JP2005292516A - Optical component comprising alicyclic structure-containing polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical component having an inorganic compound film having excellent weather resistance and heat resistance applied on a molded body prepared by molding an alicyclic structure-containing polymer composition. <P>SOLUTION: The optical component has at least one layer of an inorganic compound film deposited on at least a part of the surface of a molded body comprising an alicyclic structure-containing polymer. The first layer of the inorganic compound film is deposited by vapor deposition of niobium pentoxide at a film deposition rate of 5 to 15 Å/sec. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an optical component having at least one layer of an inorganic compound film on the surface of a substrate made of an alicyclic structure-containing polymer composition, and more specifically, an inorganic compound film having excellent weather resistance and heat resistance. It is related with the optical component which has.

Since the alicyclic structure-containing polymer is excellent in transparency, it is used in the production of optical components such as optical recording media, optical lenses, prisms, and light guide plates. On the other hand, in order to give an optical function to an optical component, it is known that an inorganic compound film such as a dielectric film or a metal film is formed on the surface of a substrate and used for a lens or a mirror. Similarly, it is known that various inorganic compound films are formed on an alicyclic structure-containing polymer in order to impart optical properties.
In Patent Document 1, a high refractive index layer such as tantalum pentoxide and niobium pentoxide is formed on the surface of a molded body obtained by molding an alicyclic structure-containing polymer composition, and a low refractive index comprising silicon oxide. A molded body having an antireflection layer having a second layer as a layer, a third layer as a high refractive index layer, and a fourth layer as a low refractive index layer is disclosed.
In Patent Document 2, a layer containing tantalum pentoxide and niobium pentoxide and containing 50% by weight or more of tantalum pentoxide is deposited on the surface of a base material made of a thermoplastic norbornene resin by vacuum deposition. An optical member is disclosed.
On the other hand, in Patent Document 3, when a high refractive material selected from the group consisting of titanium dioxide, tantalum pentoxide, zirconium dioxide, and aluminum oxide is deposited on a quartz substrate by vacuum deposition, the deposition rate of the film material is 15 angstrom / sec. In the following, it is disclosed that an optical element used for light having a wavelength of 250 nm or less without cracking or peeling of the thin film can be obtained when it is optimally produced at 5 angstrom / sec or less.

JP 2002-228845 A JP-A-6-31467 JP 2003-149404 A

However, the inorganic compound films described in Patent Documents 1 and 2 have problems that the adhesion strength of the film after being exposed to a high temperature of 80 ° C. or more is weak or cracked.
In addition, with reference to Patent Document 3, the present inventors laminated tantalum pentoxide by vacuum vapor deposition at a deposition rate of 5 angstrom / sec or less on a molded body obtained by molding an alicyclic structure-containing polymer composition. However, when exposed to high temperatures, the thin film cracked and peeled off.
Therefore, the subject of this invention is providing the optical component which has an inorganic compound film | membrane excellent in a weather resistance and heat resistance on the molded object formed by shape | molding an alicyclic structure containing polymer composition. .

In order to solve the above-mentioned problems, the present inventors have deposited various inorganic compounds under various conditions on a molded product obtained by molding an alicyclic structure-containing polymer composition, and with regard to weather resistance and heat resistance. As a result of investigation, an inorganic compound film obtained by depositing a specific inorganic compound at a specific film forming speed on a molded body formed by molding an alicyclic structure-containing polymer is remarkably excellent in the weather resistance and heat resistance of the film. This finding has led to the completion of the present invention.

Thus, according to the present invention, there is provided an optical component in which at least one layer of an inorganic compound film is formed on at least a part of the surface of a molded body comprising an alicyclic structure-containing polymer composition, An optical component is provided in which the first layer is vacuum-deposited with niobium pentoxide at a film formation rate of 5 to 15 Å / sec.
The inorganic compound film of the optical component is multi-layered, the second layer is preferably a low refractive index layer, the third layer is niobium pentoxide and the fourth layer is more preferably a low refractive index layer, It is particularly preferred that the low refractive index layer is silicon dioxide.

  According to the present invention, there is provided an optical component having an inorganic compound film excellent in weather resistance and heat resistance on a molded body obtained by molding an alicyclic structure-containing polymer composition.

  The optical component of the present invention is formed by molding at least one layer of an inorganic compound film on at least a part of the surface of a molded body made of an alicyclic structure-containing polymer. Is vacuum-deposited at a film formation rate of 5 to 15 Å / sec.

The alicyclic structure-containing polymer used in the present invention has an alicyclic structure in the main chain and / or side chain, and contains an alicyclic structure in the main chain from the viewpoint of mechanical strength, heat resistance, and the like. Those that do are preferred.
Examples of the alicyclic structure include a saturated cyclic hydrocarbon (cycloalkane) structure and an unsaturated cyclic hydrocarbon (cycloalkene) structure.
The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, more preferably 5 to 15 in the mechanical strength, The properties of heat resistance and moldability are highly balanced and suitable.
The proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer may be appropriately selected according to the purpose of use, but is preferably 50% by weight or more, more preferably 70% by weight or more, particularly Preferably it is 90 weight% or more.

  Examples of the alicyclic structure-containing polymer include norbornene polymers, monocyclic cycloalkene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof.

  As the norbornene-based polymer, a ring-opening (co) polymer of a norbornene-based monomer and a monomer copolymerizable therewith if necessary; a norbornene-based monomer and optionally copolymerized therewith Addition (co) polymers with possible monomers; and their hydrides.

  Monocyclic cycloalkene polymers include addition (co) polymers of monocyclic cycloalkene monomers and monomers copolymerizable therewith if necessary; alicyclic conjugated diene monomers Depending on necessity, the addition (co) polymer of the monomer copolymerizable with this and the unsaturated bond part hydrogenated as needed are mentioned.

  As vinyl alicyclic hydrocarbon polymers, (co) polymers of vinylcycloalkane and monomers copolymerizable therewith if necessary; copolymerizable with vinylcycloalkenes as necessary Hydrogenated unsaturated bond portion of (co) polymer with other monomers (excluding vinylcycloalkane); monomer capable of copolymerization with aromatic vinyl monomer as required And a hydride of an aromatic ring and an olefinically unsaturated bond portion of the (co) polymer.

  Of these, ring-opening (co) polymers of norbornene monomers and their hydrides and polymers of vinylcycloalkanes are preferred. Monomers that can be copolymerized with aromatic vinyl monomers as necessary. Hydrogenated aromatic copolymer and olefinic unsaturated bond hydride of (co) polymer with polymer, hydrogenated aromatic vinyl polymer with aromatic vinyl monomer unit ratio of 50% by weight or more That is particularly preferred.

  In the present invention, the norbornene-based monomer, monocyclic cycloalkene, alicyclic conjugated diene, vinylcycloalkane, and vinylcycloalkene are sometimes referred to as “alicyclic structure-containing monomer”.

Examples of the alicyclic structure-containing monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and its derivatives, tricyclo [4.3.0.1 ^2,5 ] deca-3. , 7-diene (common name: dicyclopentadiene), tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, tricyclo [4.4.0.1 ^2,5 ] undec-3,7 -Diene, tricyclo [4.4.0.1 ^2,5 ] undeca-3,8-diene, tricyclo [4.4.0.1 ^2,5 ] undec-3-ene, tetracyclo [7.4. .1 ^10,13 . 0 ^2,7] trideca -2,4,6-11- tetraene (alias: 1,4-methano -1,4,4a, 9a- tetrahydrofluorene), tetracyclo ^{[8.4.0.1 11,14.} 0 ^2,8 ] tetradeca-3,5,7,12-11-tetraene (also known as 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene), tetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10 ] norbornene monomers such as dodec-3-ene (common name: tetracyclododecene) and its derivatives;

Monocyclic cycloalkenes such as cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene;
Cycloaliphatic conjugated dienes such as cyclopentadiene and cyclohexadiene;
Vinylcycloalkenes such as vinylcyclopentene, 2-methyl-4-vinylcyclopentene, vinylcyclohexene; vinylcycloalkanes such as vinylcyclopentane, 2-methyl-4-vinylcyclopentane, vinylcyclohexane, vinylcyclooctane;
Etc.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, divinylbenzene, vinyl naphthalene, and vinyl toluene.
The alicyclic structure-containing monomer and the aromatic vinyl monomer can be used alone or in combination of two or more.

  Examples of the monomer capable of addition polymerization with an alicyclic structure-containing monomer or an aromatic vinyl monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, Chain olefins such as 3-methyl-1-pentene; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene; Examples thereof include conjugated dienes such as 1,3-butadiene, 2-methyl 1,3-butadiene and 1,3-hexadiene. These monomers can be used alone or in combination of two or more.

  The alicyclic structure-containing polymer contains polar groups such as hydroxyl group, carboxyl group, alkoxyl group, epoxy group, glycidyl group, oxycarbonyl group, carbonyl group, amide group, ester group, and acid anhydride group. Also good.

  There are no particular restrictions on the polymerization method of the alicyclic structure-containing monomer or aromatic vinyl monomer, and the hydrogenation method performed as necessary to the obtained alicyclic structure-containing polymer, and it is publicly known It can be performed according to the method.

The ring-opening (co) polymerization reaction of the norbornene-based monomer can be performed in a solvent at a temperature of −50 to 100 ° C. and a pressure of 0 to 5 MPa, usually using a ring-opening polymerization catalyst.
The ring-opening polymerization catalyst includes a metal halide such as ruthenium, palladium, osmium and platinum, a catalyst comprising a nitrate or acetylacetone compound and a reducing agent, or a metal halogen such as titanium, vanadium, zirconium, tungsten and molybdenum. And a catalyst comprising a compound or an acetylacetone compound and a co-catalyst organoaluminum compound.

The addition (co) polymerization reaction of a norbornene-based monomer and a monocyclic cycloalkene, or a monomer copolymerizable therewith, is usually performed at a temperature of −50 ° C. to 100 ° C. and a pressure of 0 to 0 using an addition polymerization catalyst. It can be performed at 5 MPa.
Examples of the addition polymerization catalyst include a catalyst composed of titanium, zirconium, or a vanadium compound and a co-catalyst organoaluminum compound.

  The polymerization reaction of the aromatic vinyl monomer, vinylcycloalkene, or vinylcycloalkane may be any of known methods such as radical polymerization, anion polymerization, and cationic polymerization. In the polymerization, the molecular weight distribution is widened and the mechanical strength of the molded product tends to be lowered, so that anionic polymerization is preferred. Further, any of suspension polymerization, solution polymerization, bulk polymerization, and the like may be used.

The anionic polymerization reaction of an aromatic vinyl monomer, vinylcycloalkene or vinylcycloalkane is usually at a reaction temperature of −70 to 150 ° C., preferably −50 to 120 ° C. using a polymerization catalyst in an organic solvent. The reaction time can be 0.01 to 20 hours, preferably 0.1 to 10 hours.
Examples of the polymerization catalyst include organic alkali metals such as n-butyl lithium and 1,4-dilithiobutane. When a Lewis base such as dibutyl ether or triethylamine is added, a polymer having a narrow molecular weight distribution is obtained. It is preferable in terms of securing strength and heat resistance.
Examples of the organic solvent include aliphatic hydrocarbons such as n-pentane, n-hexane, and isooctane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene and toluene; ethers such as tetrahydrofuran and dioxane. And the like.
The amount of the organic solvent used is preferably such that the monomer concentration is 1 to 40% by weight, more preferably 10 to 30% by weight.
The polymer may be either a random or block copolymer, but is preferably a random copolymer.
The polymer may be any of isotactic, syndiotactic and atactic.

  Polymerization of the alicyclic conjugated diene can be carried out by a known method described in, for example, JP-A-6-136057 and JP-A-7-258318.

The polymerization conversion rate of the alicyclic structure-containing polymer is preferably 95% by weight or more, more preferably 97% by weight or more, and particularly preferably 99% by weight or more. A high polymerization conversion rate is preferable because a molded product with a small amount of released organic matter can be obtained.
In the present invention, the polymerization conversion rate is a value obtained by dividing the value obtained by subtracting the weight of the unreacted monomer from the weight of the used monomer by the weight of the used monomer.

The alicyclic structure-containing polymer can hydrogenate the carbon, carbon-carbon unsaturated bonds in the ring, main chain, and side chain after the polymerization reaction.
In the alicyclic structure-containing polymer, the ratio of the number of carbon-carbon double bonds to the total number of carbon-carbon bonds in the polymer is preferably 0.15% or less, and is 0.07% or less. More preferably, it is especially preferable in it being 0.02% or less. When the ratio of the number of carbon-carbon double bonds is small, a molded product with a small amount of released organic matter is obtained, which is preferable.

In the hydrogenation reaction, the amount of hydrogenation catalyst used, the reaction temperature, the hydrogen partial pressure, the reaction time, and the reaction solution concentration can be appropriately set within the optimum range depending on the type of polymer to be hydrogenated.
Although it does not specifically limit as a hydrogenation catalyst, The homogeneous catalyst formed in combination with metal compounds, such as nickel and cobalt, and organic aluminum and organic lithium is preferable.
Further, as the hydrogenation catalyst, a support such as activated carbon, diatomaceous earth, or magnesia can be used as necessary.
The amount of the hydrogenation catalyst used is 0.01 to 50 parts by weight per 100 parts by weight of the polymer, the reaction temperature is 25 to 300 ° C., the hydrogen partial pressure is 0.5 to 10 MPa, and the reaction time is 0.5 to It is preferably 20 hours.

  The hydrogenated alicyclic structure-containing polymer can be obtained by filtering the hydrogenation reaction solution and removing the solvent and the like from the solution obtained by filtering the hydrogenation catalyst.

Examples of the method for removing the solvent include a coagulation method and a direct drying method.
The coagulation method is a method in which a polymer is precipitated by mixing a polymer solution with a poor solvent for the polymer. The precipitated small polymer (crumb) is subjected to solid-liquid separation, and the polymer is dried by heating to remove the solvent.
Examples of the poor solvent include polar solvents such as alcohols such as ethyl alcohol, n-propyl alcohol or isopropyl alcohol; ketones such as acetone or methyl ethyl ketone; esters such as ethyl acetate or butyl acetate.
The direct drying method is a method in which a polymer solution is heated under reduced pressure to remove a solvent, and known methods such as a centrifugal thin film continuous evaporation dryer, a scratched heat exchange type continuous reactor type dryer, and a high viscosity reactor device are known. This can be done using an apparatus. The degree of vacuum and temperature can be appropriately selected depending on the apparatus.

The volatile component content of the alicyclic structure-containing polymer is preferably 0.5% by weight or less. When the volatile component content is within this range, a molded product with less volatile components such as the amount of released water and the amount of released organic matter is obtained, which is preferable.
In the present invention, the volatile component content is volatilized when heated from 30 ° C. to 350 ° C. at 10 ° C./min using a differential thermogravimetric measuring device (“TG / DTA200” manufactured by Seiko Instruments Inc.). The amount of ingredients.
The method for reducing the volatile components is not particularly limited. In addition to the method of removing other released moisture and released organic substances simultaneously with the solvent from the polymer solution by the above-mentioned coagulation method and direct drying method, the steam stripping method, Examples thereof include a ripping method and a nitrogen stripping method. Among these, the coagulation method and the direct drying method are preferable because they are excellent in productivity.

The alicyclic structure-containing polymer is preferable when the solvent is removed by coagulation or direct drying, and further heating and drying under reduced pressure, since a molded product with less released water and less released organic matter can be obtained.
The pressure at the time of drying is preferably 10 kPa or less, and more preferably 3 kPa or less.
The heating temperature is preferably 260 ° C. or higher, and more preferably 280 ° C. or higher.

The glass transition temperature of the alicyclic structure-containing polymer (hereinafter sometimes referred to as Tg. A block copolymer having two or more Tg indicates a higher value) is in the range of 60 to 200 ° C. It is preferable, it is more preferable in the range of 70 to 180 ° C, and particularly preferable in the range of 90 to 160 ° C. When Tg is in this range, it is preferable in terms of heat resistance and workability.
In the present invention, Tg is a value measured using a differential scanning calorimeter.

  The weight average molecular weight (Mw) of the alicyclic structure-containing polymer is not particularly limited, but when the polymer is a block copolymer, the weight average molecular weight (Mw) is in the range of 50,000 to 300,000. Is preferable, it is more preferable in the range of 55,000 to 200,000, and particularly preferable in the range of 60,000 to 150,000. Further, when the polymer is a random copolymer or a homopolymer, the weight average molecular weight (Mw) is preferably in the range of 5,000 to 500,000, and in the range of 10,000 to 200,000. More preferably. When Mw is in this range, the mechanical strength is high and the molding time can be shortened, so that the thermal decomposition of the polymer is difficult to occur, and the organic matter release amount is reduced, which is preferable.

  The molecular weight distribution (Mw / Mn) (ratio of weight average molecular weight (Mw) and number average molecular weight (Mn)) of the alicyclic structure-containing polymer is preferably in the range of 1 to 2, preferably 1 to 1.5. Is more preferable, and it is especially preferable in the range of 1 to 1.2. It is preferable that Mw / Mn is in this range because mechanical strength and heat resistance are highly balanced.

The alicyclic structure-containing polymer can be made into an alicyclic structure-containing polymer composition by containing a known additive as required so long as the effects of the invention are not impaired.
Known additives include other polymers, fillers, antioxidants, release agents, flame retardants, antibacterial agents, wood flour, coupling agents, plasticizers, colorants, lubricants, silicone oils, foaming agents, interfaces. Activators, light stabilizers, lubricants and dispersion aids, heat stabilizers, UV absorbers, antistatic agents, dispersants, chlorine scavengers, crystallization nucleating agents, antifogging agents, organic matter fillers, neutralizing agents, decomposition Agents, metal deactivators, antifouling materials, thermoplastic elastomers and the like.
These additives can be used alone or in admixture of two or more.

Other polymers include styrene-butadiene-styrene block copolymer main chain hydride (= styrene-ethylene-butylene-styrene block copolymer [SEBS]) and styrene-isoprene-styrene block copolymer. Main chain hydride (= styrene-ethylene-propylene-styrene block copolymer [SEPS]) and the like.
Addition of such other polymer components is preferable because it becomes less likely to become clouded at high temperature and high humidity. The metal content of such other polymer components is preferably 50 ppm or less, and particularly preferably 30 ppm or less. The amount of the other polymer component is preferably in the range of 0.5 to 70 parts by weight and more preferably in the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the alicyclic structure-containing polymer. .

  As filler, glass fiber, carbon fiber, metal fiber, metal flake, glass bead, wollastonite, rock filler, calcium carbonate, talc, silica, mica, glass flake, milled fiber for the purpose of improving mechanical properties , Kaolin, barium sulfate, graphite, molybdenum disulfide, magnesium oxide, zinc oxide whisker, potassium titanate whisker and the like.

  As a method for producing an alicyclic structure-containing polymer composition, a method for obtaining a pellet-shaped resin composition by kneading an alicyclic structure-containing polymer and an additive added as necessary; Examples thereof include a method of obtaining a resin composition by mixing an alicyclic structure-containing polymer and an additive to be added if necessary in an appropriate solvent and removing the solvent.

  For kneading, a melt kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, or a feeder ruder can be used. The kneading temperature is preferably in the range of 200 to 400 ° C, and more preferably in the range of 240 to 350 ° C. Further, when kneading, the components may be added together and kneaded, or may be kneaded while adding in several times.

  The alicyclic structure-containing polymer composition can be formed into a molded body using a known molding means such as an injection molding method, a compression molding method, and an extrusion molding method. The shape of the molded body can be appropriately selected depending on the application.

The molding conditions are not particularly limited. For example, the resin temperature during molding is usually 200 ° C to 400 ° C, preferably 210 ° C to 350 ° C. In addition, when using a mold, the mold temperature t ₀ ° C is usually room temperature <t ₀ <(t ₁ +15) ° C, where the glass transition temperature of the alicyclic structure-containing polymer used is t ₁ ° C. Preferably, (t ₁ -30) <t ₀ <(t ₁ +10) ° C., more preferably (t ₁ −20) <t ₀ <(t ₁ +5) ° C. _(However, (t 1 -30) <room temperature, or _(t 1 -20) ℃ <If it is room temperature, and room temperature _{<t 0} ℃.) Resin temperature during molding, the mold temperature is within this range From the viewpoint of releasability.

(Inorganic compound film)
In the optical product of the present invention, the first layer of the inorganic compound film is made of niobium pentoxide.
The purity of niobium pentoxide is preferably 90% or more, more preferably 95% or more, and particularly preferably 97% or more. When the purity of niobium pentoxide is in this range, it is preferable in terms of optical properties and adhesion.

The film made of niobium pentoxide is formed by vacuum-depositing niobium pentoxide at a film forming rate of 5 to 15 angstroms / sec on the surface of a molded body made of the alicyclic structure-containing polymer.
Among these, the film formation rate is preferably in the range of 6 to 13 angstrom / sec, and more preferably in the range of 7 to 11 angstrom / sec.
If the film formation rate is too slow, the adhesion and crack resistance after being left under high temperature and high temperature and high humidity conditions decrease, and if it is too fast, it becomes difficult to control the optical properties.

  There are no particular restrictions on the method for adjusting the film formation speed, but there is a method for adjusting the deposition controller with a crystal oscillation film deposition controller, and the reflectivity when light is projected onto the monitor substrate and deposited on that substrate. The optical film thickness meter that controls the film thickness, the method of controlling while calculating by comparing the deposition time on the monitor substrate and the obtained film thickness, etc. A method using a crystal oscillation type film formation controller is preferable in that adjustment is possible.

The thickness of the niobium pentoxide film is preferably in the range of 10 to 10,000 angstroms, more preferably in the range of 20 to 5,000 angstroms, and in the range of 30 to 3,000 angstroms. Particularly preferred.
When the thickness of the film made of niobium pentoxide is in this range, it is preferable in terms of adhesion and crack resistance.

Other vapor deposition conditions are not particularly limited, but after evacuating the inside of the vacuum chamber to 10 ⁻⁴ to 10 ⁻² Pa using an oil rotary pump, oil diffusion pump, cryopump, etc., vapor deposition is performed as necessary. Oxygen can sometimes be introduced into a vacuum chamber at about 2.0 × 10 ^{−3 to} 1.0 × 10 ⁻¹ Pa and deposited in an oxygen atmosphere.
Although there is no particular limitation on the evaporation method of the deposited film material, usually, an electron beam heating method, a resistance heating method, or the like is used, and an electron beam method that can easily adjust the film formation rate is preferable.

In the optical component of the present invention, the second and subsequent layers can be further laminated on the first layer of niobium pentoxide film.
The film composition laminated after the second layer includes dielectric compounds such as metal oxides, inorganic oxides, metal sulfides, and metal fluorides; inorganic compounds such as metals; organic compounds; or mixtures or hybrids thereof. Is mentioned. By laminating about 1 to 7 layers of these films, the adhesion of the entire film can be further enhanced.
Among these, inorganic compounds are preferable, and it is preferable that they are excellent in adhesion to adjacent films and stable in the air and water.

  Metal oxides include aluminum oxide, bismuth oxide, cerium oxide, chromium oxide, europium oxide, iron oxide, ruthenium oxide, indium oxide, lanthanum oxide, molybdenum oxide, magnesium oxide, neodymium oxide, lead oxide, praseodymium oxide, samarium oxide And metal oxides having different acid values such as antimony oxide, scandium oxide, tin oxide, titanium oxide, tantalum oxide, tungsten oxide, yttrium oxide, zirconium oxide, zinc oxide, niobium oxide, and mixtures thereof.

  Examples of inorganic oxides include silicon dioxide and silicon monoxide, and blends thereof.

  Examples of the metal sulfide include zinc sulfide.

  Metal fluorides include aluminum fluoride, barium fluoride, cerium fluoride, calcium fluoride, lanthanum fluoride, lithium fluoride, magnesium fluoride, cryolite, thiolite, neodymium fluoride, sodium fluoride, lead fluoride Samarium fluoride, strontium fluoride, and a mixture thereof.

  Examples of the metal include gold, platinum, silver, copper, aluminum, rhodium, chromium, and the like (alloys). Of these, gold, silver, aluminum and the like are preferable for enhancing the reflection function.

  Examples of the organic compound include organic silicon compounds such as silane coupling agents, acrylic resins, vinyl resins, melamine resins, epoxy resins, fluorine resins, and silicone resins.

Further, when the film is an antireflection film, it is preferable to form a multilayer film by combining a high refractive layer and a low refractive layer.
Examples of the composition of the high refractive layer include titanium oxide, tantalum pentoxide, zirconium oxide, aluminum oxide, and niobium pentoxide. Examples of the composition of the low refractive layer include silicon dioxide and magnesium fluoride. Among them, a multilayer film in which niobium pentoxide is used as the composition of the high refractive layer and the composition silicon dioxide of the low refractive layer is alternately laminated is preferable.

Examples of the method for forming the second and subsequent layers on the optical component of the present invention include known methods such as a thermal curing method, an ultraviolet curing method, a vacuum deposition method, a sputtering method, and an ion plating method.
Among them, the vacuum deposition method is preferable, and the film formation rate after the second layer is more preferably in the range of 5 to 15 angstrom / sec, particularly preferably in the range of 6 to 14 angstrom / sec, and 7 to 13 angstrom. / Sec is most preferable.

The thickness of the second and subsequent layers is preferably in the range of 10 to 10,000 angstroms, more preferably in the range of 20 to 5,000 angstroms, and in the range of 30 to 3,000 angstroms. Is particularly preferred.
When the thickness of the film is within this range, it is preferable in terms of adhesion and crack resistance.

The thickness of the entire film is preferably in the range of 20 to 20,000 angstroms, more preferably in the range of 40 to 10,000 angstroms, and particularly preferably in the range of 60 to 5,000 angstroms.
When the thickness of the entire film is in this range, it is preferable in terms of adhesion and crack resistance.

  The optical component of the present invention has functions such as an antireflection film having a specific wavelength, a semi-transmissive film having wavelength selectivity, and a total reflection film, and is excellent in the weather resistance and heat resistance of the film.

Although there is no restriction | limiting in particular as an application of the optical component of this invention, Lenses, such as a diffraction grating; Pickup objective lens, a collimator lens, an imaging lens for cameras, a telescope lens, fθ lens for laser beams, and a Selfoc lens; fθ mirror Reflective devices such as polygon mirrors; prisms such as finder prisms and prisms with lens functions; optical discs such as optical video discs, audio discs, document file discs, and memory discs; optical materials such as optical films such as OHP films Optical semiconductor sealing materials such as photo interrupters, photo couplers, and LED lamps; sealing materials for IC memories such as IC cards; retardation plates for liquid crystal display devices, touch panels, light diffusion plates, light guide plates, polarizing plate protection Film, condensing sheet, prism sheet, lenty It can be used for optical components for flat panel displays such as a curl lens; optical fiber; optical connector;
In particular, it is suitable for reflection lenses such as pickup lenses, fθ lenses for laser beams, imaging lenses, and mirrors, and mirrors.

  Hereinafter, the present invention will be described more specifically with reference to production examples, examples and comparative examples. Moreover, this invention is not restrict | limited by these. Parts and% are based on weight unless otherwise specified. Further, the pressure is a gauge pressure unless otherwise specified.

Various physical properties were measured according to the following methods.
(1) Film weather resistance test (crack)
Crack resistance was evaluated by the following method. A film part of an optical component left after molding for 100 hours under a condition of 85 ° C. is observed with an optical microscope (manufactured by Olympus) at a magnification of 100 times. The thing was evaluated as bad (x).
(2) Film weather resistance test (adhesion)
Adhesive tape (manufactured by 3M, No. 3305, adhesive strength 9.41 N / cm) is pasted on the film part of the optical part immediately after molding left at 85 ° C. for 100 hours and then left at room temperature for 1 hour. The tape was completely attached to the deposited film. Two minutes after the tape was attached, one end of the tape was held, kept perpendicular to the vapor deposition surface, and peeled off instantaneously, and the adhesion was evaluated according to the following evaluation criteria.
(Evaluation criteria)
The test in which the peeling test was tried 6 times and peeling did not occur (○),
The case where peeling occurred within 6 times was defined as (x).
(3) Hydrogenation rate The hydrogen conversion rate to the unsaturated bond of the alicyclic structure-containing polymer was measured by ¹ H-NMR.
(4) Glass transition temperature (Tg)
The Tg of the alicyclic structure-containing polymer was measured by a differential scanning calorimeter based on JIS K7121 at a temperature increase rate of 10 ° C./min.
(5) Molecular weight The molecular weight of the alicyclic structure-containing polymer was measured by gel permeation chromatography (GPC) at 40 ° C. using cyclohexane as a solvent, and the number average molecular weight (Mn) and weight average in terms of standard polyisoprene. The molecular weight (Mw) was determined.

[Production Example 1]
A stainless steel reactor equipped with a stirrer that was dried and purged with nitrogen was charged with 300 parts of dehydrated cyclohexane, 25 parts of styrene and 0.20 part of dibutyl ether, and stirred at 60 ° C. with an n-butyllithium solution (15% (Containing hexane solution) 0.45 part was added to initiate the polymerization reaction, and the polymerization reaction was carried out for 1 hour. Next, 15 parts of styrene was added to the reaction solution, and a polymerization reaction was further performed for 1 hour. Next, 20 parts of isoprene was added to the reaction solution, and a polymerization reaction was further performed for 1 hour. Next, 40 parts of styrene was continuously added to the reaction solution over 1 hour, and the polymerization reaction was continued for 1 hour. Next, 0.2 parts of isopropyl alcohol was added to the reaction solution to stop the reaction.

400 parts of the polymerization reaction solution was transferred to a pressure-resistant reactor equipped with a stirrer, and 3 parts of a diatomaceous earth supported nickel catalyst (manufactured by JGC Chemicals; E22U) was added and mixed as a hydrogenation catalyst. Next, the gas phase inside the reactor is replaced with hydrogen gas, and hydrogen is further supplied while stirring the solution, and a hydrogenation reaction is performed at a temperature of 170 ° C. and a pressure of 4.5 MPa for 5 hours to obtain a hydrogenated polymer solution. Obtained. After completion of the hydrogenation reaction, the reaction solution is filtered to remove the hydrogenation catalyst, and then 0.1 part of an antioxidant Irganox 1010 (manufactured by Ciba Specialty Chemicals) is added and dissolved, and a thin film dryer (Buss Corporation) is added. The film and the volatile component are removed under the conditions of 260.degree. C., 9.33.times.10.sup.- ⁴ MPa (absolute pressure) and residence time of 1.2 hours. Was extruded into a strand shape from a die, cooled with water, and then cut with a pelletizer to obtain pellets.
The resulting hydrogenated polymer is a hydrogenated ternary block comprising a block containing repeating units derived from styrene, a block containing repeating units derived from isoprene, and a block containing repeating units derived from styrene. It is a copolymer resin.
Mw of the obtained hydrogenated polymer was 82,000, Mw / Mn was 1.20, the hydrogenation rate of the main chain and the aromatic ring was 99.9%, and Tg was 128 ° C.

[Production Example 2]
Under a nitrogen atmosphere, 100 parts by weight of 6-ethyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene (hereinafter abbreviated as ETCD) is added to a known metathesis. Polymerization was performed using a ring-opening polymerization catalyst system, and then hydrogenated by a known method to obtain a hydrogenated ETCD ring-opening polymer. After completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst, and then the solvent and volatile components were removed under the conditions of 260 ° C., 9.33 × 10 ⁻⁴ MPa (absolute pressure) and residence time of 1.2 hours. After removal, the polymer in a molten state was extruded from a die into a strand, cooled with water, and then cut with a pelletizer to obtain pellets.
The number average molecular weight Mn of the obtained hydrogenated polymer was 28,000, the hydrogenation rate was 99.8% or more, and Tg was 138 ° C.
0.2 parts by weight of the phenolic antioxidant pentaerythrityl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and 0.4 parts by weight per 100 parts by weight of the pellets Part of hydrogenated styrene / butadiene / styrene block copolymer (Taftec H1051, manufactured by Asahi Kasei Kogyo Co., Ltd., crumb, refractive index 1.52 at 30 ° C.), kneaded with a biaxial kneader, and strand (rod-shaped) The molten resin was extruded and cut to obtain pellets.

[Production Example 3]
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene (250 parts), 1-hexene (41 parts), and toluene (750 parts) were charged into a reaction vessel purged with nitrogen, and the solution was heated to 60 ° C. Next, 0.62 part of a toluene solution of triethylaluminum (1.5 mol / l) and tungsten hexachloride modified with t-butanol / methanol (t-butanol: methanol: tungsten) were added to the solution in the reaction vessel. Toluene solution (concentration: 0.05 mol / l) of 35 mol: 0.3 mol: 1 mol) was added, and then heated and stirred at 80 ° C. for 3 hours to obtain a ring-opening polymer solution. . The polymerization conversion rate was 97%. 4,000 parts of the resulting ring-opening polymer solution was charged into an autoclave, 0.48 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added, hydrogen pressure 100 kg / cm ² , reaction temperature 165 The mixture was heated and stirred for 3 hours under the condition of ° C to obtain a hydrogenated polymer solution.
After completion of the hydrogenation reaction, the reaction solution is filtered to remove the hydrogenation catalyst, and then 0.1 part of an antioxidant Irganox 1010 (manufactured by Ciba Specialty Chemicals) is added and dissolved, and a thin film dryer (Buss Corporation) is added. The film and the volatile component were removed under the conditions of 260 ° C., 7 Torr (9.33 × 10 ⁻⁴ MPa; absolute pressure) and residence time of 1.2 hours using a film truder. The polymer was extruded from the die into a strand, cooled with water, and cut with a pelletizer to obtain pellets.
The hydrogenation rate of the obtained hydrogenated polymer was substantially 100%.

[Production Example 4]
To a 15 liter autoclave that has been dried under reduced pressure and purged with nitrogen, 887 g of norbornene, 1100 ml of styrene, 777 ml of cyclohexane, and 3 ml of a 1 mmol / ml cyclohexane solution of triisobutyl ruminium are added at room temperature. After pressurizing to cm ² , the pressure was released, and this pressure release operation was repeated three times. Thereafter, the inside pressure of the system was increased to 1.5 kg / cm ² with ethylene, and the temperature was raised to reach 70 ° C. Thereafter, the inner pressure was increased to 6 kg / cm ² with ethylene. After stirring for 15 minutes, 13.7 ml of the previously prepared catalyst solution was added to the system to initiate copolymerization of ethylene and norbornene. The catalyst concentration at this time was 0.0123 mmol / liter of isopropylidene-bis (indenyl) zirconium dichloride and 7.5 mmol / liter of methylaluminoxane with respect to the entire system. During the polymerization, the internal pressure was maintained at 6 kg / cm ² by continuously supplying ethylene. After 60 minutes, the polymerization reaction was stopped by adding isopropyl alcohol. After depressurization, the polymer solution was taken out and washed with an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water at a ratio of 1: 1 to transfer the catalyst residue to the aqueous phase. After this contact mixed solution was allowed to stand, the aqueous phase was separated and removed, and further washed twice with distilled water, and the polymerization liquid phase was separated into oil and water. Next, the polymer liquid phase separated from oil and water was brought into contact with 3 times the amount of acetone under strong stirring to precipitate the polymer, and then washed thoroughly with acetone, and the solid part (copolymer) was collected by filtration, and nitrogen was removed. It was dried for 12 hours at 130 ° C. and 350 mmHg under circulation.
The intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. of the obtained polymer was 0.8 dl / g, Tg was 142 ° C., the norbornene content was 41.1 mol%, and the styrene content was 9.8 mol%. there were.

[Example 1]
After the pellets obtained in Production Example 1 were preliminarily heated at 100 ° C. for 4 hours, the injection molding apparatus (product number: α-100B manufactured by FANUC CORPORATION) was used for injection molding to obtain a thickness of 3 mm. A base material having a length and width of 65 mm was formed. The molding conditions were a mold temperature of 100 ° C. and a cylinder temperature of 250 ° C.
Niobium pentoxide as the material for the high refractive index vapor deposition film is set in the evaporation source (1) of the vacuum evaporation system (manufactured by Syncron Co., Ltd., BMC850), and silicon oxide is set as the material for the low refractive index vapor deposition film in the evaporation source (2) did. The base material produced by the method described above was set in the base material fixing jig above it. Further, a quartz oscillation type film formation controller (XTC vapor deposition controller, manufactured by INFICON) was used for monitoring the vapor deposition rate and film thickness. After the vacuum chamber is evacuated and the degree of vacuum becomes 10 ⁻³ Pa or less, the electron beam is irradiated to the material for the high refractive index vapor deposition film, this is dissolved, and the first layer of niobium pentoxide film is deposited. A thickness of 1061 Å was formed at 5.3 Å / sec. Next, the low refractive index material was dissolved in the same manner, and a film having a thickness of 391 Å was formed on the niobium pentoxide at a deposition rate of 10 Å / sec. Subsequently, similarly, a niobium pentoxide film was formed at a deposition rate of 5.3 angstrom / sec and a thickness of 1217 angstrom, and a silicon oxide film was formed at a deposition speed of 10 angstrom / sec and a thickness of 845 angstrom was formed. A film was produced to obtain an optical component 1 having a light reflection preventing film.
The film of the obtained optical component 1 was evaluated for weather resistance. The results are listed in Table 1.

[Example 2]
Instead of the polymer obtained in Production Example 1, the base material was molded in the same manner as in Example 1 except that the polymer obtained in Production Example 2 was used and the cylinder temperature during injection molding was changed to 270 ° C. The optical component 2 was obtained by forming an antireflection film at the same film formation rate.
The film of the obtained optical component 2 was evaluated for weather resistance. The results are listed in Table 1.

[Example 3]
Instead of the polymer obtained in Production Example 1, the base material was molded in the same manner as in Example 1 except that the polymer obtained in Production Example 3 was used and the cylinder temperature during injection molding was changed to 270 ° C. The optical component 3 was obtained by forming an antireflection film at the same film formation rate.
The film of the obtained optical component 2 was evaluated for weather resistance. The results are listed in Table 1.

[Example 4]
A base material was molded in the same manner as in Example 1 except that the polymer obtained in Production Example 4 was used instead of the polymer obtained in Production Example 1 and the cylinder temperature during injection molding was changed to 250 ° C. The optical component 4 was obtained by forming an antireflection film at the same film formation rate.
The film of the obtained optical component 4 was evaluated for weather resistance. The results are listed in Table 1.

[Example 5]
The base material was molded in the same manner as in Example 1 except that the film formation rate during the formation of niobium pentoxide was changed to 10.5 (angstrom / sec), and an antireflection film was formed at each film formation rate. Thus, an optical component 5 was obtained.
The film of the obtained optical component 5 was evaluated for weather resistance. The results are listed in Table 1.

[Comparative Example 1]
A base material was molded in the same manner as in Example 1 except that tantalum pentoxide was formed in the first and third layers, and an optical reflection preventing film was formed at the same film formation rate to obtain an optical component 6.
The film of the obtained optical component 6 was evaluated for weather resistance. The results are listed in Table 1.

[Comparative Example 2]
The base material was molded in the same manner as in Comparative Example 1 except that the film formation rate during the formation of tantalum pentoxide was changed to 3.0 (angstrom / sec), and an antireflection film was formed at the same film formation rate. Thus, an optical component 7 was obtained.
The film of the obtained optical component 7 was evaluated for weather resistance. The results are listed in Table 1.

[Comparative Example 3]
The base material was molded in the same manner as in Example 1 except that the film formation rate at the time of forming the niobium pentoxide was changed to 3.0 (angstrom / sec), and an antireflection film was formed at each film formation rate. Thus, an optical component 8 was obtained.
The film of the obtained optical component 8 was evaluated for weather resistance. The results are listed in Table 1.

[Comparative Example 4]
The base material was molded in the same manner as in Example 1 except that the film formation rate during the formation of niobium pentoxide was changed to 2.4 (angstrom / sec), and an antireflection film was formed at each film formation rate. Thus, an optical component 9 was obtained.
The film of the obtained optical component 9 was evaluated for the weather resistance. The results are listed in Table 1.

Table 1 shows the following.
An optical component in which at least one layer of an inorganic compound film is formed on at least a part of the surface of a molded body made of an alicyclic structure-containing polymer, wherein the first layer of the inorganic compound film contains 5 niobium pentoxide. An optical component formed by vacuum deposition at a film formation rate of ˜15 Å / sec has very good weather resistance. On the other hand, the optical component whose first layer is tantalum pentoxide is inferior in weather resistance (Comparative Examples 1 and 2). Further, a niobium pentoxide film deposited under a condition in which the film formation rate deviates from 5 to 15 angstrom / sec is inferior in weather resistance.

  The optical component of the present invention has an inorganic compound film excellent in weather resistance and heat resistance on a molded body formed by molding an alicyclic structure-containing polymer composition, so that it can be used for a pickup lens or a laser beam fθ. Suitable for lenses such as lenses and imaging lenses, and reflective devices such as mirrors.

Claims (4)

An optical component in which at least one layer of an inorganic compound film is formed on at least a part of the surface of a molded article comprising an alicyclic structure-containing polymer composition, wherein the first layer of the inorganic compound film is niobium pentoxide Is an optical component formed by vacuum deposition at a film formation rate of 5 to 15 Å / sec. The optical component according to claim 1, wherein the inorganic compound film is a multilayer and the second layer is a low refractive index layer. The optical component according to claim 2, wherein the third layer is niobium pentoxide and the fourth layer is a low refractive index layer. The optical component according to claim 3, wherein the low refractive index layer is silicon dioxide.