%, from the viewpoint of heat deterioration resistance and light deterioration resistance.
Or more, more preferably 99% or more.

Further, the thermoplastic norbornene resin is
Various additives may be added as long as the object of the present invention is not impaired. For example, in the case of thermoplastic norbornene-based resin, phenol-based or phosphorus-based antioxidants; phenol-based thermal deterioration inhibitors; benzophenone-based UV stabilizers; amine-based antistatic agents; aliphatic alcohols Various additives such as lubricants such as esters, partial esters of polyhydric alcohols and partial ethers; and the like may be added, and other resins, rubbers, fillers and the like may be mixed and used. In particular, it is preferable to add a filler because the linear expansion coefficient can be reduced. However, addition of a filler may impair the lightness and transparency of the thermoplastic norbornene-based resin, so care must be taken depending on the application of the adhesive.

(Substrate) The substrate used in the present invention is formed by molding a thermoplastic norbornene resin. The molding method is
There is no particular limitation. Injection molding, melt extrusion, hot pressing, solvent casting, stretching and the like, which are general molding methods for thermoplastic resins, can be used.

The shape of the molded product is not particularly limited and may be a desired shape depending on the application. For example, when it is used for an optical disc having a metal reflection film which is a metal layer or a metal compound layer, it may have a shape suitable as a component of an optical disc used as an optical disc substrate.

(Surface modification treatment) In the production of the molded article of the present invention, prior to forming a modified product layer in which a polar group is introduced into a copolymer (hydrogenated product) of a vinyl aromatic compound and a conjugated diene, A surface modification treatment may be performed on the surface to be formed. The surface tension of the untreated thermoplastic norbornene-based resin is usually about 25 to 40 dyne / cm. In one of the methods for producing a molded article of the present invention, the surface tension of the surface of the molded article made of a thermoplastic norbornene-based resin is 50 dyne / cm or more, preferably 60 dyne / cm or more, and more preferably May be modified to 70 dyne / cm or more. The surface modification treatment is not particularly limited, and specific examples thereof include energy ray irradiation treatment and chemical treatment.

Examples of the energy ray irradiation treatment include corona discharge treatment, plasma treatment, electron beam irradiation treatment, and ultraviolet ray irradiation treatment. From the viewpoint of treatment efficiency, corona discharge treatment and plasma treatment, particularly corona discharge treatment are preferable. The energy beam irradiation treatment conditions are not particularly limited as long as the desired surface modification is performed, and a known method may be used. For example, in the case of corona discharge treatment, the conditions known in JP-B-58-5314 and JP-A-60-146078 may be used.
Also, in the case of plasma treatment, the conditions known in Japanese Patent Publication No. 53-794 and Japanese Patent Laid-Open No. 57-177032 may be used.

The chemical treatment may be carried out by immersing in a potassium dichromate solution, an aqueous solution of an oxidizing agent such as concentrated sulfuric acid, and thoroughly washing with water. Although it is efficient to shake in a state of being immersed, there is a problem that the surface is dissolved and the transparency decreases when treated for a long period of time, and particularly in a thermoplastic norbornene-based resin having a polar group,
It is necessary to adjust the treatment time depending on the reactivity and concentration of the chemicals used.

(Copolymer of Vinyl Aromatic Compound and Conjugated Diene (Hydrogenate)) In the present invention, the copolymerization of the vinyl aromatic compound and the conjugated diene is carried out on the surface of the base material whose adhesion is to be improved. A layer of a modified product in which a polar group is introduced into the united product (hydrogenated product) is formed.

The copolymer (hydrogenated product) of the vinyl aromatic compound and the conjugated diene used in the present invention has excellent adhesion to the thermoplastic norbornene resin. From the viewpoint of good adhesion and the like, the repeating structural unit derived from a vinyl aromatic compound is preferably contained in an amount of 10 to 80% by weight, more preferably 20 to 70% by weight, and particularly preferably 25 to 60% by weight, and good workability is obtained. From the viewpoint of properties, the melt index (200 ° C., 5 kg) is preferably 0.1 to 60 g.
/ 10 min, more preferably 0.3-40 g / 10 m
in. In addition, in order to avoid discoloration during long-term use, it is preferable that the double bond in the conjugated diene-derived repeating structural unit is hydrogenated, and the hydrogenation rate is 7
0% or more is preferable and 80% or more is more preferable.

As the vinyl aromatic compound, styrene,
Examples thereof include o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, vinylxylene, ethylstyrene, isopropylstyrene, ethylvinyltoluene, tertiary butylstyrene and diethylstyrene, and styrene is particularly preferable.

Examples of the conjugated dienes include 1,3-butadiene, isoprene, 1,3-pentadiene and 2,3-dimethylbutadiene, with 1,3-butadiene and isoprene being particularly preferred.

Examples of copolymers (hydrogenated products) of vinyl aromatic compounds and conjugated dienes include styrene / butadiene / styrene / block copolymers and styrene / isoprene / styrene / block copolymers. Examples thereof include styrene / ethylene / butadiene / styrene / block copolymers, styrene / butadiene / random copolymers, styrene / isoprene / random copolymers, and hydrogenated products thereof. It may have a linear structure or a branched structure. A random copolymer (hydrogenated product) may be used, but a block copolymer (hydrogenated product) is preferable from the viewpoint of adhesiveness with the thermoplastic norbornene-based resin. In addition, the block copolymer may contain a tapered portion or a random copolymerized portion.

(Copolymer (hydrogenated product) modified product) In the present invention, a polar group is introduced into a copolymer (hydrogenated product) of a vinyl aromatic compound and a conjugated diene for use. The polar group to be introduced is preferably -COOH or a derivative thereof, and specifically, acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, Unsaturated carboxylic acids such as nadic acid; maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, unsaturated carboxylic acid halides such as glycyl maleate, amides, imides, anhydrides, Derivatives of esters and the like; modified products with unsaturated carboxylic acids or unsaturated carboxylic acid anhydrides are preferable because of excellent adhesion, and acrylic acid, methacrylic acid, nadic acid, nadic acid anhydride, Or a modified product with maleic acid or maleic anhydride is more preferable. Maleic acid or modified product according to maleic anhydride, are particularly preferred. These unsaturated carboxylic acids and the like may be modified by mixing two or more kinds.

The method for introducing the polar group into the copolymer (hydrogenated product) of the vinyl aromatic compound and the conjugated diene is not particularly limited, but a hydrogenated product of the copolymer of the vinyl aromatic compound and the conjugated diene is sufficient. Since it can be modified to
Graft addition is preferred. The method of graft addition is not particularly limited, and a known method may be used. For example,
A radical generator may be added and the mixture may be heated and reacted in a melt kneader or in a solvent. When a radical generator is used, a large amount of unreacted monomer generally remains, but the unreacted monomer is preferably removed by a method such as vacuum drying. The amount of monomer added is a copolymer of vinyl aromatic compounds and conjugated dienes (hydrogenated product).
1 to 15 parts by weight, preferably 2 to 100 parts by weight
-10 parts by weight.

Modified products obtained by introducing polar groups into copolymers (hydrogenated products) of vinyl aromatic compounds and conjugated dienes include vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane and γ-methacryloxy. A silane coupling agent such as propyltrimethoxysilane and γ-aminopropyltrimethoxysilane; a filler such as carbon, glass fiber and glass beads; and the like may be added.

The method for forming a modified product by introducing a polar group into a copolymer (hydrogenated product) of a vinyl aromatic compound and a conjugated diene is not particularly limited. The modified product of the polymer (hydrogenated product) is applied to the surface of the base material by a method such as brush coating, dipping, spraying, spin coating, or roll coater to volatilize the solvent. When the solvent remains in the copolymer (hydrogenated product) modified product layer, problems such as blistering and foaming may occur when the finished product using the molded product of the present invention is used at high temperature. Therefore, it is preferable to sufficiently volatilize the solvent so that the solvent does not substantially remain. Usually 3 at 20-120 ℃
Dry for about 1 minute to about 1 hour.

The solvent is not particularly limited as long as it does not dissolve or deform the base material surface or change the quality thereof, and is usually a poor solvent for a thermoplastic norbornene resin that does not substantially corrode the base material surface. To use. Examples of such a solvent include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone; ester solvents such as butyl acetate, propyl acetate, ethyl acetate; and the like, and these may be used alone or in a mixture. Further, for example, toluene and xylene are good solvents for the thermoplastic norbornene-based resin, but when diluted to 70% by weight or less with a poor solvent such as methyl isobutyl ketone,
Even if it is applied to a thermoplastic norbornene-based resin molded article, it may not be substantially corroded, and such a diluting solution can be used as a solvent for a copolymer (hydrogenated product) modified product solution.

The concentration of the copolymer (hydrogenated product) modified product solution is usually 1 to 20% by weight, preferably 2 to 15% by weight. If the concentration is too high, the viscosity will be high, and if the concentration is too low, it will be difficult to apply a predetermined thickness, and the workability will be poor.

The coating amount is such that the thickness of the modified copolymer (hydrogenated product) layer from which the solvent has been removed is 1 to 20 μm, preferably 2 to
It should be 15 μm.

(Secondary primer layer-formed product) When the molded product of the present invention is used, particularly when adhesion is required, the copolymer (hydrogenated product) of the vinyl aromatic compound and the conjugated diene is polar. A secondary primer layer may be further formed on the layer of the modified product having the group introduced therein.

The secondary primer forming the secondary primer layer is not particularly limited, and has been conventionally used as a primer except for modified products obtained by introducing polar groups into copolymers (hydrogenated products) of vinyl aromatic and conjugated dienes. What has been used is illustrated. For example, when forming an acrylic UV-curable hard coat layer, a primer for an acrylic UV-curable hard coat agent may be used.

The method for forming the secondary primer layer is not particularly limited, and may be a method depending on the secondary primer used,
Usually, the method is basically the same as the method for forming the copolymer (hydrogenated product) modified product layer of the molded article of the present invention. However, the solvent of the secondary primer solution is a copolymer (hydrogenated product)
It is necessary to select one that does not substantially erode the modified layer.

(Completed Product) The molded product of the present invention has a layer of a modified product obtained by introducing a polar group into a copolymer (hydrogenated product) of a vinyl aromatic compound and a conjugated diene via an adhesive layer. It adheres to the adherend, forms a hard coat layer on the copolymer (hydrogenated substance) modified substance layer, or deposits a metal or metal compound on the copolymer (hydrogenated substance) modified substance layer. By forming a metal layer or a metal compound layer with the use of the metal layer or the like, it is possible to obtain a final product as a target. In addition, when forming an adhesive layer or a hard coat layer, especially when optical uniformity is required, if a solvent is used, a copolymer (hydrogenated product) modified product layer, or a laminated layer thereof is used. Select a solvent that does not attack the secondary primer layer.

[0032]

[Examples] Hereinafter, reference examples, examples, and comparative examples will be described.
The present invention will be specifically described. The light transmittance was measured at a wavelength of 400 using a spectrophotometer (U-4000 type, manufactured by Hitachi).
In nm, the adhesion is determined by a so-called cross-cut peeling test, that is, by making a cut on the vapor-deposited film or the hard coat layer with a cutter at 11 mm intervals, each crossing at a right angle to the vertical and horizontal directions. A cellophane adhesive tape (manufactured by Sekisui Chemical Co., Ltd.) was applied, and the adhesive tape was pulled in a direction perpendicular to the surface and peeled off. In the high temperature test, the test piece was left in an oven at 80 ° C. for 96 hours, then returned to room temperature and the state of the laminated film was visually observed, and in the heat cycle test, the obtained test piece was tested at −30 ° C. 80 minutes
℃ · 30 minutes, in the meantime, the temperature rise and fall at a constant rate 30 each
After performing a heat cycle test of 1 cycle for 2 hours for 24 cycles, the presence or absence of microcracks in the metal film was observed with an optical microscope.

Reference Example 1 Thermoplastic saturated norbornene resin (ZEONEX 28
0, manufactured by Nippon Zeon Co., Ltd., number average molecular weight of about 28,000
(0, glass transition temperature 140 ° C.) preliminarily dried at 90 ° C. for 3 hours, and injection-molded at a mold temperature of 100 ° C. and a resin temperature of 290 ° C. to obtain a 3.0 mm × 90 mm × 55 mm test piece.

The surface tension of this plate was 32 dyne / cm.

Reference Example 2 A high-frequency oscillator (Corona Generator HV05-2, manufactured by Tamtec) was used for the test piece obtained in Reference Example 1, a wire electrode having an output voltage of 100% and an output of 250 W and a diameter of 1.2 mm was used. Electrode length 240mm, work electrode distance 1.5m
Corona discharge treatment at m for 3 seconds, surface tension is 72 dy
The surface was modified so as to be ne / cm.

Reference Example 3 Maleic anhydride-modified styrene / ethylene / butadiene /
Hydrogenated styrene / block copolymer (Tuftec M1913, manufactured by Asahi Kasei, melt index value 20
At 0 ° C., 5 kg, 4.0 g / 10 min, styrene block content 30% by weight, hydrogenation rate 80% or more, maleic anhydride addition 2%) 2 parts by weight, xylene 8 parts by weight and methyl isobutyl ketone 40 parts by weight. Dissolved in a mixed solvent of
A Teflon filter having a pore size of 1 μm was filtered to prepare only a complete solution as an unsaturated carboxylic acid-modified vinyl aromatic / conjugated diene copolymer solution.

Example 1 The test piece obtained in Reference Example 1 was dipped in the solution obtained in Reference Example 3, taken out, and dried at 100 ° C. for 10 minutes to obtain an unsaturated carboxylic acid-modified vinyl aromatic / conjugated diene. A test piece having a copolymer layer was obtained. No erosion was observed on the substrate and the layer thickness was about 4 μm.

Example 2 20 parts by weight of dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku) and 1 part by weight of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba-Geigy) were dissolved in 80 parts by weight of ethyl acetate. ,
An acrylic hard coat agent solution was prepared.

The test piece obtained in Example 1 was dipped in the acrylic hard coat agent solution, taken out, and dried at 120 ° C. for 30 minutes to remove the solvent, and the thickness of the test piece was about 3 μm. An acrylic hard coat agent layer was formed. Then, one surface of the test piece was irradiated with ultraviolet rays with an intensity of 150 mW / cm ² for 20 seconds with a high pressure mercury lamp of 80 mW to cure the acrylic hard coat agent layer to form a hard coat layer.

The surface of the test piece having the hard coat layer was examined for adhesion by a cross-cut peeling test. As a result, 100 out of 100 cells remained. Also, 1 at 90 ° C
No change in adhesion was observed even after holding for 0 minutes.

Comparative Example 1 A test piece was prepared in the same manner as in Example 2 except that the test piece obtained in Reference Example 1 was used instead of the test piece obtained in Example 1.
An acrylic hard coat agent layer having a thickness of μm was formed and cured. When the adhesiveness of the surface of the test piece having the hard coat layer was examined by a cross-cut peeling test, the remaining number was 0 out of 100.

Comparative Example 2 The procedure of Example 2 was repeated except that the test piece obtained in Reference Example 2 was used instead of the test piece obtained in Example 1, and a thickness of about 3 was obtained.
An acrylic hard coat agent layer having a thickness of μm was formed and cured. The surface of the test piece having the hard coat layer was examined for adhesion by a cross-cut peeling test.
100 of the 00 stitches remained. However, after holding at 90 ° C. for 10 minutes, the remaining number was 100 in the same test.
It was the 0th grade.

Example 3 Aluminum (purity 99.9% or more) was used as a vapor deposition material for the test piece obtained in Example 1, and oxygen gas was introduced to adjust the pressure in the chamber to 8 × 10 ⁻⁶ Torr. An aluminum vapor deposition film was formed by the vacuum vapor deposition method. The film thickness was about 1000 Å.

Adhesion of this test piece was examined by a cross-cut peeling test. As a result, 100 out of 100 cells remained, no abnormality was found in the high temperature test, and no microcracks were found in the heat cycle test. It was

Comparative Example 3 The same treatment as in Example 3 was carried out except that the test piece obtained in Reference Example 1 was used in place of the test piece obtained in Example 1, and vapor deposition of aluminum having a film thickness of about 1000 angstrom was performed on the test piece. A film was formed.

When the adhesiveness of this test piece was examined by a cross-cut peeling test, only 13 out of 100 pieces remained, a part was peeled off in the high temperature test, and microcracks were observed in the heat cycle test. It was

[0047]

The molded article of the present invention has excellent adhesion to a hard coat layer, a metal film, an adhesive layer and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Sadaji Ohara 1-2-1 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Zeon Co., Ltd. Research and Development Center

Claims (5)

[Claims] 1. A layer made of a copolymer of a vinyl aromatic compound and a conjugated diene or a modified product obtained by introducing a polar group into a hydrogenated product thereof is formed on the surface of a base material made of a thermoplastic norbornene resin. Molding. 2. The molded article according to claim 1, wherein the copolymer of the vinyl aromatic compound and the conjugated diene is a block copolymer. 3. The molded article according to claim 2, wherein the modified product introduced with a polar group is a modified product introduced with —COOH or a derivative thereof. 4. The modified product having a polar group introduced therein is a maleic acid modified product or a maleic anhydride modified product.
Or the molded article according to item 3. 5. The modified product having a polar group introduced therein, wherein the compound having a polar group is graft-added.
The molded article according to 3 or 4.