JP5093027B2 - Optical resin composition, method for producing the same, and optical component formed from the optical resin composition - Google Patents

Description

  The present invention relates to an optical resin composition containing an alicyclic structure-containing polymer and having excellent laser resistance and high light transmittance. The optical resin composition of the present invention is suitably used as a resin material for optical components such as optical lenses for blue-violet lasers in the wavelength range of 390 to 430 nm. The present invention also relates to a method for producing the optical resin composition.

  Multimedia that can transmit and receive high-speed information such as video, images, sounds, and characters using multiple different service forms such as communication and broadcasting has been developed. Personal computers, audio / visual devices, and televisions that support such multimedia Game consoles are rapidly spreading.

  Multimedia-compatible devices are equipped with optical recording media such as CD-ROM, CD-R, MD, and DVD for storing and / or reproducing information. Since the amount of information by multimedia increases year by year, it is required to increase the recording density of the optical recording medium and increase the recording capacity in order to cope with it. As the recording density of optical information recording media is increased, it is necessary to make the laser beam used for writing information to the optical information recording medium and / or reading the recorded information shorter.

  In recent years, semiconductor lasers having a short oscillation wavelength such as a blue-violet laser having a wavelength of 390 to 430 nm have been developed, and laser oscillation with a shorter wavelength than conventional red semiconductor lasers has become possible.

  In an optical information recording system using laser light, a lens (referred to as a “pickup lens”) for focusing the laser light on a recording surface is used. As the pickup lens, an aspheric plastic lens is generally used. Since plastic lenses are used under conditions where laser light is irradiated and transmitted, they have excellent laser resistance and can maintain high transparency stably without deterioration of performance due to irradiation and transmission of laser light. It is required to have performance.

  Patent Document 1 (Japanese Patent Laid-Open No. 2001-139756) proposes an optical resin composition containing an alicyclic structure-containing polymer and an antioxidant. Patent Document 1 describes that a molded article made of the optical resin composition is excellent in transparency and excellent in heat resistance and coloration resistance over a long period of time.

  Patent Document 2 (Japanese Patent Application Laid-Open No. 2003-270401) discloses an optical molding containing a vinyl alicyclic hydrocarbon polymer and a phosphorus-based antioxidant and / or a phenol-based antioxidant having a hindered phenol group. The body has been proposed. In Patent Document 2, the optical molded body has an error rate for a long period of time even when information is written to or read from an information recording medium by transmitting a short wavelength laser beam with high intensity. It does not increase, and there is no deterioration in mechanical strength.

  Patent Document 3 (International Publication No. 2004/085538 pamphlet) proposes a resin composition containing an alicyclic structure-containing polymer and a hindered amine compound. Patent Document 3 describes that a molded body made of the resin composition can maintain stable transparency without being ablated on the surface of the molded body when irradiated with a short wavelength light beam such as a blue laser. Yes.

  Thus, the resin composition containing an alicyclic structure-containing polymer and various antioxidants has various properties suitable for the use of optical parts such as optical lenses. On the other hand, a blue-violet laser having a wavelength of 390 to 430 nm has a very strong tendency to deteriorate a laser transmission object. An optical component formed by molding a conventional optical resin composition is not yet sufficient in laser resistance, and in particular, has insufficient resistance to a blue-violet laser having a wavelength of 390 to 430 nm. For this reason, optical parts molded from optical resin compositions containing conventional alicyclic structure-containing polymers gradually deteriorate in function due to irradiation and transmission of blue-violet laser, and can maintain high light transmittance over a long period of time. Have difficulty.

JP 2001-139756 A JP 2003-270401 A International Publication No. 2004/085538 Pamphlet

  An object of the present invention is an optical resin composition containing an alicyclic structure-containing polymer, and exhibits excellent resistance to irradiation and transmission of short-wavelength laser light (hereinafter referred to as “laser resistance”). Another object is to provide an optical resin composition that exhibits high light transmittance.

  In particular, an object of the present invention is to provide an optical resin composition that exhibits stable transparency over a long period of time, under the conditions of irradiation and transmission of a blue-violet laser having a wavelength of 390 to 430 nm.

  Another object of the present invention is to provide an optical component formed by molding the optical resin composition. Furthermore, another object of the present invention is an optical resin composition containing an alicyclic structure-containing polymer, and a method for producing an optical resin composition having high light transmittance and excellent laser resistance Is to provide.

  As a result of diligent research to solve the above problems, the present inventor has made the alicyclic structure-containing polymer contain an organic additive that has been heat-treated under specific conditions at a specific ratio, thereby allowing relative fluorescence. It has been found that an optical resin composition having an increased strength and high light transmittance and excellent laser resistance can be obtained.

  Examples of the organic additive include, but are not limited to, an ultraviolet absorber, a light stabilizer, a phenol-based antioxidant, a phosphorus-based antioxidant, and a release agent. It is technically important that conventionally, even when these organic additives are added to the alicyclic structure-containing polymer, a sudden increase in relative fluorescence intensity has not been observed. By using, an optical resin composition containing an alicyclic structure-containing polymer and an organic additive, the optical resin composition having an increased relative fluorescence intensity within an appropriate range is obtained. . It has been found that an optical resin composition having a high relative fluorescence intensity within an appropriate range is excellent in light transmittance and laser resistance. The present invention has been completed based on these findings.

According to the present invention, the organic additive, with respect to the alicyclic structure-containing polymer 100 parts by weight, an optical resin composition that contains a proportion of 0.01 to 10 parts by weight ,
(I) The following formula (I)
F = (F ₁ / F ₀ ) × 100 (I)
[In Formula (I), F ₁ is a plate-shaped molded product of 65 mm long × 65 mm wide × 3 mm thick molded from an optical resin composition such that the flat plate surface has an angle of 45 ° with respect to incident light. Then, using a spectrofluorometer, light having an excitation wavelength of 400 nm is incident on the shaped body with a slit width of 5.0 nm, where the photovoltage of the detector is set to 700 volts, and The maximum fluorescence peak height when the fluorescence peak is measured with a slit width of 5.0 nm over the light emitting region of 400 to 800 nm , and F ₀ is a right-angled isosceles triangle having an inner diameter of 10 mm on the bottom. In the triangular prism cell, Rhodamine B solution for spectrofluorophotometer is placed as a standard solution, and the bottom surface of the right isosceles triangle in the triangular prism cell is arranged at an angle of 45 ° with respect to the incident light. Using a fluorometer, light having an excitation wavelength of 400 nm is incident on the triangular prism cell with a slit width of 5.0 nm, and at that time, the photovoltage of the detection unit is set to 700 volts, and the slit is formed over a light emitting region of 400 to 800 nm. when performing measurement of fluorescence peak width 5.0 nm, the relative fluorescence intensity F represented by the maximum fluorescence peak is the height] of Ri der range of 2 to 250, and
(Ii) The organic additive is at least one organic additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, an antioxidant, and a release agent, and the organic additive has an oxygen concentration. in the following inert gas atmosphere 1000 ppm, at a temperature in the range from 60 ° C. below the thermal decomposition temperature of the organic additive, Ru der those heat treatment time conditions within a range from 30 minutes to 72 hours optical A resin composition is provided.

  Moreover, according to this invention, the optical component formed by shape | molding this optical resin composition is provided. The optical component is preferably a blue-violet laser optical component having a wavelength of 390 to 430 nm, and more preferably an optical lens.

Furthermore, according to the present invention, the following steps 1 and 2:
(1) At least one organic additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, an antioxidant, and a release agent is added from 60 ° C. in an inert gas atmosphere having an oxygen concentration of 1000 ppm or less. Heat treatment under conditions of a time within a range of 30 minutes to 72 hours at a temperature within the range below the thermal decomposition temperature of the agent; and (2) with respect to 100 parts by mass of the alicyclic structure-containing polymer Step 2 of mixing the organic additive and the alicyclic structure-containing polymer heat-treated in the step 1 at a ratio within the range of 0.01 to 10 parts by mass of the organic additive;
Including the following formula (I)
F = (F ₁ / F ₀ ) × 100 (I)
[In Formula (I), F ₁ is a plate-shaped molded product of 65 mm long × 65 mm wide × 3 mm thick molded from an optical resin composition such that the flat plate surface has an angle of 45 ° with respect to incident light. Then, using a spectrofluorometer, light having an excitation wavelength of 400 nm is incident on the shaped body with a slit width of 5.0 nm, where the photovoltage of the detector is set to 700 volts, and The maximum fluorescence peak height when the fluorescence peak is measured with a slit width of 5.0 nm over the light emitting region of 400 to 800 nm , and F ₀ is a right-angled isosceles triangle having an inner diameter of 10 mm on the bottom. In the triangular prism cell, Rhodamine B solution for spectrofluorophotometer is placed as a standard solution, and the bottom surface of the right isosceles triangle in the triangular prism cell is arranged at an angle of 45 ° with respect to the incident light. Using a fluorometer, light having an excitation wavelength of 400 nm is incident on the triangular prism cell with a slit width of 5.0 nm, and at that time, the photovoltage of the detection unit is set to 700 volts, and the slit is formed over a light emitting region of 400 to 800 nm. This is the maximum fluorescence peak height when measuring the fluorescence peak at a width of 5.0 nm. )
A method for producing an optical resin composition in which the relative fluorescence intensity F represented by

  According to the present invention, an optical resin composition containing an alicyclic structure-containing polymer and an organic additive, which expresses a high relative fluorescence intensity within a specific range, and thereby has a high light transmittance. An optical resin composition exhibiting excellent laser resistance is provided. In particular, according to the present invention, there is provided an optical resin composition that exhibits stable transparency over a long period of time, with deterioration and alteration being suppressed even under irradiation and transmission conditions of a blue-violet laser having a wavelength of 390 to 430 nm.

  Further, according to the present invention, an optical component such as an optical lens, which is formed by molding the optical resin composition and is excellent in the above-mentioned various characteristics, is provided. Furthermore, according to this invention, the manufacturing method of this optical resin composition is provided.

1. Alicyclic structure-containing polymer:
The alicyclic structure-containing polymer used in the present invention is a polymer having an alicyclic structure in the main chain and / or side chain, and from the viewpoint of mechanical strength, heat resistance, etc., the alicyclic structure in the main chain. Polymers containing are preferred.

  Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and a cycloalkane structure is preferable from the viewpoint of mechanical strength, heat resistance, light resistance, weather resistance, and the like. The number of carbon atoms constituting the alicyclic structure is usually in the range of 4 to 30, preferably 5 to 20, and more preferably 5 to 15 from the viewpoints of mechanical strength, heat resistance, moldability, and the like. The ratio of the repeating unit having an alicyclic structure is usually 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more, and the upper limit is 100% by weight. It is preferable from the viewpoints of transparency, heat resistance, light resistance and the like that the ratio of the repeating unit having an alicyclic structure is in this range.

  Examples of alicyclic structure-containing polymers include 1) norbornene polymers, 2) monocyclic olefin polymers, 3) cyclic conjugated diene polymers, and 4) vinyl alicyclic hydrocarbon polymers. And 5) These hydrogenated products and the like. Among these, norbornene polymers, vinyl alicyclic hydrocarbon polymers, and hydrogenated products thereof are preferable because particularly excellent laser resistance and high light transmittance are obtained, and vinyl alicyclic carbonization is preferable. A hydrogen-based polymer and a hydrogenated product thereof are more preferable.

(1) Norbornene polymer:
Examples of the norbornene polymer include a ring-opening polymer of a norbornene monomer and a hydrogenated product thereof, an addition polymer of a norbornene monomer, and an addition copolymer of a norbornene monomer and a vinyl compound.

Specific examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name “norbornene”), 5-methyl-bicyclo [2.2.1] hept-2-ene, 5, 5-dimethyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2.2.1] hept- 2-ene, 5-hexyl-bicyclo [2.2.1] hept-2-ene, 5-octyl-bicyclo [2.2.1] hept-2-ene, 5-octadecyl-bicyclo [2.2. 1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] hept-2-ene, 5-vinyl-bicyclo [ 2.2.1] Hept-2-ene, 5-propenyl- Cyclo [2.2.1] hept-2-ene, 5-methoxy-carbonyl-bicyclo [2.2.1] hept-2-ene, 5-cyano-bicyclo [2.2.1] hept-2-ene Ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-ethoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-ethoxycarbonyl-bicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-5-enyl- 2-methylpropionate, bicyclo [2.2.1] hept-5-enyl-2-methyloctanoate, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, 5-hydroxymethyl-bishi B [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) -bicyclo [2.2.1] hept-2-ene, 5-hydroxy-i-propyl-bicyclo [2. 2.1] Hept-2-ene, 5,6-dicarboxy-bicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic Acid imide, 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexenyl-bicyclo [2.2. 1] norbornene and its derivatives such as hept-2-ene and 5-phenyl-bicyclo [2.2.1] hept-2-ene; tricyclo [4.3.1 ^2,5 . 0 ^1,6 ] deca-3,7-diene (common name “dicyclopentadiene”), tricyclo [4.3.1 ^2,5 . 0 ^1,6 ] dec-3-ene, tricyclo [4.4.1 ^2,5 . 0 ^1,6 ] undeca-3,7-diene, tricyclo [4.4.1 ^2,5 . 0 ^1,6 ] undeca-3,8-diene, tricyclo [4.4.1 ^2,5 . Dicyclopentadiene and its derivatives, such as 0 ^1,6 ] undec-3-ene; tetracyclo [7.4.1 ^10,13 . 0 ^1,9 . 0 ^2,7 ] trideca-2,4,6-11-tetraene (also referred to as “1,4-methano-1,4,4a, 9a-tetrahydrofluorene”) and its derivatives; tetracyclo [8.4.1 ^{11 , 14} . 0 ^1,10 . 0 ^3,8 ] tetradeca-3,5,7,12-11-tetraene (also referred to as “1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene”) and its derivatives; And norbornene-based monomers having no norbornane ring.

Further, as the norbornene-based monomer, tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene (common name “tetracyclododecene”), 8-methyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-ethyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-methylidene-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-vinyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-propenyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-methoxycarbonyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-hydroxymethyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-carboxy-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-cyclopentyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-cyclohexenyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene, 8-phenyl-tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] tetracyclododecene and derivatives thereof, such as dodeca-3-ene; pentacyclo ^{[6.5.1 1,8.} 1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene derivatives thereof; pentacyclo ^{[7.4.1 3,6.} 1 ^10,13 . 0 ^1,9 . Norbornene monomers having a norbornane ring such as 0 ^2,7 ] pentadeca-4,11-diene and derivatives thereof;

  These norbornene monomers can be used alone or in combination of two or more. Moreover, it can be set as a copolymer using a norbornene-type monomer and the other copolymerizable monomer.

  Examples of other monomers copolymerizable with the norbornene monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3- Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, Α-olefins having 2 to 20 carbon atoms such as 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc .; cyclobutene , Cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclo Cycloolefins such as xene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1 , 4-hexadiene, non-conjugated dienes such as 1,7-octadiene; and the like. These copolymerizable monomers can be used alone or in combination of two or more.

The ring-opening polymer of the norbornene-based monomer is a catalyst system comprising a metal halide such as ruthenium, rhodium, palladium, osmium, iridium, platinum, nitrate or acetylacetone compound and a reducing agent as a ring-opening polymerization catalyst; or titanium, A catalyst system comprising a metal halide such as vanadium, zirconium, tungsten, molybdenum or the like, or an acetylacetone compound and an organoaluminum compound; in a solvent or without a solvent, usually at a polymerization temperature of −50 ° C. to 100 ° C., 0 It can be obtained by ring-opening polymerization of a norbornene-based monomer at a polymerization pressure of ˜50 kg / cm ² . When two or more kinds of norbornene monomers are used in combination, a ring-opening copolymer can be obtained. A ring-opening copolymer can also be obtained by using a norbornene-based monomer in combination with another monomer capable of ring-opening copolymerization with the norbornene-based monomer. The hydrogenated norbornene-based polymer can be obtained by a method in which a ring-opening polymer (including a ring-opening copolymer) is hydrogenated with hydrogen in the presence of a hydrogenation catalyst according to a conventional method.

An addition copolymer of a norbornene-based monomer and a copolymerizable monomer is prepared by mixing these monomer components in a solvent or without a solvent in the presence of a catalyst system composed of a titanium, zirconium or vanadium compound and an organoaluminum compound. Usually, it can obtain by the method of making it copolymerize with the polymerization temperature of -50 degreeC-100 degreeC, and the polymerization pressure of 1-50 kg / cm < ² >.

(2) Monocyclic cyclic olefin polymer:
As the monocyclic olefin polymer, an addition polymer of a monocyclic olefin monomer such as cyclohexene, cycloheptene, and cyclooctene, and a hydrogenated product thereof can be used.

(3) Cyclic conjugated diene polymer:
As the cyclic conjugated diene polymer, a polymer obtained by subjecting a cyclic conjugated diene monomer such as cyclopentadiene or cyclohexadiene to 1,2- or 1,4-addition polymerization and a hydrogenated product thereof can be used.

(4) Vinyl alicyclic hydrocarbon polymer:
Examples of vinyl alicyclic hydrocarbon polymers include polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane and hydrogenated products thereof; vinyl aromatic polymers such as styrene and α-methylstyrene. Monomer polymers and hydrogenated products thereof can be used. The steric configuration of these vinyl alicyclic hydrocarbon polymers may be any of atactic, isotactic and syndiotactic, and any one having a syndiotacticity of 0 to 100% by dyad display is used. be able to.

  The molecular weight of the alicyclic structure-containing polymer is the weight in terms of polyisoprene (polystyrene in the case of a toluene solution) measured by gel permeation chromatography (GPC) of a cyclohexane solution (a toluene solution if the polymer is not dissolved). The average molecular weight is usually 5,000 to 500,000, preferably 10,000 to 200,000, more preferably 20,000 to 100,000. The weight average molecular weight of the alicyclic structure-containing polymer is preferably in the above range in order to achieve a high balance between mechanical strength and moldability. The molecular weight distribution (Mw / Mn) of the alicyclic structure-containing polymer measured by GPC is usually 5.0 or less, preferably 2.5 or less.

  The glass transition temperature (Tg) of the alicyclic structure-containing polymer is usually 50 to 300 ° C, preferably 100 to 200 ° C, more preferably 120 to 180 ° C. The glass transition temperature is a value measured using a differential scanning calorimeter (DSC).

  When the alicyclic structure-containing polymer has an unsaturated bond, it is preferable to use it after hydrogenation from the viewpoints of laser resistance, transparency, heat resistance, and the like. The hydrogenation rate of the non-conjugated carbon-carbon double bond in the alicyclic structure-containing polymer is usually 80% or more, preferably 90% or more, more preferably 99% or more. The conjugated carbon-carbon double bond (for example, the conjugated double bond of an aromatic ring) in the alicyclic structure-containing polymer does not necessarily need to be hydrogenated, but the conjugated carbon in the alicyclic structure-containing polymer. -Hydrogenation of usually 80% or more, preferably 90% or more, more preferably 99% or more of the carbon double bond is preferred because of further excellent laser resistance and transparency.

2. Characteristic values such as relative fluorescence intensity:
The optical resin composition of the present invention contains an alicyclic structure-containing polymer and an organic additive, and has a high relative fluorescence intensity in a specific range. The optical resin composition of the present invention has excellent light transmittance and laser resistance by having a high relative fluorescence intensity in a specific range. In particular, the optical resin composition of the present invention exhibits excellent resistance to irradiation and transmission of a blue-violet laser having a wavelength of 390 to 430 nm.

In the present invention, the relative fluorescence intensity is the following formula (I)
F = (F ₁ / F ₀ ) × 100 (I)
[In Formula (I), F ₁ represents the fluorescence intensity of the optical resin composition, and F ₀ represents the fluorescence intensity of the rhodamine B standard solution for a spectrofluorophotometer. ]
The relative fluorescence intensity F represented by The optical resin composition of the present invention has a relative fluorescence intensity F in the range of 2 to 250.

More specifically, in the present invention, the fluorescence intensity F ₁ of the optical resin composition refers to a flat molded body of 65 mm length × 65 mm width × 3 mm thickness formed from the resin composition for light, and the flat plate surface is incident. Then, using a spectrofluorometer, light having an excitation wavelength of 400 nm is incident on the molded body with a slit width of 5.0 nm. It means the fluorescence intensity detected as the maximum fluorescence peak height when the photovoltage is set to 700 volts and the fluorescence peak is measured with a slit width of 5.0 nm over the emission region of 400 to 800 nm.

More specifically, in the present invention, the fluorescence intensity F ₀ of the rhodamine B standard solution for a spectrofluorophotometer is a spectral solution as a standard solution in a triangular prism cell whose bottom surface is an isosceles right triangle having an inner diameter of 10 mm. A rhodamine B solution for a fluorometer is placed, and the base of the right isosceles triangle in the triangular prism cell is arranged at an angle of 45 ° with respect to the incident light. Then, using a spectrofluorometer, an excitation wavelength of 400 nm Is incident on the triangular prism cell with a slit width of 5.0 nm. At this time, the photovoltage of the detector is set to 700 volts, and the fluorescence peak is measured with a slit width of 5.0 nm over the light emitting region of 400 to 800 nm. When performed, it means the fluorescence intensity of the standard solution detected as the maximum fluorescence peak height.

  The relative fluorescence intensity F of the optical resin composition of the present invention is in the range of 2 to 250, preferably 3 to 200, more preferably 4 to 150, and still more preferably 5 to 120. In many cases, the relative fluorescence intensity F can obtain particularly good results within the range of 5-50. When the relative fluorescence intensity F is too high, the laser resistance of the optical resin composition is improved, but the light transmittance tends to be lowered. For example, when the content ratio of the heat-treated organic additive is increased, the relative fluorescence intensity F of the optical resin composition can be increased, but the light transmittance tends to decrease.

In the present invention, laser resistance refers to a plate-like molded product of 65 mm length × 65 mm width × 3 mm thickness formed from an optical resin composition, at a temperature of 405 ± 10 nm, and an output of 2800 mW / cm ^{2 in} an environment of 60 ° C. After irradiating laser light from the laser diode of 240 hours, the light transmittance T ₁ of the molded body was measured using a spectrophotometer, and the light transmittance of the molded body sample at a wavelength of 405 ± 10 nm before laser light irradiation. It means a value obtained by a method of calculating a ratio [T ₁ / T ₀ ] × 100 (%) with respect to T ₀ .

  It shows that the laser resistance of an optical resin composition is excellent, so that the ratio of the light transmittance in wavelength 405 +/- 10nm before and behind laser irradiation of a molded object is small (it is only called "wavelength 400nm"). The laser resistance of the optical resin composition of the present invention is preferably less than 1.0%, more preferably 0.9% or less, still more preferably 0.7% or less, and particularly preferably 0.5% or less. . The lower limit of laser resistance is usually 0.01%, and in many cases 0.05%.

  In the present invention, the light transmittance of the optical resin composition means a value measured with a spectrophotometer at a wavelength of 400 nm and an optical path length of 3 mm for the flat plate-shaped body. The light transmittance of the optical resin composition of the present invention is usually 85% or more, preferably 86% or more, more preferably 87% or more, still more preferably 88% or more, and particularly preferably 89% or more. The upper limit of this light transmittance is usually 95%, and in many cases 94%.

  When the light transmittance of the optical resin composition is within the above range, the optical resin composition is converted into a semiconductor laser having a short oscillation wavelength (blue laser having a wavelength of 350 to 530 nm, preferably blue-violet laser having a wavelength of 390 to 430 nm) When used in an optical lens for a short wavelength light source LED, a diffraction grating, a prism, etc., it is preferable because it has high light transmittance and is unlikely to undergo discoloration or deformation due to ablation due to poor light transmission.

  Therefore, the transparency of the alicyclic structure-containing polymer is enhanced by adding a heat-treated organic additive to the alicyclic structure-containing polymer and controlling the relative fluorescence intensity F in the range of 2 to 250. The laser resistance can be remarkably improved while holding.

3. Organic additives:
The organic additive used in the present invention means various organic additives generally used as a polymer additive. From the viewpoint of highly balancing laser resistance and transparency, preferred organic additives include, for example, at least one organic compound selected from the group consisting of ultraviolet absorbers, light stabilizers, antioxidants, and mold release agents. Additives can be mentioned. These organic additives are liquid or solid, but heat treatment is easy, it is difficult to bleed on the surface of the molded body, low volatility, and excellent laser resistance and transparency can be maintained over a long period of time. It is preferably a solid such as powder or granular material at room temperature (20 ± 15 ° C.). The organic additive may be one in which a metal atom such as phosphorus or silicon is bonded to an organic group.

  Examples of ultraviolet absorbers include salicylate derivatives, 2-hydroxybenzophenone derivatives, 2- (2'-hydroxyphenyl) benzotriazole derivatives, 2- (4,6-diphenyl-1,3,5-triazin-2-yl)- 5-hexyloxyphenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5-octyloxyphenol and the like are preferable.

  More specifically, examples of the ultraviolet absorber include phenyl salicylate, 4-t-butylphenyl salicylate, 4-t-octylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t. -Salicylate derivatives such as butyl-4-hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy -4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2 ', 4,4'-tetrahydroxybenzophenone, etc. 2-hydroxybenzophenone derivatives; 2- (2- Droxy-5-methylphenyl) benzotriazole, 2- (3 ′, 5′-di-t-butyl-2′-hydroxyphenyl) benzotriazole, 2- (5′-t-butyl-2′-hydroxyphenyl) Benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- ( 3,5-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-s-butyl-2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3', 5'-di-t-amyl-2'-hydroxyphenyl) Benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, methyl 3- [3-tert-butyl-5- (2H-benzo) 2- (2′-hydroxyphenyl) benzotriazole derivatives such as condensates of triazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol (molecular weight about 300); 2- (4,6-diphenyl-1 , 3,5-triazin-2-yl) -5-hexyloxyphenol and 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5 -Octyloxyphenol is mentioned. These ultraviolet absorbers can be used alone or in combination of two or more.

  As the light stabilizer, a hindered amine light stabilizer (HALS) is preferable. Hindered amine light stabilizers are classified into NH type (H = hydrogen atom), NMe type (Me = methyl group), and NR type (R = organic group other than methyl group), focusing on the bonding mode of nitrogen atoms. can do. Any of these types can be used in the present invention.

  Examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N- Cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl) -4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2-bis (3,5-di-t-butyl) -4-hydroxybenzyl) -2-butylmalonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -1- [2- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) Ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6- Tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2, , 6-Pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4- Mixed esterified product of piperidinol and 1-tridecanol, mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, 1, 2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8 , 10-Tetraoxaspiro [5.5] undecane, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidi A mixed esterified product of diol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, dimethyl succinate and 1- ( 2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [(6-morpholino-1,3,5-triazine-2,4-diyl) [( 2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [[6- (1,1,1, 3,3-tetramethylbutyl) -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2, 6,6-tetramethyl-4-pi Lysyl) imino]], dibutylamine, 1,3,5-triazine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, N- (2,2, 6,6-tetramethyl-4-piperidyl) butylamine condensation polymer and the like. These hindered amine light stabilizers can be used alone or in combination of two or more.

  As antioxidant used by this invention, a phenolic antioxidant and a phosphorus antioxidant are preferable.

  Examples of phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,2'-thiobis (6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol)], 2,2′-methylenebis (4- Methyl-6-cyclohexylphenol), 2,2'-methylenebis (4,6-di-t-butylphenol), 2,2'-ethylidenebis (4,6-di-t) Butylphenol), 4,4'-methylenebis (6-t-butyl-2-methylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-butylidenebis (3-methyl) -6-tert-butylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1,3- Tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, ethylene glycol bis [3,3-bis-3'-t-butyl-4'-hydroxyphenyl) butyrate], 2-t-butyl -6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,4-di-t-pentyl-6- [1- ( 2-hydroxy-3,5-di-t-pentylphenyl) ethyl] phenyl acrylate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1 , 3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-phenoxy) -1,3,5-triazine, 1,3,5-tris (4-t- Butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, bis (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, tris [2- (3 ', 5'-di-t -Butyl-4'-hydroxycinnamoyloxy) ethyl] isocyanurate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, di-n-octadecyl-3,5-di-t-butyl 4-hydroxybenzylphosphonate, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoester, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate, neopentanetetrayltetrakis (3,5-di-t-butyl-4-hydroxycinnamate), thiodiethylenebis (3,5-di-t-butyl-4-hydroxycinnamate), 1, 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,6-dioxaoctamethylenebis (3,5-di-t-butyl) -4-hydroxycinnamate), hexamethylene bis (3,5-di-t-butyl-4-hydroxycinnamate), triethylene glycol bis ( -T-tyl-4-hydroxy-3-methylcinnamate), 3,9-bis [2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1 -Dimethylethyl] -2,4,8,10-tetraoxaspiro [5 · 5] undecane, N, N′-bis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) ) Propionyl] hydrazine, N, N′-bis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionyl] hexamethylenediamine, and the like. These phenolic antioxidants can be used alone or in combination of two or more.

  Examples of phosphorus antioxidants include tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, and bis (2,4-di-). t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) ) Pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-diphenylenediphosphonite, 2,2'-methylenebis (4,6-di-t-butylphenyl) ) 2-Ethylhexyl phosphite, 2,2'-ethylidenebis (4,6-di-tert-butylphenyl) fluorophosphine Bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5-butyl-1, 3,2-oxaphosphorinane, 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl-2,2 '-Diyl) phosphite, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetrakis-t-butyldibenzo [d, f] [1.3.2] Dioxaphosphepine and the like. These phosphorus antioxidants can be used alone or in combination of two or more.

  Examples of the release agent include hydrocarbon release agents, fatty acid release agents, alcohol release agents, aliphatic ester release agents, fatty acid amide release agents, fatty acid metal soap release agents. And silicone release agents.

Specifically, as the release agent, for example, paraffins, naphthenes, aromatics, low molecular polyethylene wax, low molecular polypropylene wax, low molecular polystyrene wax or oxides thereof, carboxylic acid, hydroxyl group, ester group, etc. Hydrocarbon release agents such as modified products of: lauric acid, myristylic acid, palmitic acid, stearic acid, behenic acid, hydroxystearic acid, erucic acid, oleic acid, coconut fatty acid, phthalic acid, adipic acid, trimellitic acid, Fatty acid release agents such as hydroxyheptadecanoic acid, hydroxyoctadecanoic acid, hydroxyeicosanoic acid, hydroxydocosanoic acid, hydroxyhexacosanoic acid, hydroxytriacontanoic acid; glycerol, trimethylolpropane, pentaerythritol, diglycerol, triglycerose , Dipentaerythritol, ethylene glycol, stearyl alcohol, 1,6,7-trihydroxy-2,2-di (hydroxymethyl) -4-oxoheptane, sorbitan, sorbitol, polyoxyethylene sorbitan, polyoxyethylene sorbitol, ethylene Glycol, polyethylene glycol, propylene glycol, 2-methyl-1,6,7-trihydroxy-2-hydroxymethyl-4-oxoheptane, 1,5,6-trihydroxy-3-oxohexane, hexadecanol, hepta Decanol, octadecanol, decyltetradecanol, hexacosanol, triacontanol, 1,2-hexadecanediol, 2,3-heptadecanediol, 1,3-octadecanediol, 1,2-decyltetradecane Alcohol-based mold release agents such as all; glycerin stearate, butyl stearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, 12-hydroxystearic acid triglyceride, 12- Stearic alcohol hydroxystearate, pentaerythritol-tetra-12-hydroxystearate, ethylene glycol-di-12-hydroxystearate, propylene glycol-di-12-hydroxystearate, etc. Certain aliphatic ester release agents; stearic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, hexamethylene bi Svehenic acid amide, N-stearyl stearic acid amide, N-oleyl stearic acid amide, ethylene biscaprylic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisisostearic acid amide, m-xylylene bis stearic acid amide , Hexamethylenebisoleic acid amide, dioleyl adipic acid amide, dioleyl sebacic acid amide, stearoid ethyl stearate [C ₁₇ H ₃₅ CONH (CH ₂ ) ₂ OCOC ₁₇ H ₃₅ ], etc., fatty acid and ammonia or ethylenediamine, etc. Fatty acid amide release agent that is a condensate of the above; fatty acid metal soap release agent that is a metal salt of a metal and the fatty acid such as calcium stearate; silicone release agent; That.

  Among these release agents, paraffin wax; stearyl stearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, 12-hydroxystearic acid triglyceride, glycerin tristearate is low in volatility. Fatty acid ester release agents, such as N-stearyl stearate amide, N-oleyl stearate amide, ethylene bis stearate amide, hexamethylene bisbehenate amide, ethylene bis oleate amide, etc. Is preferred.

  The molecular weight of the organic additive is preferably in the range of 200 to 10,000, more preferably 300 to 8,000, and even more preferably 500 to 5,000, but is not limited to these ranges. When the molecular weight of the organic additive is within the above range, mixing with the alicyclic structure-containing polymer is easy, and adhesion as a gas to the mold at the time of injection molding of the optical resin composition or surface of the molded body This is preferable because appearance defects due to bleeding and flashing are reduced.

  When the organic additive is solid and exhibits a melting point, the melting point is preferably 70 ° C. or higher, more preferably 100 ° C. or higher. The upper limit of the melting point of the organic additive is usually about 350 ° C or 300 ° C. The melting point of the organic additive can be measured using a differential scanning calorimeter.

  The 5% mass reduction temperature of the organic additive is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, still more preferably 280 ° C. or higher, and particularly preferably 300 ° C. or higher. The upper limit of the 5% mass reduction temperature of the organic additive is usually about 450 ° C. or 430 ° C. The 5% mass reduction temperature of the organic additive is a value measured using a differential thermogravimetric measuring apparatus (TG / DTA200, manufactured by Seiko Instruments Inc.) under a nitrogen atmosphere under a temperature rising condition of 10 ° C./min. When the 5% mass reduction temperature of the organic additive is in the above range, in addition to easy heat treatment, adhesion as a gas to the mold during the injection molding of the optical resin composition, and the surface of the molded body This is preferable because appearance defects due to bleeding and flashing are reduced.

  The color tone of the organic additive is 85% or more, preferably 86% or more, more preferably 87% or more, still more preferably 88% or more, particularly preferably 89% or more when incorporated in the alicyclic structure-containing polymer. It is preferable that the color tone is such that an optical resin composition exhibiting a light transmittance of the above can be obtained.

  The organic additive is usually in the range of 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, more preferably 0.05 to 2 parts by weight with respect to 100 parts by weight of the alicyclic structure-containing polymer. Add in. If the ratio of the organic additive is too small, the relative fluorescence intensity of the optical resin composition cannot be made sufficiently high, and it becomes difficult to make the laser resistance and the light transmittance high. When the ratio of the organic additive is excessive, the laser resistance is improved, but the light transmittance tends to decrease. On the other hand, if the content ratio of the organic additive is too large, adhesion as a gas to the mold, and appearance defects of the molded body due to bleeding, flashing, etc. are likely to occur. By including the organic additive in the above-described proportion in the alicyclic structure-containing polymer, the relative fluorescence intensity can be controlled within a predetermined range, and the ultraviolet absorption property, light stability, antioxidant property, release property can be controlled. The original functions of each organic additive such as moldability can be exhibited.

  In the present invention, it is preferable to use an organic additive that has been heat-treated in advance under predetermined conditions. Specifically, in an inert gas atmosphere with an oxygen concentration of 1000 ppm or less, heating is performed at a temperature within the range of 60 ° C. to less than the thermal decomposition temperature of the organic additive for a period of time within a range of 30 minutes to 72 hours. Use treated organic additives. The heat treatment conditions will be described in detail later.

  By including the heat-treated organic additive in the alicyclic structure-containing polymer, a) the relative fluorescence intensity F is in the range of 2 to 250, and b) the laser resistance is 0.01% or more. An optical resin composition that is in the range of less than 0% and c) has a light transmittance in the range of 85 to 95% can be obtained.

4). Other additives:
The optical resin composition of the present invention includes a filler, a flame retardant, an antibacterial agent, a wood powder, a coupling agent, a plasticizer, a colorant, a lubricant, a silicone oil, and a foam as long as the intended purpose is not impaired. Various additives such as an agent, a surfactant, and a fluorescent brightening agent can be blended. Other additives include organic additives that have not been heat-treated.

5. Method for producing optical resin composition:
The optical resin composition of the present invention comprises the following steps 1 and 2:
(1) An organic additive in an inert gas atmosphere having an oxygen concentration of 1000 ppm or less, at a temperature within the range of 60 ° C. to less than the thermal decomposition temperature of the organic additive, and for a time within a range of 30 minutes to 72 hours Step 1 for heat treatment below; and (2) Step 2 for mixing the organic additive heat-treated in Step 1 and the alicyclic structure-containing polymer;
It can manufacture with the manufacturing method containing. By the production method of the present invention, an optical resin composition having a relative fluorescence intensity F represented by the formula (I) in the range of 2 to 250 can be produced.

  The heat treatment of the organic additive is performed at an oxygen concentration of 1000 ppm or less, preferably 800 ppm or less, more preferably 500 ppm or less. If the oxygen concentration in the atmosphere during the heat treatment is too high, the organic additive is likely to be thermally decomposed and deteriorated. The lower limit of the oxygen concentration is usually 1 ppm, and in many cases about 5 ppm.

  The lower limit of the heat treatment temperature is 60 ° C., but it is preferable to increase the heat treatment temperature as much as possible according to the type of the organic additive. The heat treatment temperature is preferably a temperature equal to or higher than the melting point of the organic additive in order to shorten the heat treatment time and to easily increase the relative fluorescence intensity F by the heat treatment.

  The heat treatment temperature is lower than the thermal decomposition temperature of the organic additive. In the present invention, the thermal decomposition temperature of the organic additive means a 5% mass reduction temperature. If the heat treatment temperature is too high, the organic additive may be thermally deteriorated during the heat treatment, or undesirable alteration may occur. The heat treatment temperature can usually be in the range of 200 to 350 ° C, and in many cases 230 to 300 ° C.

  The heat treatment time is in the range of 30 minutes to 72 hours, preferably 1 to 24 hours, more preferably 1 to 10 hours, and particularly preferably 1 to 8 hours. The heat treatment time is desirably adjusted according to the type of organic additive and the heat treatment temperature. When the heat treatment temperature is increased, the heat treatment time can be shortened. By increasing the heat treatment temperature, in many cases, the heat treatment time can be in the range of 2.5 to 5 hours.

  Therefore, in the present invention, the heat treatment of the organic additive is carried out in an inert gas atmosphere having an oxygen concentration of 1000 ppm or less within a temperature range of not less than the melting point of the organic additive and less than 5% mass reduction temperature (thermal decomposition temperature). It is desirable to carry out by a method of heat treatment for 8 hours. If the melting point of the organic additive is less than 60 ° C., appearance defects due to adhesion as a gas to the mold during injection molding of the optical resin composition, bleeding or flashing on the surface of the molded product, and the like are likely to occur.

  When the organic additive is heat-treated at a temperature equal to or higher than its melting point, the color tone and transparency of the optical resin composition obtained by adding the heat-treated organic additive to the alicyclic structure-containing polymer are well maintained. Thus, the laser resistance can be remarkably improved.

  The optical resin composition of the present invention can be produced by a method of mixing an alicyclic structure-containing polymer and a heat-treated organic additive. If the organic additive heat-treated at a temperature equal to or higher than the melting point is partially or wholly fused or melted and solidified, if necessary, it is pulverized and then mixed with the alicyclic structure-containing polymer. be able to.

  The mixing method is not particularly limited, and various known mixing methods can be employed. For example, using a mixer such as a Henschel mixer, a V-blender, a ribbon blender, or a tumbler blender, the alicyclic structure-containing polymer pellets, the heat-treated organic additive, and other additives as necessary. A method of mixing and further melt-kneading using a single screw extruder, a twin screw extruder, a pressure kneader, a roll mill or the like; an organic additive heat-treated in a resin solution of an alicyclic structure-containing polymer, and if necessary The method of removing volatile components, such as a solvent, after mixing other additives is mentioned. Among these, the mixing method by the melt kneading method is preferable.

6). Optical components:
An optical component can be produced by molding the optical resin composition of the present invention. The optical component of the present invention can be suitably produced by heat-melt molding an optical resin composition. As a molding method, for example, a normal molding method such as an injection molding method, an extrusion molding method, a press molding method, a blow molding method, a cast molding method, or the like can be used. In order to manufacture a three-dimensional optical component such as an optical lens, it is preferable to employ an injection molding method.

  Examples of the optical component of the present invention include lenses such as a pickup lens, a video camera lens, a telescope lens, and an fθ lens for a laser beam; optical discs such as an optical video disc, an audio disc, a document file disc, and a memory disc; Optical materials such as optical films such as OHP films; optical semiconductor sealing materials such as photo interrupters, photo couplers, and LED lamps; retardation plates for liquid crystal display devices, light diffusion plates, light guide plates, polarizing plate protective films, collectors And various optical members such as a light sheet.

  The optical component of the present invention is suitable for use in an apparatus using a blue-violet laser having a wavelength of 390 to 430 nm as a lens such as a pickup lens or a laser beam fθ lens. The shape of the optical component of the present invention is arbitrary such as a spherical shape, a rod shape, a plate shape, a fiber shape, a cylindrical shape, and other three-dimensional shapes.

  Hereinafter, the present invention will be described more specifically with reference to production examples, examples, and comparative examples, but the present invention is not limited only to these examples. In the following production examples, examples and comparative examples, parts and% are based on mass unless otherwise specified. The measuring methods of various physical properties and characteristics are as follows.

(1) Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn):
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were determined by standard polyisoprene conversion by gel permeation chromatography using cyclohexane as an eluent.

(2) Glass transition temperature:
The glass transition temperature was measured according to Japanese Industrial Standard JIS K 6911 using a differential scanning calorimeter (“DSC 6220” manufactured by SII Nanotechnology).

(3) Hydrogenation rate:
The hydrogenation rate of the alicyclic structure-containing polymer was calculated from the ¹ H-NMR spectrum.

(4) Fluorescence intensity:
Relative fluorescence intensity F of the optical resin composition, the standard solution (spectrofluorometer for rhodamine B solution, manufactured by Wako Pure Chemical Industries, Ltd., product code "284-52953") of the optical resin composition on the fluorescence intensity F ₀ of It was evaluated as a percentage of the fluorescence intensity F _1. More specifically, in the present invention, the relative fluorescence intensity F is a value calculated by the following formula (I).
F = (F ₁ / F ₀ ) × 100 (I)

The fluorescence intensity F ₁ of the optical resin composition is a flat molded body of 65 mm long × 65 mm wide × 3 mm thick molded from the optical resin composition, and the flat plate surface has an angle of 45 ° with respect to incident light. Then, using a spectrofluorometer ("F-4500" manufactured by Hitachi, Ltd.), light having an excitation wavelength of 400 nm is incident on the molded body with a slit width of 5.0 nm, Was set to 700 volts, and a fluorescence peak was measured at a slit width of 5.0 nm over a light emitting region of 400 to 800 nm, and the maximum fluorescence peak height was measured.

The fluorescence intensity F ₀ of the standard solution is a rhodamine for a spectrofluorometer as a standard solution in a triangular prism cell (“Fluorescent Triangular Cell SF3” manufactured by Starna Co., Ltd.) whose bottom is an isosceles triangle with an inner diameter of 10 mm. B solution (product code “284-52953” manufactured by Wako Pure Chemical Industries, Ltd., distributor: Hitachi, Ltd.) is put, and the base surface of the right isosceles triangle in the triangular prism cell is at an angle of 45 ° with respect to the incident light. Then, using a spectrofluorometer ("F-4500" manufactured by Hitachi, Ltd.), light having an excitation wavelength of 400 nm is incident on the triangular prism cell with a slit width of 5.0 nm. When the photomultiplier voltage was set to 700 volts and the fluorescence peak was measured with a slit width of 5.0 nm over the emission region of 400 to 800 nm, the maximum fluorescence peak height was measured.

A xenon lamp (30 KV, 150 W) was used as the lamp of the fluorometer. The fluorescence intensity F ₀ of the standard solution was 1673.

(5) Light transmittance:
The light transmittance (%) of the molded product was measured at a wavelength of 400 nm and an optical path length of 3 mm using a spectrophotometer (“V-570” manufactured by JASCO Corporation).

(6) Laser resistance:
Laser resistance is obtained by applying a laser beam from a laser diode (“TC35-40200-4.5” manufactured by Neoarc) having a wavelength of 405 ± 10 nm and an output of 2800 mW / cm ^{2 to} the molded body in an environment of 60 ° C. The light transmittance of the molded article after irradiation with laser for a period of time was measured using a spectrophotometer (“V-570” manufactured by JASCO Corporation), and the ratio of light transmittance before and after irradiation (reduction rate) (%) It was evaluated with. It shows that it is excellent in laser resistance, so that the decreasing rate of the light transmittance of wavelength 400nm before and behind laser irradiation of a molded object sample is small.

[Production Example 1]
76 parts by mass of styrene and 4 parts by mass of isoprene were sealed in a stainless steel pressure-resistant container substituted with dry nitrogen, and stirred to prepare a mixed monomer. Next, 320 parts by mass of dehydrated cyclohexane, 4 parts by mass of mixed monomer, and 0.1 part by mass of dibutyl ether were charged into a stainless steel autoclave equipped with an electromagnetic stirring device substituted with dry nitrogen, and these were stirred at 50 ° C. Then, 0.18 parts by mass of a hexane solution (concentration 15%) of n-butyllithium was added to initiate polymerization. When 0.5 hour had elapsed from the start of the reaction (conversion rate of 96%), 76 parts by mass of the mixed monomer was continuously added to the polymerization reaction solution over 1 hour to continue the polymerization reaction. When 0.5 hour had passed since the end of the mixed monomer addition (conversion rate 95%), 0.1 part by mass of isopropyl alcohol was added to stop the polymerization reaction. In this way, a polymer (A1) was obtained. The polymer (A1) had a weight average molecular weight (Mw) of 150,000 and a molecular weight distribution (Mw / Mn) of 1.12.

  Next, 8 parts by mass of a stabilized nickel hydrogenation catalyst E22U (“60% nickel-supported silica-alumina carrier” manufactured by JGC Chemical Industries, Ltd.) is added to 400 parts by mass of the reaction solution containing the polymer (A1). A stainless steel autoclave was charged. The inside of the autoclave was replaced with hydrogen gas, hydrogen was supplied so that the pressure in the mass part in the autoclave was maintained at 4.5 MPa, and a hydrogenation reaction was performed at 160 ° C. for 6 hours. Next, using a pressure filter ("Hunda filter" manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd.) using Radiolite # 800 as a filter bed, the solution was filtered under pressure at a pressure of 0.25 MPa to obtain a colorless and transparent solution from which the catalyst was removed. Obtained.

  The hydrogenation reaction solution was poured into a mixed solution of 250 parts by mass of acetone and 250 parts by mass of isopropanol while stirring to precipitate the hydrogenated product, and then collected by filtration. The recovered hydrogenated product was further washed with 200 parts by mass of acetone, and then dried for 24 hours in a vacuum dryer at 100 ° C., which was decompressed to 1 mmHg or less, to obtain a hydrogenated product (A2). The yield of the hydrogenated product (A2) was 99%.

  The hydrogenated product (A2) thus obtained (hereinafter sometimes abbreviated as “SI hydrogenated product (A2)”) has a hydrogenation rate of 99.8% and a weight average molecular weight (Mw). Was 100,000, the molecular weight distribution (Mw / Mn) was 1.28, and the glass transition temperature was 125 ° C.

[Example 1]
1. Preparation of resin composition:
6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetrakis-t-butyldibenzo [d, f] [d] 1.3.2] Dioxaphosphepine was heat-treated at a temperature of 270 ° C. for 4 hours in a nitrogen atmosphere having an oxygen concentration of 450 ppm.

  100 parts by mass of the SI hydrogenated product (A2) synthesized in Production Example 1, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8, 10-tetrakis-t-butyldibenzo [d, f] [1.3.2] dioxaphosphepine (5% mass reduction temperature 330 ° C.) 0.3 part by mass, and poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] 0.1 parts by mass was mixed with a twin-screw kneader (“TEM-35B” manufactured by Toshiba Machine Co., Ltd., screw diameter = 37 mm, L / D = 32, screw rotation speed = 250 rpm, resin temperature = 2 0 ° C., by kneading a feed rate = 10 kg / hour), melt-extruded, and pelletized to obtain a resin composition (A2-1).

2. Fabrication of molded body:
The resin composition (A2-1) is dried by heating at 80 ° C. for 4 hours, and then using an injection molding device (manufactured by FANUC CORPORATION, product number “α-100B”), the resin temperature is 250 ° C., the mold temperature. Injection molding was performed at 115 ° C., an injection speed of 20 mm / sec, and a holding pressure of 80 MPa to obtain a flat molded body (a) of 65 mm × 65 mm × 3 mm. Table 1 shows the measurement results of fluorescence intensity F ₁ , relative fluorescence intensity F, light transmittance, and laser resistance at a wavelength of 400 nm of the obtained molded product (a).

[Example 2]
Dibutylamine, 1,3,5-triazine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, N- (2,2,6, 6-Tetramethyl-4-piperidyl) butylamine condensation polymer (5% mass reduction temperature 405 ° C.) was heat-treated at a temperature of 270 ° C. for 4 hours in a nitrogen atmosphere with an oxygen concentration of 450 ppm. In Example 1, instead of 0.3 parts by mass of the heat-treated phosphorus-based antioxidant, the heat-treated dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6, A resin composition (A2-2) was prepared in the same manner as in Example 1 except that 0.5 part by mass of the polycondensate with 6-tetramethylpiperidine was used. Next, a molded body (b) was molded in the same manner as in Example 1 using the resin composition (A2-2). The results are shown in Table 1.

[Example 3]
As a mold release agent, pentaerythritol tristearate (5% mass reduction temperature 348 ° C.) was heat-treated at a temperature of 270 ° C. for 4 hours in a nitrogen atmosphere having an oxygen concentration of 450 ppm. In Example 1, in place of 0.3 part by mass of the heat-treated phosphorous antioxidant, 0.5 part by mass of the above-mentioned heat-treated pentaerythritol tristearate was used in the same manner as in Example 1. Thus, a resin composition (A2-3) was prepared. Next, a molded body (c) was molded in the same manner as in Example 1 using the resin composition (A2-3). The results are shown in Table 1.

[Comparative Example 1]
A resin composition (A2-4) and a molded body (d) were obtained in the same manner as in Example 1, except that the heat-treated phosphorus antioxidant was not added. The results are shown in Table 1.

[Comparative Example 2]
In Example 1, the heat treatment time of the phosphorus-based antioxidant was changed from 4 hours to 2 hours, and the use ratio of the heat-treated phosphorus-based antioxidant was changed from 0.3 parts by mass to 0.005 parts by mass. A resin composition (A2-5) was prepared in the same manner as in Example 1 except for the change. Next, a molded body (d) was molded in the same manner as in Example 1 using the resin composition (A2-5). The results are shown in Table 1.

(footnote)
(* 1) Antioxidant: 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetrakis-t, which is a phosphorus-based antioxidant -Butyldibenzo [d, f] [1.3.2] dioxaphosphine,
(* 2) Light stabilizer: Dibutylamine, 1,3,5-triazine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, N- (2, 2,6,6-tetramethyl-4-piperidyl) butylamine condensation polymer,
(* 3) Mold release agent: pentaerythritol tristearate.

<Discussion>
When the heat-treated organic additive is not contained, the laser resistance is insufficient (Comparative Example 1). If the ratio of the heat-treated organic additive (phosphorus antioxidant) is too small, the relative fluorescence intensity is low and the laser resistance is not sufficient (Comparative Example 2).

  On the other hand, when an appropriate amount of a heat-treated organic additive is added to the alicyclic structure-containing polymer, it has a relative fluorescence intensity within a predetermined range, and has a high level of light transmittance and laser resistance. Balanced optical resin compositions (Examples 1 to 3) can be obtained.

  The optical resin composition of the present invention has high light transmittance and excellent laser resistance, and can be used as a resin material for various optical articles. As the optical article, an optical lens such as a blue-violet laser pickup lens is preferable.

Claims (7)

Organic additives, relative to the alicyclic structure-containing polymer 100 parts by weight, an optical resin composition that contains a proportion of 0.01 to 10 parts by weight,
(I) The following formula (I)
F = (F ₁ / F ₀ ) × 100 (I)
[In Formula (I), F ₁ is a plate-shaped molded product of 65 mm long × 65 mm wide × 3 mm thick molded from an optical resin composition such that the flat plate surface has an angle of 45 ° with respect to incident light. Then, using a spectrofluorometer, light having an excitation wavelength of 400 nm is incident on the shaped body with a slit width of 5.0 nm, where the photovoltage of the detector is set to 700 volts, and The maximum fluorescence peak height when the fluorescence peak is measured with a slit width of 5.0 nm over the light emitting region of 400 to 800 nm , and F ₀ is a right-angled isosceles triangle having an inner diameter of 10 mm on the bottom. In the triangular prism cell, Rhodamine B solution for spectrofluorophotometer is placed as a standard solution, and the bottom surface of the right isosceles triangle in the triangular prism cell is arranged at an angle of 45 ° with respect to the incident light. Using a fluorometer, light having an excitation wavelength of 400 nm is incident on the triangular prism cell with a slit width of 5.0 nm, and at that time, the photovoltage of the detection unit is set to 700 volts, and the slit is formed over a light emitting region of 400 to 800 nm. when performing measurement of fluorescence peak width 5.0 nm, the relative fluorescence intensity F represented by the maximum fluorescence peak is the height] of Ri der range of 2 to 250, and
(Ii) The organic additive is at least one organic additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, an antioxidant, and a release agent, and the organic additive has an oxygen concentration. in the following inert gas atmosphere 1000 ppm, at a temperature in the range from 60 ° C. below the thermal decomposition temperature of the organic additive, Ru der those heat treatment time conditions within a range from 30 minutes to 72 hours optical Resin composition.   The optical resin composition according to claim 1, wherein the laser resistance is in the range of 0.01% or more and less than 1.0%.   The optical resin composition according to claim 1 or 2, wherein the light transmittance is in the range of 85 to 95%. The optical component formed by shape | molding the optical resin composition of any one of Claims 1 thru | or 3 . The optical component according to claim 4, which is an optical component for a blue-violet laser having a wavelength of 390 to 430 nm. The optical component according to claim 4 or 5, wherein the optical lens. Steps 1 and 2 below:
(1) At least one organic additive selected from the group consisting of an ultraviolet absorber, a light stabilizer, an antioxidant, and a release agent is added from 60 ° C. in an inert gas atmosphere having an oxygen concentration of 1000 ppm or less. Heat treatment under conditions of a time within a range of 30 minutes to 72 hours at a temperature within the range below the thermal decomposition temperature of the agent; and (2) with respect to 100 parts by mass of the alicyclic structure-containing polymer Step 2 of mixing the organic additive and the alicyclic structure-containing polymer heat-treated in the step 1 at a ratio within the range of 0.01 to 10 parts by mass of the organic additive;
Including the following formula (I)
F = (F ₁ / F ₀ ) × 100 (I)
[In Formula (I), F ₁ is a plate-shaped molded product of 65 mm long × 65 mm wide × 3 mm thick molded from an optical resin composition such that the flat plate surface has an angle of 45 ° with respect to incident light. Then, using a spectrofluorometer, light having an excitation wavelength of 400 nm is incident on the shaped body with a slit width of 5.0 nm, where the photovoltage of the detector is set to 700 volts, and The maximum fluorescence peak height when the fluorescence peak is measured with a slit width of 5.0 nm over the light emitting region of 400 to 800 nm , and F ₀ is a right-angled isosceles triangle having an inner diameter of 10 mm on the bottom. In the triangular prism cell, Rhodamine B solution for spectrofluorophotometer is placed as a standard solution, and the bottom surface of the right isosceles triangle in the triangular prism cell is arranged at an angle of 45 ° with respect to the incident light. Using a fluorometer, light having an excitation wavelength of 400 nm is incident on the triangular prism cell with a slit width of 5.0 nm, and at that time, the photovoltage of the detection unit is set to 700 volts, and the slit is formed over a light emitting region of 400 to 800 nm. This is the maximum fluorescence peak height when measuring the fluorescence peak at a width of 5.0 nm. )
The manufacturing method of the resin composition for optics in which the relative fluorescence intensity F represented by these is in the range of 2-250.