JP2005131917A - Manufacturing method for composite optical element, and composite optical element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture a composite optical element, which is composed of a glass substrate and a resin layer, by one-time molding, and to impart characteristics wherein a loss of light on an interface between the glass substrate and the resin layer is reduced to a low level. <P>SOLUTION: Metallic oxide particulates with a mean primary particle diameter of 1-20 nm are turned into an organosol wherein an organic compound serves as a dispersion medium; and after the organosol is mixed into an acrylic resin, the dispersion medium is removed so that a resin composition for the optical element can be manufactured. After the composition is applied to the glass substrate, a mold is positioned and brought into contact with the resin composition for the optical element, so that an optical form can be transferred; and in this state, the resin composition for the optical element is cured and molded, so that the composite optical element, wherein the glass substrate and the resin for the optical element are integrated together by forming the interface, can be manufactured. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for manufacturing a composite optical element and a composite optical element, in which a glass substrate and an optical element resin are integrated by forming an interface.

  Various types of composite optical elements composed of a glass substrate and a resin for optical elements have been proposed. In this composite optical element, at the interface between the glass substrate and the resin layer, the resin is cured and contracted during molding of the resin layer on the surface of the glass substrate, and the glass substrate and resin after molding are thermally expanded and contracted. It is necessary to have sufficient adhesive strength against the accompanying stress and change with time. In particular, when the resin layer constituting the composite optical element forms a relatively thick layer or when the thickness deviation between the center side and the peripheral side of the resin layer is large, the resin cure shrinkage or thermal expansion / Due to the stress accompanying the shrinkage, transfer defects such as sinks and distortions in the resin layer and molding defects such as bubbles mixed in the resin layer are likely to occur.

Japanese Patent No. 2849299 proposes the following method as a method of manufacturing a composite optical element without causing such molding defects. In this method, a mold for molding a resin layer is formed with an optical shape inverted with respect to the completed shape of the resin layer to form a cavity, and a reaction of approximately the same volume as the cavity is formed in the cavity. A first molding step of forming a first resin layer by filling and curing a curable liquid resin, and a small amount of the reaction curable liquid resin is dropped on the open cured surface of the first resin layer. A second molding step of forming a second resin layer by placing and curing a glass substrate on the reaction-curable liquid resin, a glass substrate, a first resin layer, and a second And a mold release step of releasing the molded product integrated with the resin layer from the mold.
Japanese Patent No. 2849299

  However, performing the molding process in two steps as in the method described above greatly increases the number of molding steps, and when the upper surface of the second resin layer has an optical curved surface, High-precision positioning of the lower surface of the first resin layer and the upper surface of the second resin layer formed thereafter is indispensable, and the molding operation becomes complicated.

  In addition, the refractive index of the resin layer is considerably higher than the refractive index of the glass, and this refractive index difference causes a significant loss of light at the interface between the glass substrate and the resin layer.

  Furthermore, when a glass prism is used as the glass substrate and a resin layer is formed on the surface of the glass prism, the thickness is extremely different between the edge side (pointed side) and the base side (thick side) of the prism. Therefore, there is a problem that the surface shape is likely to change on the edge side of the optical surface of the prism due to thermal expansion / contraction or curing shrinkage of the resin layer.

  The present invention reduces the number of molding steps by performing the molding process in the background art described above in two steps, or by requiring highly accurate positioning of the first resin layer and the second resin layer. It was made in view of the problem of a significant increase and the problem of loss of light at the interface between the glass substrate and the resin layer due to the difference in refractive index between the glass substrate and the resin layer. Even when a relatively thick layer is formed or when the resin layer has a large thickness deviation, it can be molded in a single molding process, and the loss of light at the interface between the glass substrate and the resin layer is kept small. In particular, an object of the present invention is to provide a composite optical element manufacturing method and composite optical element capable of reducing changes in the surface shape of the glass prism even when the glass substrate is a glass prism.

  In order to achieve the above object, a method for producing a composite optical element according to the first aspect of the present invention is to use metal oxide fine particles having an average primary particle diameter of 1 to 20 nm as an organosol using an organic compound as a dispersion medium. After kneading in the resin, the dispersion medium is removed to prepare a resin composition for optical elements, and this is applied to a glass substrate, and then the mold is positioned and brought into contact with the optical element resin composition for optical use. By transferring the shape and curing and molding the optical element resin composition in this state, it is possible to produce a composite optical element in which the glass substrate and the optical element resin are integrated to form an interface. Features.

  According to the first aspect of the present invention, an organic sol in which metal oxide fine particles having a specific average primary particle size are dispersed in an organic compound is mixed with an acrylic resin, and then the dispersion medium is removed. The metal oxide fine particles can be dispersed in the acrylic resin while being dispersed therein. For this reason, it can disperse | distribute uniformly in an acrylic resin, without raise | generating secondary aggregation, and an optical characteristic is not impaired by the uneven distribution of a metal oxide microparticle, etc.

  Acrylic resin can be mixed with metal oxide fine particles in a liquid state, and can be obtained as a highly transparent optical resin after curing, as well as a compound for obtaining desired mechanical and thermal properties compared to other resins. There is an advantage that it is easy to do.

  In addition, the optical element formed on the glass substrate by uniformly containing metal oxide fine particles having an average primary particle diameter of 1 to 20 nm in the resin composition for optical elements applied to the surface of the glass substrate. Since the thermal expansion coefficient of the element resin and the shrinkage due to the curing reaction can be reduced as compared with the case of curing the acrylic resin alone, even when the resin layer is relatively thick or the thickness deviation of the resin layer is large In addition to being able to be molded in a single molding process, there is no change in the surface shape of the optical surface during molding or over time.

  A second aspect of the invention is a method for producing a composite optical element according to the first aspect, wherein the metal oxide fine particles are made of spherical silicon oxide.

  In the invention of claim 2, by using spherical silicon oxide as the metal oxide fine particles, the dispersibility in the acrylic resin is improved and the compatibility with the acrylic resin and the chemical bondability are expressed by an appropriate treatment. Can be made.

  The composite optical element of the invention of claim 3 is formed by integrating an optical element resin composition comprising at least a metal oxide fine particle having an average primary particle diameter of 1 to 20 nm and an acrylic resin and a glass substrate to form an interface. It is characterized by.

  In invention of Claim 3, since the resin composition for optical elements is formed with the metal oxide fine particles and the acrylic resin, the thermal expansion coefficient of the resin for optical elements formed on the glass substrate and the shrinkage due to the curing reaction are reduced. Since it can be reduced as compared with the case where the acrylic resin alone is cured, there is no change in the surface shape of the optical surface at the time of molding or over time. Moreover, the surface hardness of the resin for optical elements molded on the surface of the glass substrate can be improved as compared with the case where the acrylic resin alone is cured. Further, by mixing metal oxide fine particles having a refractive index different from that of the acrylic resin into the optical element resin composition, the difference in refractive index between the glass of the substrate and the cured optical element resin is reduced. Therefore, the loss of light at the interface between the glass substrate and the resin layer can be kept small.

  A fourth aspect of the invention is a method for producing a composite optical element according to the first or second aspect, wherein a glass prism is used as the glass substrate.

  A fifth aspect of the present invention is the composite optical element according to the third aspect, wherein the glass substrate is a glass prism.

  When the glass substrate is a glass prism, the substrate thickness on the edge side (pointed side) and base side (wall thickness side) of the prism is often non-uniform. However, in many cases, the thermal expansion coefficient and the curing reaction of the optical element resin are present. Since the shrinkage due to can be reduced as compared with the case where the acrylic resin alone is cured, the resin for an optical element can also be formed on the surface of the substrate having a non-uniform thickness such as a prism.

  According to the method for manufacturing a composite optical element of the present invention, the metal oxide fine particles can be uniformly dispersed in the acrylic resin without causing secondary aggregation. The characteristics are not impaired. Moreover, since the thermal expansion coefficient of the resin for optical elements formed on the glass substrate and shrinkage due to the curing reaction can be reduced, even when the resin layer forms a relatively thick layer or when the resin layer has a large thickness deviation, In addition to being able to be molded in a single molding process, there is no change in the surface shape of the optical surface during molding or with time. And since the refractive index difference of the glass of a base material and resin for optical elements after hardening can be made small, the loss of the light in the interface of a glass base material and a resin layer can be suppressed small.

  According to the composite optical element of the present invention, since the thermal expansion coefficient of the resin for optical elements on the glass substrate and the shrinkage due to the curing reaction can be reduced, the surface shape of the optical surface changes during molding or over time. Nothing will happen. Moreover, the surface hardness of the resin for optical elements molded on the surface of the glass substrate can be improved. Furthermore, since the difference in refractive index between the glass of the base material and the cured resin for optical elements can be reduced, the loss of light at the interface between the glass base material and the resin layer can be kept small.

  In this embodiment, an organosol of metal oxide fine particles using an organic compound as a dispersion medium is prepared, and after kneading this organosol in an acrylic resin, the dispersion medium is removed to prepare a resin composition for an optical element. The metal oxide fine particles have an average primary particle diameter of 1 to 20 nm, and the resin composition for an optical element contains the metal oxide fine particles having the above particle diameter, an acrylic resin, and a reaction initiator. The reaction initiator may be added to the organic compound, may be added to the acrylic resin, or may be added during or after the dispersion medium is removed.

  After coating the resin composition for optical elements thus produced on the surface of the glass substrate, a mold for molding the resin composition into an optical shape is positioned with respect to the glass substrate, and the resin composition for optical elements Contact the object and transfer the optical shape. In this state, the resin composition is cured and molded. Thus, a composite optical element in which the glass substrate and the cured optical element resin are integrated by forming an interface is produced.

  When producing the resin composition for an optical element, the dispersibility of the metal oxide fine particles in the acrylic resin is improved. As a result, the surface shape of the optical surface does not change even with a change with time during molding or after curing. Also, the composite optical element can be molded on the glass substrate in a single molding process. Furthermore, since the refractive index of the resin layer is lowered by the metal oxide fine particles contained in the resin layer, the loss of light at the interface between the glass substrate and the resin layer can be suppressed to a small level, and the transparency, surface hardness A composite optical element having a desired shape and thickness excellent in durability and durability can be obtained.

  In such an embodiment, an organosol in which metal oxide fine particles having an average primary particle diameter of 1 to 20 nm are dispersed in a dispersion medium made of an organic compound is dispersed in an acrylic resin, and a reaction initiator is added and kneaded. Thereafter, the organic compound used as the dispersion medium for the metal oxide fine particles is removed by a method such as heating and vacuum distillation to obtain a resin composition for an optical element having a high viscosity. Alternatively, an organosol in which metal oxide fine particles are dispersed in a dispersion medium made of an organic compound is dispersed in an acrylic resin, and then the organic compound used as the dispersion medium for the metal oxide fine particles is removed by a method such as heating or vacuum distillation. Then, a reaction initiator is added and kneaded to obtain a resin composition for an optical element.

  And after apply | coating these resin compositions with high viscosity on a glass base material, a glass base material and a type | mold are positioned, a type | mold is made to contact the resin composition for optical elements on a glass base material, and it is for optical elements. The optical shape of the mold is transferred to the resin composition, and the resin layer is cured and molded into a composite optical element.

  Metal oxide fine particles having an average primary particle diameter of 1 to 20 nm include silicon oxide, zirconium oxide, titanium oxide, tin oxide, antimony oxide, niobium oxide, cerium oxide, aluminum oxide, and zinc oxide. Fine particles such as materials can be used. The shape of the particles can be spherical, polygonal, indeterminate, flake, fiber, needle, chain, etc., but it can achieve homogeneous and highly filled dispersion with acrylic resin, ensuring transparency In order to achieve this, a spherical shape is preferred.

  The metal oxide fine particles may be composite oxide fine particles containing a plurality of the above components, and the surface of the metal oxide fine particles treated with other metal oxides, organosilicon compounds, organometallic compounds, etc. Modified fine particles may also be used.

  As the composite oxide fine particles, for example, composite oxide fine particles of cerium oxide and titanium oxide, composite oxide fine particles of silicon oxide, cerium oxide, titanium oxide, or the like can be used. The surface-modified fine particles can be obtained, for example, by precipitating silicon oxide on the surface in a dispersion medium of titanium oxide fine particles. An example of treating the surface of a metal oxide with an organosilicon compound or an organometallic compound is as follows: a desired organosilicon compound or organometallic compound is added to a dispersion medium containing fine metal oxide particles, followed by heating and stirring. There is a way.

  Further, by modifying the surface of the metal oxide fine particles, it is possible to adjust the properties of the original metal oxide fine particles. For example, in the case of silicon oxide fine particles, it is possible to develop compatibility and chemical bonding with an acrylic resin by pretreatment with various functional group-containing polyisocyanates. Further, in the case of titanium oxide fine particles, the photocatalytic action is large depending on the form. It is possible to reduce the effect.

  The metal oxide fine particles are kneaded in the form of an organosol using an organic compound made of a liquid having an affinity for an acrylic resin as a dispersion medium. This makes it possible to uniformly disperse in the acrylic resin, eliminates the need for dust removal equipment required when handling the powder, and provides an effect of improving the working environment.

  As an organic compound used as a dispersion medium, an organic compound having a low viscosity such as an acrylic monomer as well as an organic solvent may be used as long as it is highly compatible with an acrylic resin. Further, when the organic compound used as the dispersion medium is an organic compound that is not highly compatible with the acrylic resin, or when the viscosity of the acrylic resin is large and kneading is difficult, the dispersibility may be increased by heating.

  After the acrylic resin and the metal oxide fine particles are dispersed, the organic compound as the dispersion medium is removed by kneading, heating, and decompressing to obtain a resin composition for an optical element in which the metal oxide fine particles are dispersed. . If bubbles are generated in the acrylic resin during heating and decompression, the acrylic resin thickens and foams and a transparent body cannot be obtained. Adjust the temperature and degree of vacuum so that bubbles do not occur. It is preferable to do.

  In order to obtain an organosol in which the metal oxide fine particles have an organic compound as a dispersion medium, an aqueous sol may be used. This is because the aqueous sol is easier to obtain a sol containing finer fine particles or a sol other than silica. In the case of using an aqueous sol, the aqueous dispersion medium is solvent-substituted with an organic compound having a low viscosity such as an acrylic monomer having compatibility with an acrylic resin, and as a result, an organosol using the organic compound as the dispersion medium may be used. . When replacing the water-based sol with an organic compound having compatibility with the acrylic resin, it is necessary to carry out so that the metal oxide fine particles do not cause secondary aggregation. There may be mentioned a method which is carried out while sufficiently diluting with a solvent so as not to exceed wt%.

  As the metal oxide fine particles used in the present invention, those having an average particle diameter of 1 to 20 nm are used, and those having an average particle diameter of 1 to 10 nm are more preferable. When the particle diameter of the metal oxide fine particles is less than 1 nm, the metal oxide fine particles are difficult to stably exist as primary particles, and a stable quality resin composition for optical elements cannot be obtained. In this case, the opacity is easily developed.

  In addition, when the visible light wavelength is 400 nm to 600 nm, if the refractive index difference between the metal oxide fine particles and the acrylic resin is up to about 0.15, the optical element resin is several tens of mm thick on the glass material. Transparency can be expressed even if it is molded in the same manner. When silicon oxide having a refractive index of about 1.45 is used as the metal oxide fine particles, the refractive index of a normal acrylic resin is in the range of 1.55 ± 0.05. In combination, the refractive index can be in the range of more than 1.45 and less than 1.50 or less than 1.60, so that most transparent cured products can be molded.

  It is preferable that the compounding quantity of metal oxide microparticles | fine-particles is 10 to 70 weight% of solid content in the resin composition for optical elements. If it is less than 10% by weight, the thermal expansion coefficient of the optical element resin composition and the shrinkage due to the curing reaction cannot be sufficiently reduced as compared with the case where the acrylic resin alone is cured, and the surface hardness and the adhesion to the inorganic vapor deposition film are also reduced. It becomes insufficient. On the other hand, if it exceeds 70% by weight, cracks are likely to occur or white turbidity tends to occur, resulting in insufficient transparency.

  As acrylic resin to be used, various oligomers such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, silicone (meth) acrylate, aliphatic acrylate, alicyclic acrylate Various monomers such as monofunctional acrylates and polyfunctional acrylates such as aromatic acrylates and various functional group-containing acrylates can be selected, and one or more of these can be used in combination. These acrylic resins are sufficiently purified, and it is preferable to use those in a liquid state that is as colorless and transparent as possible.

  As the reaction initiator, various azo compounds such as azoisobutyronitrile and thermal polymerization initiators for radical reactions such as various peroxides such as benzoyl peroxide can be used, but acetophenone-based, benzophenone-based, Photopolymerization initiators such as benzoin, thioxanthone, benzyl, acylphosphine oxide, camphorquinone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone (BTTB) can be used for shape transfer and It is good in terms of excellent mass productivity. The proportion of the reaction initiator in the optical element resin composition is preferably 0.01 to 10% by weight, more preferably 0.5 to 7% by weight. If it exceeds 10% by weight, the storage stability of the composition and the properties of the cured product may be adversely affected. If it is less than 0.01% by weight, the curing rate may be reduced.

  In addition to the above, curing accelerators such as dye sensitizers and amine sensitizers may be added, and silicone surfactants, fluorine surfactants, and nonionic surfactants may be added. . In addition, thixotropic agents such as silica fine powder, aluminum silicate, inorganic powder such as talc can be added to give thixotropy, but the amount and particle size should not affect the optical properties. is necessary. Moreover, you may add a silicone oil, an antistatic agent, etc. as a slip agent for giving slipperiness.

  Furthermore, in order to improve the weather resistance, an ultraviolet absorber or an antioxidant may be used in combination, and an additive such as a colorant, a coupling agent, a modifier, a stress reducing agent, a release agent, etc. may be used in combination. Also good. In this case, the coupling agent may be used by previously treating the surface of the glass substrate with the coupling agent without adding it to the optical element resin composition.

  In the case where the glass substrate is a glass material with poor adhesion, a vapor deposition layer of silicon oxide or aluminum oxide is previously provided on the surface of the glass substrate, a silyl isocyanate compound, a chlorosilane compound, perhydropolysilazane, an aluminum organic compound, alumina sol, Surface treatment with a titanate compound, a zirconium alcoholate compound or the like is desirable.

  In the present invention, a composite optical element that is molded by curing a resin composition for an optical element on a glass substrate is obtained by adding a predetermined amount of a reaction initiator to an acrylic resin in which metal oxide fine particles are uniformly dispersed. After stirring and mixing, defoaming and applying onto a glass substrate such as a glass prism, positioning a predetermined mold, contacting the resin composition for optical elements, transferring the optical shape, and curing Thus, the glass substrate and the optical element resin are integrally formed by forming an interface. The resin composition for optical elements to be applied may be slightly diluted with a solvent having an appropriate boiling point for viscosity adjustment, and a step of volatilizing and removing the solvent before curing or at the beginning of the curing process may be performed. The viscosity range to be adjusted is preferably from several hundred mPa · s to several thousand mPa · s although it depends on the shape to be transferred.

  When a single optical element such as a glass prism has a plurality of optical surfaces, the above-described coating process to curing process are performed simultaneously or sequentially on each surface of the single optical element to produce a composite optical element. You may do it.

(Example 1)
50 g of organosilica sol (trade name “MEK-ST-UP”, manufactured by Nissan Chemical Industries, Ltd.) containing 20% by weight of silica spherical fine particles having an average primary particle size of about 15 nm in methyl ethyl ketone as metal oxide fine particles 10 g of 1,6-hexanediol diacrylate (trade name “HDODA”, manufactured by Daicel Chemical Industries, Ltd.) was added as an acrylic resin, and 3- (trimethoxysilyl) propyl methacrylate (trade name “MPTMOS” was used as a coupling agent. “) 10 g was added, the solvent was removed with a rotary evaporator, and the mixture was stirred on a hot plate at 80 ° C. for 5 hours. When the viscosity is increased, 0.1 g of a photopolymerization initiator (trade name “Irgacure 500”, manufactured by Ciba Specialty Chemicals Co., Ltd.) consisting of a mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone is added, and defoamed. As a result, a resin composition for optical elements was obtained.

  Next, this optical element resin composition is filled in a coating machine, and as shown in FIG. 1A, the glass material is made of BSL-7 (manufactured by OHARA INC.), And is a metal thin film formed by vacuum deposition. Then, the glass triangular prism 2 whose slope is the mirror surface 5 was set in a molding machine, and the optical element resin composition 1 was applied to the A surface which is one of the optical surfaces.

  Next, as shown in FIG. 1B, the concave lens mold 3 having releasability is brought into contact with the optical element resin composition 1 so that bubbles do not enter, and the optical element resin composition is placed in the concave lens mold 3. After filling 1, the concave lens mold 3 was positioned at a predetermined position of the glass triangular prism 2 and irradiated with ultraviolet rays from the B surface which is the other optical surface. The resin composition 1 for optical elements was cured by irradiation with ultraviolet rays to form the concave lens portion 6, and then the concave lens mold 3 was released to obtain a composite optical element 4 shown in FIG.

The glass triangular prism 2 used had A and B optical surfaces of about 1 cm square. The cured product of the concave lens portion 6 formed on the A surface of the glass triangular prism 2 was a concave lens shape having a diameter of about 10 mm, a center thickness of about 0.5 mm, a peripheral thickness of about 4.5 mm, and a curvature radius of about 4.5 mm. . Moreover, the integrated light quantity of the irradiated ultraviolet rays was about 4000 mJ / cm ² .

  Using the optical element resin composition 1, a disk for measuring physical properties having a diameter of 20 mm and a thickness of 5 mm was produced by the same molding process. The total light transmittance of 400 nm to 600 nm of the obtained molded product was 95%. Moreover, the obtained concave lens part was also excellent in transparency, and the pencil hardness was 7H. In the disk for measuring physical properties, the thermal expansion coefficient was about 70 ppm, and the curing shrinkage due to ultraviolet rays was about 7%. The refractive index of the acrylic resin used is nd = 1.510, the refractive index of the silicon oxide fine particles is nd = 1.457, and the refractive index of the cured product of the resin composition for optical elements 1 is nd = 1.492. there were.

  On the other hand, a cured product obtained by curing the above acrylic resin alone using the same photopolymerization initiator (trade name “Irgacure 500”) has a pencil hardness of 2H, a thermal expansion coefficient of about 120 ppm, and a curing shrinkage due to ultraviolet rays of about 120 ppm. 11%.

  Instead of the optical element resin composition 1 used in the above process, a composite optical element as a comparative example was molded by the same treatment using only an acrylic resin and a photopolymerization initiator. The change of the surface shape of the concave lens surface was compared with the composite optical element 4 of the above-described embodiment. As a result, in the composite type optical element of the comparative example using a single acrylic resin, the surface shape was broken so that the Newton stripes could not be seen even immediately after molding. In the composite type optical element 4 of this example, the Newton stripes were discriminated. It was possible. Furthermore, when the composite optical element of the comparative example and the example was put into 10 cycles with a cooling cycle of maintaining at 20 ° C. for 30 minutes to 80 ° C. for 30 minutes as one cycle, the composite of the comparative example using an acrylic resin alone In the mold type optical element, the interface between the glass substrate and the resin layer began to peel off, but in the composite type optical element of this example, no peeling was observed, and Newton stripes could be discriminated.

  Further, after each of the surface of the concave lens portion 6 and the surface of the disk in the composite optical element 4 obtained in this example was subjected to plasma processing using argon plasma under conditions of an output of 40 W and a processing time of 60 seconds, In order toward the outside, an antireflection multilayer film composed of five layers of silicon oxide / zirconium oxide / silicon oxide / zirconium oxide / silicon oxide was formed by vacuum deposition. The optical thickness of each layer is as follows: the first silicon oxide layer, the equivalent zirconium oxide layer combined with the next zirconium oxide layer and the silicon oxide layer, the next zirconium oxide layer, and the uppermost silicon oxide layer. It was formed so as to be λ / 4, and the design wavelength λ was 520 nm. The reflection interference color of the obtained multilayer film was green.

  The adhesion of the antireflection film applied as described above was inspected based on a cross-cut peel test (JIS D-0202) with respect to a disk. In this inspection, 100 squares of 1 mm 2 are formed on the surface of the glass substrate by cutting at intervals of 1 mm, and a cellophane adhesive tape (trade name “Cello Tape”, manufactured by Nichiban Co., Ltd.) is strongly applied thereon. After pressing, the film was suddenly pulled away from the surface in the direction of 90 degrees, and then the remaining grid of the reflective coat film was used as an adhesion index. As a result, it was found that all 100 eyes remained and the adhesion was excellent.

  In such an embodiment, a composite optical element in which the surface shape of the optical surface does not change at the time of molding or with time change in one molding process without losing the feature of easy molding of the synthetic resin. Could be molded. In addition, in the composite optical element, it is possible to suppress light loss at the interface between the glass substrate and the resin layer, while having transparency as a material for various optical elements. It is also possible to ensure adhesion and surface convenience that can form an antireflection thin film.

(Example 2)
Instead of the metal oxide fine particles (trade name “MEK-ST-UT”) used in Example 1, an organosilica sol (trade name) containing 25% by weight of silica spherical fine particles having an average primary particle size of 9 nm in isopropyl alcohol. A composite optical element and a disc for measuring transmittance were prepared in the same manner as in Example 1 except that 40 g of “IPA-ST-S” (manufactured by Nissan Chemical Industries, Ltd.) was used.

  Using the obtained disc for measuring transmittance, the total light transmittance from 400 nm to 600 nm was measured in the same manner as in Example 1, and it was 96%. Moreover, the obtained concave lens part was also excellent in transparency. Further, the pencil convenience was 7H, and in the disk for measuring physical properties, the thermal expansion coefficient was about 70 ppm, and the cure yield probability by ultraviolet rays was about 7%.

  Furthermore, as in Example 1, when the peel test of the antireflection film formed on the disk, the surface shape immediately after molding and the observation of the surface shape after the cooling test were performed, the same results as in Example 1 were obtained.

  As a result, in this embodiment as well, a composite mold that does not cause a change in the shape of the optical surface at the time of molding or changes with time in one molding process without losing the feature of easy molding of the synthetic resin. The optical element could be molded. In addition, in the composite optical element, it is possible to suppress light loss at the interface between the glass substrate and the resin layer, while having transparency as a material for various optical elements. It is also possible to ensure adhesion and surface convenience that can form an antireflection thin film.

(Example 3)
Instead of the metal oxide fine particles (trade name “MEK-ST-UP”) used in Example 1, a silica sol containing 20 wt% silica spherical fine particles with an average primary particle size of 5 nm in water (trade name “ST-ST-UP”). OXS "(manufactured by Nissan Chemical Industries, Ltd.) 50 g of water was used after adding excess n-propyl alcohol and then distilling as a water-alcohol azeotrope to remove the water and solvent substitution. A composite optical element and a disk for measuring transmittance were produced in the same manner as in Example 1 except that.

  Using the obtained disk for transmittance measurement, the total light transmittance from 400 nm to 600 nm was measured in the same manner as in Example 1 and found to be 98%. Moreover, the obtained concave lens part was also excellent in transparency. Further, the pencil hardness was 8H, and in the disk for measuring physical properties, the thermal expansion coefficient was about 60 ppm, and the curing shrinkage due to ultraviolet rays was about 6%.

  Furthermore, as in Example 1, when the peel test of the antireflection film formed on the disk, the surface shape immediately after molding and the observation of the surface shape after the cooling test were performed, the same results as in Example 1 were obtained.

  Thereby, without losing the feature of easy molding of the synthetic resin, molding a composite optical element that does not cause a change in the shape of the optical surface during molding or over time in a single molding process. I was able to. In addition, in the composite optical element, it is possible to suppress light loss at the interface between the glass substrate and the resin layer, while having transparency as a material for various optical elements. It is also possible to ensure adhesion and surface convenience that can form an antireflection thin film.

Example 4
After the concave lens portion 6 in the composite optical element 4 in Example 1 is molded, as shown in FIG. 2A, the other optical surface, B-side, is set on the molding machine, and Example 1 In the same manner as in Example 1, the optical element resin composition 1 was applied on the B surface using the optical element resin composition 1 used in the above. Then, as shown in FIG. 2 (b), the free curved surface mold 7 having excellent releasability and ultraviolet transparency is brought into contact with the optical element resin composition 1 so that no bubbles are mixed into the free curved surface mold 7. After filling the optical element resin composition 1, the free-form surface mold 7 is positioned and adjusted by the concave lens portion 6 and the optical centering adjuster, and irradiated with ultraviolet rays from the free-form surface mold 7 side, thereby the resin composition for the optical element. Product 1 was cured. After the free-form surface lens portion 8 was formed by curing the resin composition 1 for optical elements, the free-form surface mold 7 was released to obtain a composite optical element 10 shown in FIG.

  Also in this embodiment, a composite optical element that does not lose the characteristic of easy molding of the synthetic resin and does not change the surface shape of the optical surface at the time of molding or change with time in one molding process. Could be molded. In addition, in the composite optical element, it is possible to suppress light loss at the interface between the glass substrate and the resin layer, while having transparency as a material for various optical elements. It is possible to ensure adhesion and surface convenience that can form an antireflection thin film.

(Comparative Example 1)
Instead of the metal oxide fine particles of Example 1 (trade name “MEK-ST-UP”), an organosilica sol containing 30% by weight of silica spherical fine particles having an average primary particle size of 75 nm in isopropyl alcohol (trade name “ It was molded in the same manner as in Example 1 except that 33 g of “IPA-ST-ZL” (manufactured by Nissan Chemical Industries, Ltd.) was used. The obtained cured product was completely turbid and transparency could not be secured.

(A)-(c) is sectional drawing which shows the manufacturing process of Example 1. FIG. (A)-(c) is sectional drawing which shows the manufacturing process of Example 4. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Resin composition for optical elements 2 Glass base material 3 Concave lens type | mold 4 Composite type optical element 6 Concave lens part

Claims (5)

A metal oxide fine particle having an average primary particle size of 1 to 20 nm is used as an organosol having an organic compound as a dispersion medium. The organosol is kneaded in an acrylic resin, and then the dispersion medium is removed to prepare a resin composition for an optical element. After applying this to the glass substrate, the mold is positioned and brought into contact with the optical element resin composition to transfer the optical shape, and in this state, the optical element resin composition is cured and molded. A method for producing a composite optical element, comprising producing a composite optical element in which a glass substrate and a resin for an optical element are integrated by forming an interface. 2. The method of manufacturing a composite optical element according to claim 1, wherein the metal oxide fine particles are made of spherical silicon oxide. A composite optical element characterized in that an optical element resin composition comprising at least an average primary particle diameter of 1 to 20 nm of metal oxide fine particles and an acrylic resin and a glass substrate are integrated to form an interface. The method of manufacturing a composite optical element according to claim 1, wherein a glass prism is used as the glass substrate. The composite optical element according to claim 3, wherein the glass substrate is a glass prism.

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