WO2002020662A1 - Composition de copolymere bloc styrene hydrogene - Google Patents

Composition de copolymere bloc styrene hydrogene Download PDF

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Publication number
WO2002020662A1
WO2002020662A1 PCT/JP2001/007592 JP0107592W WO0220662A1 WO 2002020662 A1 WO2002020662 A1 WO 2002020662A1 JP 0107592 W JP0107592 W JP 0107592W WO 0220662 A1 WO0220662 A1 WO 0220662A1
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styrene
block copolymer
hydrogenated
weight
hydrogenated styrene
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PCT/JP2001/007592
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English (en)
Japanese (ja)
Inventor
Hideaki Nitta
Takeshi Sasaki
Shunichi Matsumura
Nobuaki Kido
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Teijin Limited
Bayer Ag
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Priority to AU2001282602A priority Critical patent/AU2001282602A1/en
Publication of WO2002020662A1 publication Critical patent/WO2002020662A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
    • G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins

Definitions

  • Patent application title Hydrogenated styrene-based block copolymer composition and optical disc substrate using the same
  • the present invention relates to a composition using a hydrogenated styrene-based block copolymer. More specifically, the present invention relates to a copolymer composition suitable for an optical component having excellent transparency, mechanical strength, rigidity, heat resistance, and moldability, particularly a copolymer composition suitable for an optical disk substrate.
  • Plastics used for optical components such as optical disc substrates and optical lenses have various characteristics such as optical isotropy (low birefringence), dimensional stability, weather resistance, and thermal stability in addition to transparency.
  • optical isotropy low birefringence
  • dimensional stability dimensional stability
  • weather resistance thermal stability
  • thermal stability in addition to transparency.
  • polycarbonate or methyl methyl acrylate has been mainly used for these optical applications.However, polycarbonate has a large intrinsic birefringence and tends to cause optical anisotropy in molded products. Methyl methacrylate had problems of poor dimensional stability due to its extremely high water absorption and low heat resistance.
  • amorphous polyolefin as an alternative material to polycarbonate
  • hydrogenated polystyrene in which the aromatic ⁇ of polystyrene is hydrogenated by hydrogenation to form a polyvinylcyclohexane structure has been proposed (Japanese Patent Publication No. 7-114300).
  • Such a resin has a great advantage that it can be produced at a lower cost than other amorphous polyolefins, but has a drawback that it is mechanically brittle.
  • Such a hydrogenated styrene-conjugated gen block copolymer has an effect of improving mechanical brittleness by introducing a certain amount of a rubber component. There is a possibility that transparency may be reduced due to phase separation due to a decrease in rigidity and aggregation of the rubber component.
  • An object of the present invention is to provide a hydrogenated styrene-based block copolymer composition, and to provide a material for an optical disc substrate, particularly a polymer composition capable of meeting the characteristics required for a high recording density optical disc substrate. Is to do. More specifically, compared to the conventional hydrogenated styrene-conjugated gen block copolymer, it has the characteristics of higher melt fluidity, toughness, less decrease in elastic modulus, and less warpage after disk molding. It is to provide a polymer composition.
  • the inventors of the present invention focused on a blend of a low molecular weight component and a high molecular weight component as a hydrogenated styrene-based block copolymer composition, and studied.
  • the low molecular weight component, the high molecular weight component, the molecular weight of each component, the ratio of the conjugated component, and the blend ratio of the two within a certain range, the fluidity of the polymer is high, and the impact is high.
  • the present inventors have found that a material having excellent strength and a small decrease in elastic modulus can be obtained, and arrived at the present invention.
  • the present invention comprises two main inventions, one of which relates to a hydrogenated styrene-based block copolymer composition, and the other relates to an optical disk substrate using the same.
  • the first invention of the present invention is as follows.
  • the second invention of the present invention and preferred embodiments thereof are as follows. 10. An optical disc substrate using the hydrogenated styrene-based block copolymer composition according to any one of 1 to 9 above, 11. The optical disc substrate according to 10 above, wherein the substrate thickness is 0.7 mm or less.
  • the copolymer composition of the present invention is suitably used not only for optical disk substrates but also for optical components such as optical lenses.
  • the two kinds of hydrogenated styrene-based block copolymers having different molecular weights used in the composition of the present invention are, in a broad sense, hydrogenated aromatic vinyl compound-based block copolymers, and are preferably aromatic This is a copolymer obtained by hydrogenating a block copolymer of a vinyl compound and a conjugated gen.
  • the aromatic vinyl compound means an aromatic hydrocarbon (benzene, naphthylene, etc.) which may have a substituent (an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, etc.).
  • one hydrogen atom bonded to the aromatic ring is replaced with a vinyl group or an ethylenically unsaturated group.
  • the total number of blocks obtained by addition polymerization of the aromatic vinyl compound or the conjugated diene and the degree of polymerization of each block can be arbitrarily selected.
  • an aromatic vinyl compound-conjugated gen-aromatic vinyl compound ternary block-type copolymer is hydrogenated. Things are preferred.
  • the hydrogenated styrenic block copolymer composition of the present invention preferably has a structure in which blocks of styrene and conjugated gen are linearly arranged, and is derived from a conjugated gen component in the block copolymer of styrene and conjugated gen.
  • a hydrogenated styrene block copolymer obtained by hydrogenating 90% by mole or more of all the double bonds and the aromatic ring derived from styrene.
  • “hydrogenating all of the double bonds derived from the conjugated gen component” refers to hydrogenating at least 99 mol% of the double bonds generated by addition polymerization of the conjugated gen. .
  • aromatic vinyl compound which is one of the copolymer components
  • styrene is preferably used, but other aromatic vinyl compounds such as monomethyl styrene and 4-methyl It is also possible to use styrene, 2-methylstyrene, vinyl naphthylene, etc. together with styrene. When two or more aromatic vinyl compounds are used in combination, the weight percentage of the total amount of the aromatic vinyl compound is used as the amount of the aromatic vinyl compound in the block copolymer composition.
  • a conjugated gen is used as the other of the copolymer components.
  • the conjugated diene include isoprene, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentanogen, and 1,3-hexadiene. Of these, isoprene or 1,3-butadiene is preferred from the viewpoint of polymerization activity and economy. These may be used alone or in combination of two or more.
  • the hydrogenated styrene-based block copolymer used in the present invention is preferably a copolymer obtained by hydrogenating a terpolymer of styrene-conjugated di-styrene, and styrene-isoprene-styrene (SIS)
  • SIS styrene-isoprene-styrene
  • the copolymer is a hydrogenated tertiary block copolymer of styrene-butane-styrene (SBS).
  • the present invention is characterized in that it is a composition of a low molecular weight hydrogenated styrene block copolymer and a high molecular weight hydrogenated styrene block copolymer.
  • the ratio of the conjugated gen component in the styrene-conjugated gen copolymer before hydrogenation is preferably in the range of 1 to 20% by weight. If the content is less than 1% by weight, the toughness properties such as impact resistance cannot be improved. If the content is more than 20% by weight, the elastic modulus is greatly reduced, and the component derived from the conjugated gen is likely to aggregate and crystallize. As a result, transparency decreases, which is not preferable. More preferably, the conjugated component is 1 to 15% by weight, even more preferably the styrene component is 85 to 95% by weight, and the conjugated component is 5 to 15% by weight.
  • the weight average molecular weight (Mw) after hydrogenation is preferably 40,000 to 100,000.
  • Mw represents the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) in a THF solvent. If this Mw is lower than 40,000, it is difficult to maintain the toughness of the composition even when blended with a high molecular weight component, which is not preferable. If it is higher than 100,000, , But the toughness is high, but high melt fluidity cannot be obtained. Is not preferred. More preferably, Mw is in the range of 50,000 to 90,000.
  • the ratio of the conjugated gen component in the styrene-conjugated gen copolymer before hydrogenation is preferably in the range of 1 to 16% by weight. It is preferable to increase the amount of the conjugated component in terms of toughness such as impact resistance.However, when the conjugated component is large, the decrease in the elastic modulus is large as in the case of the low molecular weight copolymer, and the conjugated component is also high. Agglomeration and crystallization of the components derived from the water increase the possibility of cloudiness.
  • the effect of improving the toughness by copolymerizing the conjugated gen component is increased because the conjugated gen component has a longer chain length per molecular chain even if the conjugated gen component amount is the same. . More preferably, the amount of the conjugated component is 2 to 15% by weight.
  • the preferred molecular weight of the high molecular weight hydrogenated styrenic block copolymer is in the range of 200,000 to 600,000 in weight average molecular weight (Mw), and in the range of 200,000 to 500,000. More preferred. If 1 is less than 200,000, the effect of maintaining toughness is not sufficient when blended with low molecular weight components, which is not preferable. If ⁇ [is greater than 600,000, the melt viscosity becomes too high and the melt becomes too high. It is not preferable from the viewpoint of fluidity.
  • composition ratio of the polymer composition in the present invention is determined in consideration of the low molecular weight copolymer (a) and the high molecular weight copolymer (b) and the respective molecular weights and conjugated component amounts.
  • (a) / (b) 50/50 to 98/2. If the low molecular weight copolymer component is less than this range, the melt fluidity becomes too high, which is not preferable. On the contrary, if it is too large, it becomes difficult to maintain toughness.
  • the modulus of elasticity of a hydrogenated styrene-based block copolymer is more affected by the amount of the conjugated component than by the molecular weight of the copolymer.
  • the amount of the conjugated gen component in the entire copolymer composition is preferably from 12 to 5% by weight, and more preferably from 10 to 5% by weight, from the viewpoint of the elastic modulus.
  • the flexural modulus of the copolymer composition is preferably 1.8 GPa or more. It is more preferably 1.8 GPa or more and 2.5 GPa or less.
  • a known method such as melting and kneading the previously isolated polymers with an extruder or mixing them in a solution state and then removing the solvent is used. Can be.
  • the styrene-conjugated gen-block copolymer which is a copolymer before hydrogenation, can be polymerized by a known method such as anion polymerization using organic lithium as an initiator.In such a polymerization method, the polymerization reaction is usually carried out. This is performed using a hydrocarbon solvent.
  • aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane and cyclooctane; benzene, toluene, xylene and the like
  • aromatic hydrocarbons Among these hydrocarbon solvents, cyclohexane or methylcyclohexane is preferably used in terms of solubility and reactivity.
  • a polar solvent may be used for the purpose of controlling the polymerization reaction, controlling the microstructure of the conjugated gen moiety, and the like.
  • polar solvents include ethers such as tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, getyl ether, methyl ethyl ether, and methyl tert-butyl ether; amines such as triethylamine and tetraethylethylene diamine; phosphines. And the like.
  • an organic lithium compound is generally used, and specifically, ethyl lithium, n-propyl lithium, isopropyl lithium, ⁇ -butyl lithium, sec-butyl lithium, tert-butyl lithium, etc. Is mentioned.
  • n-butyllithium or sec-butyllithium is preferably used because of the availability and the ability to initiate the polymerization reaction.
  • the polymerization temperature is usually ⁇ 20 ° C.
  • the polymerization must be performed in an atmosphere of an inert gas such as nitrogen or argon to prevent deactivation of the catalyst and the active terminal of the polymer during the polymerization.
  • an inert gas such as nitrogen or argon
  • anion polymerization is the only reaction whose main reaction is chain initiation and growth. No response. Therefore, a styrene-based block copolymer having a low or high molecular weight can be obtained by adjusting the charging ratio of the polymerization initiator and the monomers such as styrene and conjugated gen.
  • the structure of the finally obtained copolymer differs depending on how styrene and the conjugated diene are copolymerized.
  • a styrene-conjugated genblock copolymer having a tertiary block type structure of styrene-conjugated genstyrene is preferred because the mechanical properties of the molded article are well balanced. Further, in the present invention, it is not a so-called taper type in which each copolymer component is mixed and mixed at a boundary thereof, but a block copolymer which is as completely separated as possible.
  • the rubber-derived component specifically refers to a component derived from a conjugated diene.
  • styrene is first polymerized, then conjugated gen, and finally styrene are added to the polymerization reaction system in that order, and in each polymerization step, the previously added monomer is added. It is desirable to add the next monomer after almost complete reaction.
  • the hydrogenation reaction may be performed after the copolymer after the polymerization reaction is completely isolated, but can be performed in a solution state after the polymerization reaction, which is preferable from the economical viewpoint.
  • the hydrogenation catalyst used in the present invention is not particularly limited, and a known catalyst capable of subjecting an aromatic ring to nuclear hydrogenation (nuclear hydrogenation) can be used. Specifically, a noble metal such as nickel, palladium, platinum, cobalt, ruthenium, and rhodium, or a compound such as an oxide, a salt, or a complex thereof is used to form a porous material such as silica, alumina, silica, silica and alumina diatomaceous earth. A solid catalyst supported on a carrier may be used.
  • nickel, palladium, and platinum supported on alumina, silica, and silica-alumina diatomaceous earth are preferably used because of their high reactivity.
  • a hydrogenation catalyst is preferably used in the range of 0.5 to 40% by weight based on the copolymer, depending on its catalytic activity.
  • the hydrogenation reaction condition is usually a hydrogen pressure of 2.94 to 40% by weight. 24.5 MPa (30 to 250 kgf / cm 2 )
  • the reaction is carried out at a temperature of 70 to 250 ° C. When the reaction temperature is lower than 70 ° C, the reaction does not easily proceed, and when the reaction temperature is higher than 250 ° C, the molecular weight is liable to decrease due to molecular chain cleavage.
  • Preventing molecular weight reduction due to molecular chain breakage In order for the reaction to proceed smoothly, it is preferable to carry out the hydrogenation reaction at an appropriate temperature and hydrogen pressure appropriately determined by the type and concentration of the catalyst used, the solution concentration of the copolymer, the molecular weight and the like.
  • the solvent used in the hydrogenation reaction it is preferable to select a solvent that does not become a catalyst poison of the hydrogenation catalyst.
  • Saturated aliphatic hydrocarbons such as cyclohexane and methyl cyclohexane used as the solvent in the polymerization reaction
  • a system solvent can be suitably mentioned.
  • ethers such as tetrahydrofuran, dioxane, methyl tert-butyl ester and the like; esters; alcohols, etc., for the purpose of increasing the activity of the reaction or suppressing a decrease in molecular weight due to molecular chain cleavage.
  • a polar solvent may be added to the above solvent as long as the solubility of the copolymer is not hindered.
  • the solution after the polymerization reaction may be used as it is or in a solvent system to which a necessary polar solvent is further added.
  • a method of performing a hydrogenation reaction is preferably mentioned.
  • the above hydrogenation reaction is a so-called nuclear hydrogenation reaction, in which the double bond derived from the conjugated gen in the copolymer is completely hydrogenated, while the aromatic ring derived from styrene has a cyclic hexane structure.
  • the term “completely hydrogenated” as used herein means that the degree of hydrogenation is substantially 99% by mole or more.
  • the hydrogenation rate of the aromatic ring of such a copolymer is at least 90 mol%, preferably at least 98 mol%, more preferably more than 98 mol%, and most preferably at least 99 mol%. is there.
  • the hydrogenation rate is less than 90 mol%, there are problems such as a decrease in transparency of the obtained hydrogenated copolymer, a decrease in heat resistance, and an increase in the birefringence of a molded product, and therefore, such is not preferred. It is desirable that the hydrogenation rate be as high as possible, but in practice, it includes the physical properties of the hydrogenated copolymer obtained and the equipment and operation aspects of the hydrogenation process required to achieve the hydrogenation rate. It is determined in consideration of the economic efficiency.
  • the hydrogenation rate can be calculated by a method such as NMR measurement described below.
  • the catalyst can be removed by a known post-treatment method such as centrifugation or filtration.
  • a known post-treatment method such as centrifugation or filtration.
  • the amount of the residual catalyst metal is preferably 10 ppm or less, more preferably 1 ppm or less.
  • the desired hydrogenated copolymer can be obtained by a method such as evaporation of the solvent, stripping, or reprecipitation.
  • the hydrogenated copolymer composition of the present invention includes a hindered material such as “Ilganox 101 0” or “Ilganox 11076” (manufactured by Ciba Geigy Co., Ltd.) in order to improve the thermal stability during melt molding.
  • a hindered material such as “Ilganox 101 0” or “Ilganox 11076” (manufactured by Ciba Geigy Co., Ltd.) in order to improve the thermal stability during melt molding.
  • Phenol type partially acrylated polyvalent phenol type represented by "Sumilyzer-1 GS” and “Sumilyzer-1 GM” (manufactured by Sumitomo Chemical Co., Ltd.); It is preferable to add a stabilizing agent represented by a phosphite-based compound such as, for example, a releasing agent such as a long-chain aliphatic alcohol or a long-chain aliphatic ester, other lubricants, plasticizers, and ultraviolet absorbers, if necessary. Additives such as an antistatic agent can be added.
  • the hydrogenated styrene-based block copolymer composition of the present invention has a relaxation spectrum at 200 ° C. of the following formula (I):
  • H (r)-r) ⁇ 6.0 (1 0 ⁇ 2 ⁇ r ⁇ 1 0 4 ) ⁇ ⁇ (I) (where log is the common logarithm, and the relaxation time (seconds), H ( (P a) represents the relaxation spectrum at 200 ° C.
  • the relaxation spectrum When the relaxation spectrum is out of the range of the above formula (I), it tends to be difficult to satisfy sufficient transferability and warpage especially as a resin for an optical disc substrate for high-density recording. If the relaxation time is outside the range of (I), it takes too much time to relax the flow orientation at the time of disk molding, and there is a tendency that it is difficult to eliminate the warpage resulting from the relaxation. Also, regarding the land-group structure and pit transfer, the residual stress does not relax, which tends to cause poor transferability and reduced shape stability in a high-temperature environment.
  • Such relaxation spectra are described, for example, in “New Physics Advance Series 8 Rheology 1” (by Sanzo Yamamoto, Arebi Shoten, published in 1964), based on the results of complex elastic modulus obtained from vibration experiments and the like. Can be determined by the following method.
  • the range of the relaxation spectrum from the viewpoint of transferability and warpage, the smaller the product in the above formula (I), the smaller H (te) 'r, the better, but a too small one has a low molecular weight. Practical Not a target.
  • a more preferable range of the relaxation spectrum is the range of the following formula (II).
  • the copolymer composition of the present invention preferably has a heat distortion temperature (HDT) of 96 ° C or more, and more preferably has a heat distortion temperature of 96 ° C or more and 120 ° C or less.
  • HDT heat distortion temperature
  • the hydrogenated copolymer composition of the present invention can be molded by a known molding method such as injection molding, extrusion molding, and solution casting. In particular, it can be suitably used for manufacturing an optical disk substrate by injection molding. Such an optical disk substrate can be injection-molded at a molding temperature of 270 to 350 ° C.
  • the hydrogenated styrene-based block copolymer composition of the present invention it is possible to reduce the thickness of the substrate, which is suitable for producing an optical disk substrate having a substrate thickness of 0.7 mm or less.
  • the copolymer composition of the present invention is used as a precise optical material such as an optical disk substrate, it is preferable that the content of foreign matter is small, specifically, a foreign matter having a particle size of 0.5 zm or more. Is preferably not more than 20,000 Zg, more preferably not more than 10,000 / g, even more preferably not more than 5,000 / g.
  • the foreign substance is anything that is incompatible with the copolymer composition, such as impurities contained in the raw material, impurities mixed in the production process, gelled polymer, polymerization catalyst, and hydrogenation catalyst. Residue and the like.
  • the bit error rate is large when an optical disc substrate for high density recording is formed using the copolymer composition. This is not preferable because the recording / reproducing characteristics of the disc deteriorate.
  • These contaminants can be efficiently removed by a method such as filtration with a filter in each manufacturing step, or performing a step of cleaning in a clean room.
  • the hydrogenated styrene-based block copolymer composition comprising the low molecular weight component and the high molecular weight component of the present invention, not only excellent transparency and heat resistance but also excellent melt fluidity, high toughness, and elasticity are obtained. Small decrease in rate, warpage after disk molding It has become possible to provide a material having a characteristic that the size is small. Due to such characteristics, the copolymer composition of the present invention can be suitably used as an optical disk substrate material corresponding to a high recording density.
  • FIG. 1 shows the relaxation spectrum of the resins of Examples 1 to 3 based on 200 ° C.
  • the solid line in FIG. C shows the case where the equality holds in equation (I), and the dotted line shows the equation ( II) shows the case where the equality holds.
  • n-Butyllithium was purchased from Kanto Chemical Co., Ltd. with a 1.57M n-hexane solution and used as is.
  • Ni / silica 'alumina catalyst Ni loading 65% by weight was purchased from Aldrich and used as it was.
  • Tg Glass transition temperature
  • Weight average molecular weight Measured by gel permeation chromatography (GPC manufactured by Showa Denko KK, “Shodex System-11”) using THF as a solvent to determine the weight average molecular weight Mw in terms of polystyrene.
  • GPC gel permeation chromatography
  • Haze value An automatic digital haze meter UDH-20D manufactured by Nippon Denshoku Industries Co., Ltd. was used.
  • Izod impact strength A molded sample was subjected to an impact test with and without a notch using UF IMPACT TESTER manufactured by Kamishima Seisakusho in accordance with JISK-7110.
  • Heat distortion temperature (HDT) was measured by the following procedure according to JIS K-7207. Width 4. 0 Omm, height 12 mm, and a test piece of length 11 Omm, support two points the distance between fulcrums 10 Omm, applying a 181. Load of 3N / cm 2 in the central portion between the fulcrum. Fill the area around the test piece with silicone oil and raise the temperature at a heating rate of 2 ° C / min. The temperature when the deformation of the specimen reached 0.27 mm was measured.
  • Flexural modulus and flexural strength were performed according to the following procedure in accordance with JIS K-7203. That is, using Orientec UCT-1T, a three-point bending measurement was performed with a sample thickness of 3 mm, a sample width of 12 mm, an edge span width of 46 mm, and a crosshead speed of 2 mm / min. ⁇
  • Relaxation spectrum RDA II type manufactured by Rheometric Science Co., Ltd., cone-plate type, 200 ° C; 230. A vibration experiment was performed at C and 280 ° C. The temperature and temperature were converted from the obtained curve, and a master curve based on 200 ° C was created. Using the master curve, conversion to a relaxation spectrum was performed by the method described in “New Physics Advance Series 8 Rheology 1” (written by Sanzo Yamamoto, Bookstore, published in 1964). .
  • Disc substrate molding Injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., product name “MO40D 3H”) is used to mold a die for DVD with a disc diameter of 120mm and a stamper (DVD-RAM standard) with a land group structure. A stamper with a compliant single-sided storage capacity of 2.6 GB was used, and a 0.6 mm thick disk substrate was molded by injection compression molding.
  • the copolymer was polymerized to obtain a cyclohexane solution of the copolymer.
  • Table 1 shows the physical properties of the obtained hydrogenated copolymer.
  • the hydrogenation ratio of the isoprene component was all at least 99 mol%. From this, it was considered that the double bond derived from the conjugated gen component was substantially completely hydrogenated.
  • a hydrogenated styrene-isoprene copolymer was polymerized in the same manner as in Production Example 1 except that the amount was changed to 705 g, and a cyclohexane solution of the copolymer was obtained.
  • Table 1 shows the physical properties of the obtained hydrogenated copolymer.
  • the melt viscosity of the polymer measured at 137 ° C. and 300 ° C. was 57 Pa ⁇ s at a shear rate of 1 ( ⁇ 65 Pa ⁇ s at shear rate and 103 s- 1 at shear rate).
  • injection molding was performed at a cylinder temperature of 300 ° C. and a mold temperature of 70 ° C. to obtain various molded products for measuring physical properties. 9%, haze value was 1.5%, which was sufficiently transparent as a material for optical parts, and the impact strength of the molded product was measured by an Izod impact test to be 1.3 kJ.
  • the solution was heated and depressurized in a sealed system to prevent foreign substances from entering from outside, and the solvent was distilled off.Then, the outlet was formed into a pellet using an extruder in a clean room. A colorless and transparent pellet was obtained.
  • the physical properties of the pellets were the same as those obtained in Example 1, but when the amount of residual catalyst metal in the polymer was examined by ICP emission analysis, Ni was 0.34 ppm and 81 was 0. It was found that 25 ppm and 3 ⁇ were 0.28 ppm and both were 1 ppm or less. Further, the pellet was dissolved in cyclohexane in a clean room, and the number of foreign substances having a particle size of 0.5 ⁇ m or more was quantified.
  • a 0.6-mm thick disk substrate for DVD-RAM was formed with a cylinder temperature of 320 ° C, an injection mold temperature of 100 ° C on the movable side, and 105 ° C on the fixed side.
  • a cylinder temperature of 320 ° C 320 ° C
  • an injection mold temperature 100 ° C on the movable side
  • 105 ° C on the fixed side.
  • Atomic force microscopy showed that the transferability of the stamper shape was sufficiently high. Also, the warpage of the formed disk was small enough to bond the two disks, and it was a good disk substrate.
  • the initial charge is 198 g of styrene, 1244 g of cyclohexane, 6.77 mmol of n-butyllithium, 74 g of isoprene to be added, 150 g of cyclohexane, and then styrene to be added.
  • a hydrogenated styrene-isoprene copolymer was synthesized in the same manner as in Production Example 1 to obtain a cyclohexane solution of the copolymer. .
  • Table 1 shows the physical properties of the obtained hydrogenated copolymer.
  • the melt viscosity was low and the impact strength and bending strength of the molded product were high as in the case of the copolymer composition of Example, but the flexural modulus was 1.5 GPa. It was low and warped and deformed easily.
  • the initial charge is 176 g of styrene, 1108 g of cyclohexane, 6.59 mmol of n-butyllithium, 36 g of isoprene to be added, 80 g of cyclohexane, and then A hydrogenated styrene-isoprene copolymer was synthesized in the same manner as in Production Example 1, except that the added styrene was changed to 152 g and the cyclohexane to 750 g, and a solution of the copolymer in cyclohexane was prepared. I got Table 1 shows the physical properties of the obtained hydrogenated copolymer.
  • the molded product had a low melt viscosity and the same flexural modulus of the molded product, but the impact strength was 1.lkJ / m 2 (notched), 4 Since it was as low as 2 kJ / m 2 (no notch), it was extremely brittle and extremely difficult to handle after molding.
  • Sp / c was 0.30 dL / g, and the weight average molecular weight Mw was 72,000.
  • the weight ratio of the low molecular weight hydrogenated polystyrene solution and the solution of the high molecular weight hydrogenated styrene-isoprene copolymer D obtained in Production Example 4 was hydrogen.
  • Table 2 shows the physical properties of such a polymer and the physical properties of a molded article molded in the same manner as in Example 1.
  • the molded article was an extremely brittle resin having an impact strength as low as 1. Ok J / m 2 (with notch) and 4. lkJZm 2 (without notch).
  • the molded product was a brittle resin having a low impact strength of 1.2 kJ / m 2 (with a notch) and 4.6 kJ / m 2 (with no notch).
  • Table 2 Example Example Example Example Comparative example Comparative example Comparative example Comparative example

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Abstract

L'invention concerne un copolymère bloc styrène hydrogéné obtenu par mélange: a) d'un copolymère bloc styrène hydrogéné de bas poids moléculaire comprenant des unités styréniques et des unités diéniques conjuguées; et b) d'un copolymère bloc styrène hydrogéné de poids moléculaire élevé dans un rapport en poids donné; ce qui donne une composition polymérique présentant une aptitude à l'écoulement à chaud et une ténacité élevées et un faible module. Cette composition donne, au moulage, un disque à gauchissement réduit.
PCT/JP2001/007592 2000-09-07 2001-09-03 Composition de copolymere bloc styrene hydrogene WO2002020662A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001282602A AU2001282602A1 (en) 2000-09-07 2001-09-03 Hydrogenated styrene block copolymer composition and optical disk substrate obtained therefrom

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000-271396 2000-09-07
JP2000271396A JP2004269548A (ja) 2000-09-07 2000-09-07 水素化スチレン系ブロック共重合体組成物およびそれを用いた光ディスク用基板

Publications (1)

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WO2002020662A1 true WO2002020662A1 (fr) 2002-03-14

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PCT/JP2001/007592 WO2002020662A1 (fr) 2000-09-07 2001-09-03 Composition de copolymere bloc styrene hydrogene

Country Status (4)

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JP (1) JP2004269548A (fr)
AU (1) AU2001282602A1 (fr)
TW (1) TW572963B (fr)
WO (1) WO2002020662A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4525398B2 (ja) * 2005-03-17 2010-08-18 Ｊｓｒ株式会社 水素化芳香族ビニル系共重合体組成物及びその成形品

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03115349A (ja) * 1989-09-28 1991-05-16 Mitsubishi Kasei Corp 水素化ビニル芳香族炭化水素重合体組成物及び光ディスク基板
EP0505110A1 (fr) * 1991-03-18 1992-09-23 Mitsubishi Chemical Corporation Composition des polymères aromatiques de vinyle hydrogenées et support de disque optique
JPH10279773A (ja) * 1997-04-04 1998-10-20 Jsr Corp 水添ブロック共重合体組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03115349A (ja) * 1989-09-28 1991-05-16 Mitsubishi Kasei Corp 水素化ビニル芳香族炭化水素重合体組成物及び光ディスク基板
EP0505110A1 (fr) * 1991-03-18 1992-09-23 Mitsubishi Chemical Corporation Composition des polymères aromatiques de vinyle hydrogenées et support de disque optique
JPH10279773A (ja) * 1997-04-04 1998-10-20 Jsr Corp 水添ブロック共重合体組成物

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TW572963B (en) 2004-01-21
JP2004269548A (ja) 2004-09-30
AU2001282602A1 (en) 2002-03-22

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