JPH11189614A - Optical material for light transmission - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optical material excellent in various properties by using a product of hydrogenation of a homopolymer of 1,3-cyclohexadiene or of a copolymer of this monomer with another comonomer. SOLUTION: This material consists of a hydrogenation polymer obtained by hydrogenating at least 50% of the C-C double bonds of a polymer having a main chain represented by the formula: [-(A)a -(B)b -(C)c -(D)d -(E)e -] and having an Mn of 5,000-5,000,000, a light transmittance of 87% or above, and a Tg of 210-250 deg.C. In the formula, A to E are monomer units which constitute the main chain of the polymer and may be arranged in arbitrary order, (a) to (e) are each the wt.% of each monomer based on the total weight of A to E, the sum of (a) to (e) is 100, 60<=a<=100, and (b), (c), (d), and (e) satisfy 0<=b, c, d, or e<40). A is a 1,3-cyclohexadiene monomer unit, B is a chain-like conjugated diene monomer unit, C is a vinylaromatic monomer unit, D is a polar monomer unit; and E is an ethylene/α-olefin unit.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for producing a polymer obtained by copolymerizing 1,3-cyclohexadiene alone or a copolymerizable monomer with another copolymerizable monomer in the presence of a specific organometallic polymerization catalyst. The present invention relates to an optical material for light transmission comprising a hydrogenated polymer obtained by addition.

[0002]

2. Description of the Related Art Transparent resins have been widely used as molding materials for automobile parts, lighting equipment, electric parts and the like which require ordinary transparency. Furthermore, in recent years, higher-performance transparent resins have become lighter, have better moldability, impact resistance, and lower prices, and as optical plastics, have been used as optical lens materials for steel cameras, optical pickups, copying machines, and video cameras. It is widely used for disks, compact disks, optical disks capable of recording / erasing / reproducing, liquid crystal plastic substrates, optical fibers, eyeglass lenses, and the like.

[0003] Plastics for light transmission optical materials include:
Conventionally, polymethyl methacrylate (PMMA), polycarbonate (PC), and the like have been mainly used, but the former has problems such as water absorption, and the latter has problems such as birefringence during injection molding. Furthermore, the glass transition temperatures of PMMA and PC are as low as about 105 ° C. and 140 ° C., respectively, and the heat distortion temperatures are about 80-90 ° C. and about 120-140 ° C., respectively. Moreover, PMMA undergoes a decomposition reaction based on depolymerization at a relatively low temperature, and since PC is a condensation polymer, there is a concern that hydrolysis may occur due to residual moisture during molding. hard. Various PMMAs, PCs, and the like have been developed as optical grades in response to such problems, but at present, it is increasingly difficult to meet the needs of sophisticated users.

Recently, various cyclic polyolefins using a polycyclic norbornene-based monomer have been developed as a new polymer material for improving the disadvantages of these polymer materials. For example, Japanese Patent Publication No. 2-9619 and Japanese Unexamined Patent Publication No.
JP-A-26024 describes that a hydride of a ring-opening copolymer of tetracyclododecenes and norbornenes is excellent in transparency, water resistance and thermal properties. Further, Japanese Patent Application Laid-Open Nos. 60-168708 and 61-29
No. 2601 discloses that an addition polymer of a tetracyclododecene or a polycyclic norbornene monomer or more and an α-olefin is excellent in transparency, heat resistance, chemical resistance, water resistance and the like. ing. In addition, Tokuhei 8-26
No. 124 discloses a polymer obtained by polymerizing a tetracyclododecene derivative having various functional groups to improve heat resistance, optical properties and low water absorption. Further, it is shown that the glass transition temperature of the novel cyclic olefin polymer described in these publications is a high value of about 190 ° C., and the heat deformation temperature is 120 to 165 ° C.

However, the cyclic structure of these polymers in the molecular skeleton is a five-membered ring structure or a bicyclo or higher polycyclo structure, compared to a six-membered ring structure known as a specifically stable structure. Then, the strain energy of the skeleton is high. Therefore, when these polymers are exposed to external stimuli such as heat or light for a long time, long-term heat resistance or weather resistance (light resistance) is expected to have a fundamental limit, and it is said that they are optimal as raw materials for optical materials. hard. In fact, there is a wide variety of needs for plastics for optical materials at present, and in fields where heat resistance is required, a heat distortion temperature of 120 is required.
Even when the temperature is up to 165 ° C., the dimensional stability may be insufficient. For example, a headlamp reflector (reflection plate) for an automobile, particularly in the vicinity of the headlamp, becomes extremely hot, so that high heat resistance, that is, long-term stability at high temperatures is required.

The same applies to lenses (such as lenses for in-vehicle CDs and plastic optical fibers) used for equipment which may become hot when mounted on automobiles and airplanes. The demand for optical plastic materials for transmission is expected to increase in the future with the development of next-generation technologies such as the space industry. Further, a headlamp lens for an automobile is required as a place where weather resistance is required. It is expected that the transition from halogen to metal halide in headlamps will be in full swing in the future, and this is in response to the demand for materials that can withstand a large amount of ultraviolet rays generated at this time. This problem can be avoided to some extent by conventional techniques such as coating with an ultraviolet absorber. However, in order to fundamentally solve these problems, it is required to reexamine the polymer from its primary structure and to design a plastic for high-performance optical materials having a heat distortion temperature exceeding 120 to 165 ° C. .

[0007]

DISCLOSURE OF THE INVENTION The present invention is extremely excellent in heat resistance and weather resistance, and has transparency, low birefringence, low water absorption, high rigidity, impact resistance, abrasion resistance, chemical resistance and the like. It is an object of the present invention to provide an optical material for light transmission, which has various characteristics indispensable for the above optical material in good balance.

[0008]

Therefore, the present inventors have adopted 1,3-cyclohexadiene (hereinafter abbreviated as CHD) as a conjugated diene monomer having a 6-membered ring structure which is extremely stable thermally, and have adopted light. As a result of intensive studies to develop a transmission optical plastic or a polymer material suitable as a raw material thereof, a polymer obtained by polymerizing CHD, or a polymer obtained by copolymerizing with another comonomer, if necessary, is hydrogenated. Has excellent water resistance, transparency, low birefringence, low water absorption, high rigidity, impact resistance, abrasion resistance, chemical resistance, and particularly high glass transition, which are essential for use as optical materials for light transmission Since it has a temperature and a heat deformation temperature, it has been found that it is most suitable as an optical material which requires the above-mentioned heat resistance and weather resistance, and has led to the present invention.

That is, the present invention provides: A hydrogenated polymer obtained by hydrogenating a carbon-carbon double bond portion of a polymer having a polymer main chain represented by the following formula (I) by 50% or more and having a number average molecular weight of 5,000
0 to 5,000,000, a light transmission optical material comprising a hydrogenated polymer having a light transmittance of 87% or more and a glass transition temperature of 210 to 250 ° C, [-(A) a- (B) b- (C) c- (D) d- (E) e-] (I) (In the formula (I), A to E represent monomer units constituting a polymer main chain, and A to E are arranged in any order. A to e represent wt% of each of the monomer units A to E based on the total weight of the monomer units A to E,
e satisfies the following relationship. a + b + c + d + e = 10
0, 60 ≦ a ≦ 100, 0 ≦ b <40, 0 ≦ c <40,
0 ≦ d <40 and 0 ≦ e <40. (A): 1,3-cyclohexadiene monomer unit. (B): One or more monomer units selected from chain conjugated diene monomer units. (C): selected from vinyl aromatic monomer units,
One or more monomer units. (D): One or more monomer units selected from polar monomer units. (E): One or more monomer units selected from ethylene and α-olefin-based monomer units. ) 2. 2. The optical material for light transmission according to 1, wherein the hydrogenated polymer is a block copolymer; 1,2-bond and 1,4-bond in a chain ((A) a) composed of 1,3-cyclohexadiene monomer units of a polymer having a polymer main chain represented by the formula (I) The molar ratio of the isomers (1,2-conjugated / 1,4-conjugated) is 4
3. The optical material for light transmission according to 1 or 2, which is 0/60 to 90/10. A display substrate comprising the optical material for light transmission according to 1, 2, or 3.

Hereinafter, the present invention will be described in detail. The optical material for light transmission of the present invention may be a CHD homopolymer or a CHD
It comprises a hydrogenated polymer obtained by hydrogenating a copolymer obtained by copolymerizing a monomer and another copolymerizable monomer. In the copolymer used in the present invention, as a monomer copolymerizable with CHD (hereinafter, abbreviated as a comonomer), chain monomers such as 1,3-butadiene, isoprene, 1,3-pentadiene, and 1,3-hexadiene are used. Conjugated diene monomer, styrene, α
-Methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinyl aromatic monomers such as vinylstyrene, methyl methacrylate, methyl acrylate, acrylonitrile, methyl vinyl ketone,
Examples thereof include polar vinyl monomers such as methyl α-cyanoacrylate, polar monomers such as ethylene oxide, propylene oxide, cyclic lactone, cyclic lactam, and cyclic siloxane, and ethylene and α-olefin monomers. In particular, from the viewpoint of imparting impact resistance to a molded article, 1,3-butadiene and isoprene belonging to a chain conjugated diene-based monomer are preferable. In general, a 1,2-butadiene and a 1,4-bond are present in a 1,3-butadiene polymer chain, and when the molar ratio of the 1,2-bond is less than 40, when hydrogenated, It becomes crystalline. The incorporation of crystalline regions in the polymer results in non-uniformity of the polymer structure and significantly impairs transparency. Therefore, the molar ratio of the 1,2-conjugate in the 1,3-butadiene polymer chain is 40
It is preferably larger.

In the present invention, the copolymerization ratio (weight ratio) with the above comonomer is CHD / comonomer = 60/40 to 10
0/0, preferably 70/30 to 100/0, more preferably 75/25 to 100/0, particularly preferably 90/10 to 100/0. If the amount of the comonomer is too large, the optical properties and heat resistance derived from CHD decrease, and the elastic modulus of the molded article also decreases, which is not preferable.

Examples of the copolymer in the present invention include a random copolymer and a block copolymer. In order to maintain high heat resistance (high glass transition temperature and high heat deformation temperature), the CHD chain length is required. Since a larger value is preferable, a block copolymer is optimal. In the polymerization of CHD of the present invention, there are a 1,2-conjugate and a 1,4-conjugate as a polymerization mode. In the polymer of the present invention, the molar ratio of the 1,2-bond and the 1,4-bond in the CHD polymer chain (hereinafter abbreviated as 1,1,1,4 ratio) is 40/60 to 90/10.
It is preferred that More preferably 40/60 to 7
The range is 0/30. The 1,2,1,4 ratio is ¹ H-
It can be calculated by NMR.

The hydrogenated polymer used in the present invention is a carbon-carbon double bond portion of the above-mentioned CHD homopolymer or a copolymer obtained by copolymerizing a CHD monomer with another copolymerizable monomer. Is a hydrogenated polymer having a hydrogenation rate of 50% or more, preferably 80% or more, and more preferably 90% or more. When the hydrogenation rate is less than 50%, the obtained hydrogenated polymer is insufficient because heat resistance and weather resistance are developed. Incidentally, the hydrogenation rate represents a hydrogenation rate based on all carbon-carbon double bonds contained in the polymer represented by the formula (I).

The number average molecular weight of the hydrogenated polymer is 5,000 to 5,000,000, preferably 10,000.
The range is from 00 to 500,000. When the number average molecular weight is less than 5,000, it becomes a very fragile solid or viscous liquid, and its value as an industrial material becomes extremely low. On the other hand, when the number average molecular weight is 5,000
If it exceeds 000, undesired results in industrial production such as a long polymerization time and a remarkably high solution viscosity will be caused. Considering such characteristics of the hydrogenated polymer, the CHD homopolymer has a number average molecular weight of 1
The range of 000 to 200,000 is particularly preferable, and the range of 5,000 to 400,000 is particularly preferable for the block copolymer.

[0015] The number average molecular weight in the present invention means that a polymer is dissolved in 1,2,4-trichlorobenzene,
It is a number average molecular weight in terms of standard polystyrene of a polymer chain measured by a (gel permeation chromatography) method. The glass transition temperature of the hydrogenated polymer of the present invention is from 210 to 250 ° C, preferably from 215 to 240 ° C. When the glass transition temperature is lower than 210 ° C., the heat distortion temperature is lowered, and the heat resistance becomes insufficient. On the other hand, when the temperature exceeds 250 ° C., the melting temperature becomes extremely high and molding becomes difficult.

The glass transition temperature in the present invention is defined as DSC
The value measured by the method, and in the case of a copolymer, CH
The value on the high temperature side derived from the D polymer chain was defined as the glass transition temperature. The light transmittance of the hydrogenated polymer used in the present invention is 87% or more, preferably 90% or more.
When the light transmittance is less than 87%, the industrial value as an optical material for light transmission is lost.

The pre-hydrogenated polymer having a polymer main chain represented by the formula (I) of the present invention may be obtained by any production method and is not particularly limited. However, from the viewpoints of reaction temperature, polymerization yield, catalyst cost, and the molecular weight, molecular weight distribution, and primary structure control of the polymer, the following industrially preferred polymerization methods are exemplified. This method comprises converting 1,3-cyclohexadiene from an alkyl lithium such as n-butyl lithium and an amine such as N, N, N ', N'-tetramethylethylenediamine (TMEDA) at a specific ratio. Living polymerization is carried out using an organometallic complex obtained in combination as a catalyst.The characteristics of the polymer thus obtained are that the glass transition temperature becomes relatively higher than those obtained by other methods, There are advantages such as various molecular designs, which are advantageous depending on the application.

A conventional living anion polymerization catalyst is CH
A thermally stable 6-membered monomer having no sufficiently high polymerization activity that can be industrially used for a monomer having a large steric hindrance and difficult to polymerize such as D It has been difficult to introduce quantitatively into the polymer chain. On the other hand, when a method of using an organometallic compound containing a Group IA metal and an organic compound (complexing agent) capable of forming a complex with the organometallic compound as a polymerization catalyst is used, the polymerization of CHD can be performed in a living manner. As a result, an unprecedented high molecular weight 1,3-cyclohexadiene polymer (hereinafter abbreviated as PCHD) was obtained, and it became possible to quantitatively introduce other copolymerized monomers.

In this polymerization method, since the reaction proceeds in a living manner, the molecular weight of PCHD can be freely adjusted, and the molecular weight can be designed according to the purpose. Further, even when copolymerized with another monomer, the obtained polymer has extremely high blockability, and can add toughness while maintaining the inherently high glass transition temperature of PCHD. As described in the embodiment of the present invention, CHD and styrene (Sty) are actually converted to a monomer weight ratio of CHD /
When the copolymer was copolymerized with Sty = 80/20, the glass transition temperature derived from the polystyrene (PSty) chain and the PCHD (unhydrogenated) chain was clearly separated in the DSC measurement of the obtained polymer. When the spin-spin relaxation time (T2) of all the protons in the polymer was measured at 170 ° C. using a pulse NMR apparatus (JNM-MU25 manufactured by JEOL Ltd.), the relaxation component (T2 = 11 μs) was found to be relatively quantitative at 75 mol%, indicating that the blockability of the copolymer, especially PCHD
It was found that the blockability of the chain was high. Therefore, by hydrogenating such a block polymer, the polymer of the present invention is excellent not only in optical properties but also in heat resistance, and also has a very excellent balance of mechanical properties by imparting toughness by copolymerization. It became possible to provide.

The polymerization catalyst used in the above polymerization method is IA
It is composed of an organic metal compound containing a group metal and an organic compound (complexing agent) capable of forming a complex therewith. Group IA metals that can be used for the organometallic compound include:
Lithium, sodium, potassium, rubidium, cesium, and francium, and lithium is a particularly preferred Group IA metal. These Group IA metals may be one kind or, if necessary, a mixture of two or more kinds.

The organic lithium compound suitably used for the polymerization catalyst is a compound containing one or more lithium atoms that binds to an organic molecule or an organic polymer containing at least one carbon atom. The organic molecule includes a C1 to C20 alkyl group, a C2 to C20 unsaturated aliphatic hydrocarbon group, a C5 to C20 aryl group,
A C3-C20 cycloalkyl group; and a C4-C20 cyclodienyl group.

Examples of the organic lithium compound used for the polymerization catalyst include methyl lithium, ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, n-hexyllithium, allyllithium, cyclohexyllithium, phenyllithium, hexamethylenedilithium, cyclopentadienyllithium, indenyllithium, butadienyldilithium, isoprenyldilithium or the like, or polybutadienyllithium, polyisolithium Conventionally known oligomeric or polymeric organic lithiums containing a lithium atom in a part of the polymer chain, such as prenyllithium and polystyryllithium, can be exemplified. Preferred organic lithium compounds include methyllithium, ethyllithium,
Examples thereof include n-butyllithium and cyclohexyllithium. In particular, n-butyllithium can be exemplified as the most preferred organic lithium compound that can be industrially employed.

The organometallic compound containing a Group IA metal employed in the polymerization catalyst may be one kind or, if necessary, a mixture of two or more kinds. As the organic compound (complexing agent) capable of forming a complex with an organometallic compound containing a Group IA metal, amines, ethers, and thioethers are preferable, and one of these complexing agents may be used if necessary. Mixtures of more than one species may be used.

Particularly, preferred complexing agents used in the present invention have high complexing ability, and amines are widely used industrially. Among them, tertiary (tertiary) amines are most preferable. Specific examples of the tertiary amine compound include trimethylamine, triethylamine, N, N-
Dimethylaniline, N, N, N ', N'-tetramethyldiaminomethane, N, N, N', N'-tetramethylethylenediamine, N, N, N ', N'-tetramethyl-
1,3-propanediamine, tetramethyldiethylenetriamine, 1,8-diazabicyclo [5,4,0] undecene-7, diazabicyclo [2,2,2] octane,
4,4′-bipyridyl and the like, and the most preferred tertiary amine compound is 1,2 / 2 / of the PCHD chain.
Tetramethylethylenediamine (TMEDA) capable of controlling the microstructure of the polymer, including the 1,4 ratio.

The method for preparing the polymerization catalyst comprising the above-mentioned organometallic compound and complexing agent is not particularly limited, and any conventionally known technique can be employed if necessary. For example,
Under an inert gas atmosphere, an organic metal is dissolved in an organic solvent, an amine solution is added thereto, and the solution is maintained for a certain period of time. Then, without isolating a polymerization catalyst (complex), a monomer is added to perform polymerization. It is also possible to do.

[0026] In preparing the polymerization catalyst, the mixing ratio of the organic metal compound and a complexing agent constituting a complexing agent M ₁ mol, when the organometallic compound and _{M 2 mol, M 1 / M} 2 = 30
/ 1 to 1/30, preferably M ₁
/ M ₂ = 20/1 to 1/20 is most preferable in order to obtain a polymer in high yield. The polymerization method is not particularly limited, and gas phase polymerization, bulk polymerization, solution polymerization, or the like can be employed. Polymerization solvents that can be used in the case of solution polymerization include aliphatic hydrocarbons such as n-butane, n-pentane, n-hexane, and n-heptane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, Examples include alicyclic hydrocarbons such as decalin, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and ethers such as diethyl ether and tetrahydrofuran. These polymerization solvents may be one kind or a mixture of two or more kinds.

The polymerization can be carried out at a temperature of -100 to 120 ° C, most preferably 0 to 100 ° C. Further, from an industrial viewpoint, it is advantageous to carry out the reaction in the range of room temperature to 80 ° C. The pressure of the polymerization system is not particularly limited, as long as the pressure is sufficient to maintain the monomer and / or solvent in the liquid phase within the above-mentioned polymerization temperature range.

Although the time required for the polymerization reaction varies depending on the purpose and the polymerization conditions, it is not particularly limited. However, it is usually within 48 hours, particularly preferably 1 to 10 hours. Is done. The polymerization atmosphere is desirably an inert gas atmosphere of dry nitrogen, argon, helium, or the like. In the polymerization method in this reaction, prior to polymerization, some or all of the catalyst components are preliminarily reacted or aged, and a complex compound serving as a polymerization catalyst is synthesized in advance to obtain the polymer of the present invention. This is the preferred method.

As the polymerization terminator in the present invention, water,
Alcohol, polyhydric alcohol, phenol and the like are used. The amount of the terminator added is generally 0.00
It is used in the range of 1 to 10 wt%. The hydrogenated polymer of the present invention can be produced by carrying out a hydrogenation reaction on the carbon-carbon double bond portion of the polymer after the polymerization reaction has achieved a predetermined conversion.

The hydrogenation reaction is carried out under a hydrogen atmosphere in the presence of a polymer and a hydrogenation catalyst. A conventionally known method can be adopted as the reaction format. For example, any of a batch system, a semi-batch system, a continuous system, and a combination thereof can be adopted. As the hydrogenation reaction catalyst, any of conventionally known homogeneous catalysts and heterogeneous catalysts can be used, and if the hydrogenation rate of the present invention is satisfied, in particular, the type,
The amount is not limited.

Industrially particularly preferable metals contained in the hydrogenation catalyst include titanium, cobalt, nickel, ruthenium, rhodium, palladium and the like. These metals may be used as a homogeneous catalyst in combination with an organic compound (ligand) having a functional group such as ether, amine, thiol, phosphine, carbonyl, olefin, diene, or activated carbon, alumina, barium sulfate. , Silica, titania, zeolite, cross-linked polystyrene or the like, and used as a heterogeneous catalyst. From an industrial point of view, particularly preferred are heterogeneous catalysts from which the hydrogenation catalyst can be recovered. The amount of the hydrogenation catalyst used in this reaction is appropriately selected depending on the hydrogenation conditions, but is generally 10% by weight of the metal relative to the polymer.
The range is from ppm to 50 wt%.

Preferred examples of the solvent used for the hydrogenation reaction include aliphatic hydrocarbons such as n-butane, n-pentane, n-hexane and n-heptane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and the like. Examples include alicyclic hydrocarbons such as cycloheptane and decalin, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, and ethers such as diethyl ether and tetrahydrofuran. These hydrogenation reaction solvents may be one kind or a mixture of two or more kinds.

[0033] The temperature of the hydrogenation reaction is in the range of 0 to 300 ° C, particularly preferably 30 to 200 ° C. The pressure of the hydrogenation reaction is generally 1~250kgf / cm ^2, particularly preferably 5~150kgf / cm ^2.
The time required for the hydrogenation reaction is not particularly limited because it is related to the concentration of the polymer solution, the temperature and the pressure of the reaction system, but it can be generally carried out in the range of 5 minutes to 240 hours.

The polymer of the present invention can be formed into a light transmitting optical material by a known method. That is, injection molding, compression molding, extrusion molding, inflation molding, blow molding, injection blow molding, cutting molding, rotational molding, vacuum molding, rolling molding, calendering, cast molding, and the like can be employed. Polymer of the present invention, in order to improve impact resistance, flexibility, etc.,
Commonly used modifiers such as styrene / butadiene diblock and triblock copolymers (hydrogenated)
And various graft copolymers obtained by polymerizing a monomer selected from ethylene, ethyl acrylate, methyl methacrylate, styrene, vinyl acetate, acrylonitrile, propylene, glycidyl methacrylate, etc., and further polycarbonate / acrylonitrile /
It is also possible to use a blend of a styrene-based graft copolymer or the like.

The cyclohexadiene-based polymer and the hydrogenated polymer used in the present invention may have a reactive functional group in the molecular chain or at the terminal. In order to provide a reactive functional group, a known compound which is generally known to react with an anionic polymerization terminal or a double bond may be added following the polymerization reaction. Examples of such compounds include methyldimethoxysilane, methyltrimethoxysilane, diethyldiethoxysilane, phenyldimethoxysilane, dichlorodimethoxysilane, methyltris (ethylmethylketoxime) silane, methyltris (N, N'-diethylaminoxy) silane Silylating agents such as ethylene oxide, propylene oxide, butene oxide, etc., titanium compounds such as tetrabutoxytitanium, halogens such as chlorine, bromine and hydrogen chloride, and peroxides such as hydrogen peroxide and metachloroperbenzoic acid. And aluminum isopropoxide, triisopropoxy borane, ethyl chloroacetate and the like.

Further, the polymer of the present invention may contain various additives. For example, as a substance capable of reacting with a cyclohexadiene-based polymer, a partially or completely hydrogenated polymer thereof, and a cyclohexadiene-based polymer having a reactive functional group in a molecular chain or at a molecular chain terminal, a carbon-carbon double bond Or a general compound which can react with various functional groups can be used. Specifically, unsaturated compounds such as divinylbenzene, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallyl citrate, triallyl trimellitate, and silane compounds such as methyldimethoxysilane, methyltrimethoxysilane, and diethyldiethoxysilane , 4,4'-diphenylmethane diisocyanate, isocyanate compounds such as tolylene diisocyanate, mercaptan compounds such as dithioadipic acid and pentamethylenedithiol, and compounds generally used as crosslinking agents such as diamines, aldehydes, dicarboxylic acids, and dicarboxylic dichlorides Examples of the optical material for light transmission of the present invention include known antioxidants such as 2,6-di-tert-butyl-4-methylphenol and 2,2′-dioxy-3,3′-di-. ter t-butyl-5,5′-dimethyldiphenylmethane, phenyl-β-naphthylamine, etc., or an ultraviolet absorber such as 2,4-dihydroxybenzoquinone, 2-hydroxy-4-methoxybenzophenone, 2′-hydroxy-4
It is possible to stabilize by adding -methoxy-2'-carboxybenzophenone and the like. Further, a lubricant or the like may be used for improving workability.

The optical material for light transmission according to the present invention has an inorganic compound, an organic silicon compound, an acrylic monomer, a vinyl monomer, or the like, on the surface thereof by a method such as a thermosetting method, an ultraviolet curing method, a vacuum evaporation method, or a sputtering method. By hard coating with melamine resin, fluorine resin, silicone resin, etc., heat resistance, optical properties, chemical resistance,
It is also possible to improve abrasion resistance, transparency, high rigidity, abrasion resistance and the like.

The polymer thus obtained in the present invention is
As is clear from the high glass transition temperature, it has particularly excellent heat resistance and weather resistance, and also has characteristics such as low water absorption, high transparency, low birefringence, and high chemical resistance. Therefore, the optical material for light transmission of the present invention is a material for light transmission that requires particularly heat resistance, an optical lens, a headlight lens for an automobile, a headlight reflector for an automobile, an optical disk (for blue laser), an optical fiber, and a GI type. It can be used in optical fields such as optical fiber cores and glass windows.

The application of the optical material for light transmission according to the present invention is not particularly limited, and it can be used over a wide range. For example, a semiconductor (EPR) which needs light transmissivity
OM) sealing resin, protective layer of magneto-optical recording film, low-pass filter, optical memory disk transparent container packaging material, light diffusion plate, prism, solar cell, power optics, phase plate for liquid crystal display, having transparency Plastic substrate, reflective liquid crystal film substrate, moisture-proof layer for information recording medium element, light guide plate, waveguide, polarizing film, magneto-optical disk substrate, infrared cut filter, optical character reading device such as facsimile, optical bandpass filter, Optical and electrical and electronic parts and equipment such as a wire covering material, a protective layer for an electrophotographic photoreceptor, a flexible substrate, a dustproof cover for a photomask, a water tank for a steam iron, and parts for a microwave oven. In particular, it is preferably used as a substitute for a glass substrate used in plasma displays, liquid crystal displays, touch panels, EL displays, field emission displays, and the like. Glass substrates used for these displays are widely used because of their excellent optical properties and heat resistance. However, glass has drawbacks of being higher in specific gravity and inferior in impact resistance than plastic. In particular, when a liquid crystal display is mounted on a portable device, a thin glass substrate having a thickness on the order of several hundreds of μm is used for weight reduction. However, glass is brittle, so that the manufacturing process is difficult. Further, breakage of the glass substrate during the production of a liquid crystal display and the use of equipment has become a major problem. In the case of a plasma display, thinning and weight reduction are indispensable conditions for increasing the screen size. Plastic has a lower production cost than glass, can be easily molded, and can be molded into various shapes.

In addition, a flexible layer having low water absorption, good mechanical strength and excellent folding resistance in place of a protective layer for an electrophotographic photoreceptor and a polyimide having high water absorption which require excellent transparency and abrasion resistance. Use as a substrate is also advantageous. It is also advantageous to be used as a material for μ-TAS or a medical instrument which requires heat resistance and weather resistance enough to withstand γ-rays with excellent transparency and high-temperature sterilization, for example, a drug solution container, a vial, and an ampoule. , Infusion bags, infusion tubes, sterile containers for medical instruments and the like.

[0041]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to examples and comparative examples. The chemicals used in the present invention were of the highest purity available. A general solvent was degassed according to a conventional method, dehydrated and degassed in an active metal atmosphere under an inert gas atmosphere, and then distilled and purified.

The number average molecular weight is the value in terms of standard polystyrene obtained by dissolving in 1,2,4-trichlorobenzene and obtained by GPC. The GPC apparatus was measured at 140 ° C. using a high-temperature GPC system (PL-GPC210) manufactured by Polymer Laboratory. The hydrogenation rate is ¹ H-NMR
(LA-300WB manufactured by JEOL Ltd.), and calculated from disappearance of olefin and benzene ring proton peaks.

The 1,2-conjugate and 1,4 in the PCHD chain
-The conjugate molar ratio is described in Polym. Sci. , Pa
rtB: Polym. Phys. , 36, 1657 (1
998) by ¹ H-NMR (LA-300WB, manufactured by JEOL Ltd.). The glass transition temperature was measured at a heating rate of 10 ° C./min using DSC (DSC-7 manufactured by PerkinElmer).

For the chemical resistance (acetone resistance), weather resistance and heat resistance, the obtained hydrogenated polymer was treated at a cylinder temperature of 300 ° C.
Was performed using an injection molding machine (Labo Plastomill, manufactured by Toyo Seiki Co., Ltd.) set as described above, and a test piece having a thickness of 3 mm was obtained. The test piece was used as follows.・ Chemical resistance (acetone resistance) is 20
Judgment was made from the appearance of the test piece after immersion for a time. No change was indicated by ○, swelling (devitrification, whitening) was indicated by Δ, and dissolution was indicated by X. -The weather resistance was determined from the appearance of the test piece after 1000 hours under a rainy condition at a black panel temperature of 83 ° C using a sunshine weather meter (abbreviated as SWOM). ◎ indicates no change in appearance, ○ indicates slight yellowing, and △ indicates slight deformation (warpage) and yellowing. Heat resistance is rated as ◎ when the temperature at which the deflection of the test piece reaches 0.254 mm exceeds 165 ° C, ○ when the temperature is 120 to 165 ° C, and x when the temperature is less than 120 ° C according to the ASTM method (D648). did.

The specific gravity was measured by the ASTM method (D792), the water absorption was measured by the ASTM method (D570), the light transmittance was measured by the ASTM method (D1003), the refractive index and the birefringence were measured by the ASTM method (D542), and the Izod impact strength was measured. Is the ASTM method (D
256).

[0046]

Example 1 400 g of dehydrated cyclohexane was placed in a 1 liter pressure-resistant autoclave which had been thoroughly dried and purged with dry nitrogen, followed by 10 mmol of n-butyllithium (n-BuLi) and 10 mmol of TMEDA.
Was put. After raising the temperature to 70 ° C. and keeping it for 10 minutes,
The temperature was lowered to 0 ° C. to obtain a catalyst solution. 100g of 1,
3-Cyclohexadiene (CHD) was added, and the mixture was stirred at 40 ° C for 6 hours. After the reaction was stopped by adding 10 g of methanol, the reaction solution was poured into a large amount of acetone.
The precipitate was washed again with acetone, filtered and dried to obtain a white polymer. The yield of the obtained polymer was 98 wt%, the number average molecular weight was 3.18 × 10 ⁴ , and the molecular weight distribution [weight average molecular weight / number average molecular weight (Mw / Mn)] was 1.23. The 1,2 / 1,4 ratio in the PCHD chain of the polymer calculated from ¹ H-NMR was 51/49.
Met.

Next, 80 g of the obtained polymer, 16 g of a hydrogenation catalyst (5% -Pd / BaSO ₄ ) in which 5 wt% of palladium is supported on barium sulfate, and 800 g
Was placed in a similarly dried pressure-resistant autoclave, and the polymer was once dissolved at 100 ° C., and the inside was replaced with hydrogen. The initial hydrogen pressure was 50 kgf / cm ² , the temperature was raised to 150 ° C., and the hydrogenation reaction was performed for 4 hours. After cooling the pressure-resistant autoclave to room temperature, Pd /
BaSO ₄ was removed by filtration under pressure, and the filtrate was poured into acetone, filtered and dried to obtain a white hydrogenated polymer. ¹ H-N
The hydrogenation rate of the polymer calculated from MR was 100%,
Number average molecular weight is 3.23 × 10 ⁴ , molecular weight distribution is 1.2
It was 6. The glass transition temperature measured by a DSC method was 219 ° C. After molding, the measured various properties are shown in Tables 1 and 2 together with the above polymerization conditions and the like.

[0048]

Example 2 400 g of dehydrated cyclohexane was placed in a 1 liter pressure-resistant autoclave which had been thoroughly dried and purged with nitrogen, followed by 5 mmol of sec-butyllithium (sec-BuLi) and 6.5 mmol of TMEDA. After raising the temperature to 70 ° C. and keeping it for 10 minutes,
The temperature was lowered to ° C to obtain a catalyst solution. 100g of 1,3
-Cyclohexadiene (CHD) was added, and the mixture was stirred at 40 ° C for 8 hours. The reaction was stopped by adding 10 g of methanol, followed by 20 g of 5% -Pd / BaS.
O ₄ was added, and the inside was replaced with hydrogen. Initial hydrogen pressure is 60k
gf / cm ² , and the temperature was raised to 150 ° C. to carry out a hydrogenation reaction for 5 hours. After cooling the autoclave to room temperature,
The hydrogenation catalyst was removed by filtration from the content, and the filtrate was poured into acetone, filtered and dried to obtain a white hydrogenated polymer. ¹ H
In the polymer before hydrogenation calculated by NMR
The 1,2 / 1,4 ratio in the D chain is 50/50, the hydrogenation rate of the hydrogenated polymer is 98%, and the number average molecular weight is 4.33.
× 10 ⁴ , molecular weight distribution was 1.30. Also DSC
The glass transition temperature measured by the method was 222 ° C. After molding, the measured properties are shown in Tables 1 and 2 together with the above polymerization conditions and the like.

[0049]

Example 3 A polymerization reaction was carried out in the same manner as in Example 1 except that the monomers to be added were 95 g of CHD and 5 g of 1,3-butadiene (Bd). The order of addition was 1,3-butadiene (Bd) and then CHD. The fact that all the monomers were consumed in the polymerization reaction in the order in which they were added was determined by gas chromatography (GC-14, manufactured by Shimadzu Corporation).
A). The yield of the obtained diblock polymer is 9
5 wt%, the number average molecular weight was 3.22 × 10 ⁴ , and the molecular weight distribution was 1.36. The copolymerization ratio of the copolymer calculated from ¹ H-NMR was almost quantitative. Subsequently, a hydrogenation reaction was carried out in the same manner as in Example 1, and after a predetermined treatment, a white hydrogenated polymer was obtained. A clear glass transition point was observed at 218 ° C. by the DSC method. After molding, the measured properties are shown in Tables 1 and 2 together with the above polymerization conditions and the like.

[0050]

EXAMPLE 4 90 g of CHD and 10 g of monomers to be added
A hydrogenated diblock polymer was obtained in the same manner as in Example 1 except that 1,3-butadiene (Bd) was used. The order of addition was 1,3-butadiene (Bd) and then CHD. It was confirmed by gas chromatography (GC-14A, manufactured by Shimadzu Corporation) that all of the monomers were consumed in the polymerization reaction in the order in which they were added. The measured characteristics are
The results are shown in Tables 1 and 2 together with the polymerization conditions.

[0051]

Example 5 70 g of CHD and 30 g of monomers to be added
1,3-butadiene (Bd), and sec-BuLi
Was changed to 2.5 mmol and TMEDA was set to 3.25 mmol, and a hydrogenated triblock polymer was obtained in the same manner as in Example 1. The order of addition was 35 g of CHD, 30 g of 1,3-butadiene (Bd), and 35 g of CHD. Gas chromatography (manufactured by Shimadzu Corporation) indicates that all monomers were consumed in the polymerization reaction in the order in which they were added.
GC-14A). The measured properties are shown in Tables 1 and 2 together with the polymerization conditions and the like.

[0052]

Example 6 The monomers to be added were 90 g of CHD and 10 g
A hydrogen diblock polymer was obtained in the same manner as in Example 1 except that isoprene (Ip) was used. The order of addition was in the order of isoprene (Ip) and CHD. The fact that all the monomers were consumed in the polymerization reaction in the order in which they were added was determined by gas chromatography (GC-14, manufactured by Shimadzu Corporation).
A). The measured properties are shown in Tables 1 and 2 together with the polymerization conditions and the like.

[0053]

Example 7 Monomers to be added were 80 g of CHD and 20 g
A hydrogenated diblock polymer was obtained in the same manner as in Example 1 except that styrene (Sty) was used. The order of addition was styrene (Sty) and then CHD. The fact that all the monomers were consumed in the polymerization reaction in the order in which they were added was determined by gas chromatography (GC-14, manufactured by Shimadzu Corporation).
A). The measured properties are shown in Tables 1 and 2 together with the polymerization conditions and the like.

[0054]

Example 8 The monomers to be added were 70 g of CHD and 30 g
A hydrogen diblock polymer was obtained in the same manner as in Example 1 except that styrene (Sty) was used. The order of addition was styrene (Sty) and then CHD. The fact that all the monomers were consumed in the polymerization reaction in the order in which they were added was determined by gas chromatography (GC-14, manufactured by Shimadzu Corporation).
A). The measured properties are shown in Tables 1 and 2 together with the polymerization conditions and the like.

[0055]

Comparative Example 1 50 g of CHD and 50 g of monomers to be added were used.
A hydrogen triblock polymer was obtained in the same manner as in Example 1 except that 1,3-butadiene (Bd) was used. The order of addition was 25 g of CHD and 50 of 1,3-butadiene (Bd).
g, and 25 g of CHD. It was confirmed by gas chromatography (GC-14A, manufactured by Shimadzu Corporation) that all of the monomers were consumed in the polymerization reaction in the order in which they were added. The measured properties are shown in Tables 1 and 2 together with the polymerization conditions and the like.

[0056]

Comparative Examples 2 and 3 Optical grade polymethyl methacrylate (PMMA) and polycarbonate (PC) were molded in the same manner as in Example 1, and various physical properties were measured. The results are shown in Table 2 in comparison. As is clear from Table 2, when the hydrogenated polymer of the present invention is used, it has a high heat resistance, that is, a high glass transition temperature and a high heat deformation temperature, which has not been seen so far, and further has optical properties and low hygroscopicity. An optical plastic material having excellent weather resistance and solvent resistance can be provided.

[0057]

Example 9 A hydrogenated polymer was obtained in the same manner as in Example 1. The hydrogenation rate of the obtained polymer was 100%, the number average molecular weight was 3.38 × 10 ⁴ , and the molecular weight distribution was 1.30. Using the test piece after molding, the flexural modulus evaluated by ASTM D790 was 6100 MPa.
Rockwell R hardness evaluated by TMD785 is 12
6 or more.

[0058]

Example 10 Using the hydrogenated polymer obtained in Example 7, a transparent substrate having a thickness of 0.2 mm was formed using a mirror-finished mold. When the thicknesses of all of these transparent substrates were measured, they were in the range of 0.2 ± 0.001 mm, and were excellent in film thickness uniformity.

[0059]

[Embodiment 11] FIG. 1 is a schematic diagram showing a cross-sectional shape of a liquid crystal display panel. An epoxy resin was applied to the transparent plastic substrate 1 obtained in Example 8 as a hard coat layer 2 for preventing scratches, and then baked at 130 ° C. The thickness was about 1 μm. On the opposing surface of the transparent plastic substrate 1, SiOx was deposited as an undercoat layer 3 to a thickness of about 0.1 μm, and then indium tin oxide was deposited as a transparent conductive film 4 by sputtering to a thickness of about 0.2 μm. Further, a top coat layer 5 and a polyimide were spin-coated to a thickness of about 0.05 μm to form an alignment film 6. Further, a polarizing plate 7 was laminated on the outermost surface facing the liquid crystal contact portion. In this manner, five panel materials using the transparent optical material of the present invention as a substrate as a glass substitute substrate were produced. Observation of the obtained panel cross section and surface with a scanning electron microscope revealed that no defects such as pinholes and cracks were observed in all panel materials.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

According to the present invention, light transmission excellent in heat resistance and weather resistance, and excellent in transparency, low birefringence, low water absorption, high rigidity, impact resistance, abrasion resistance, chemical resistance, etc. It has become possible to provide optical materials for use.

[Brief description of the drawings]

FIG. 1 is a schematic partial cross-sectional view of a liquid crystal display panel.

[Description of sign]

 Reference Signs List 1 transparent plastic substrate 2 hard coat layer 3 undercoat layer 4 transparent conductive film 5 top coat layer 6 alignment film 7 polarizing plate

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G11B 7/24 526 G11B 7/24 526N

Claims (4)

[Claims] 1. A hydrogenated polymer obtained by hydrogenating a carbon-carbon double bond portion of a polymer having a polymer main chain represented by the following formula (I) by 50% or more, and having a number average molecular weight: An optical material for light transmission comprising a hydrogenated polymer having a light transmittance of 5,000 to 5,000,000, a light transmittance of 87% or more, and a glass transition temperature of 210 to 250 ° C. [-(A) a- (B) b- (C) c- (D) d- (E) e-] (I) (In the formula (I), A to E are monomers constituting a polymer main chain. Represents a unit, and A to E may be arranged in any order, and a to e represent wt% of each of the monomer units A to E with respect to the total weight of the monomer units A to E.
e satisfies the following relationship. a + b + c + d + e = 10
0, 60 ≦ a ≦ 100, 0 ≦ b <40, 0 ≦ c <40,
0 ≦ d <40 and 0 ≦ e <40. (A): 1,3-cyclohexadiene monomer unit. (B): One or more monomer units selected from chain conjugated diene monomer units. (C): selected from vinyl aromatic monomer units,
One or more monomer units. (D): One or more monomer units selected from polar monomer units. (E): One or more monomer units selected from ethylene and α-olefin-based monomer units. ) 2. The optical material for light transmission according to claim 1, wherein the hydrogenated polymer is a block copolymer. 3. A 1,2-bond in a chain ((A) a) composed of 1,3-cyclohexadiene monomer units of a polymer having a polymer main chain represented by the formula (I): 3. The optical system according to claim 1, wherein the molar ratio of the 1,4-conjugate (1,2-conjugate / 1,4-conjugate) is 40/60 to 90/10. material. 4. A display substrate comprising the optical material for light transmission according to claim 1, 2 or 3.