CN100495077C - Laminated Optical Components - Google Patents

Abstract

Disclosed is a multilayer optical device which is a composite optical device wherein an optical resin layer is arranged on an optical base such as a glass base. This multilayer optical device is excellent in reliability since the optical resin layer is hardly separated even under high temperature, high humidity conditions. Specifically disclosed is a multilayer optical device comprising an optical base (1) made of an optical material, an intermediate layer (2) arranged on the optical base (1), and an optical resin layer (3) arranged on the intermediate layer (2). This multilayer optical device is characterized in that the optical resin layer (3) is a resin layer made of an organic metal polymer having an -M-O-M- bond (wherein M represents a metal atom), a metal alkoxide having one hydrolyzable group and/or a hydrolysis product thereof, and an organic polymer having an urethane bond and a methacryloxy or acryloxy group. The intermediate layer (2) is a layer wherein fine particles of a metal oxide are dispersed in a matrix resin which is made of a metal alkoxide having a radically polymerizable group and a hydrolyzable group and/or a hydrolysis product thereof.

Description

Laminated Optical Components

technical field

The present invention relates to a laminated optical element, which is used in various coating materials such as substrates for electrical wiring, materials for mechanical parts, antireflection films and surface protection films, optical transmission and reception modules, optical switches, Optical communication devices such as modulators, light propagation path structures such as optical waveguides, optical fibers, and lens arrays, and optical devices such as beam splitters including them, integrator lenses, microlens arrays, reflectors, light guide plates, projections Optical components related to display devices such as screens (displays or liquid crystal projectors, etc.), glasses, optical systems for CCDs, lenses, composite aspheric lenses, 2P (Photoreplication Process) lenses, filters, diffraction gratings, interferometers, optical Couplers, optical multiplexers, optical sensors, holographic optical elements, materials for other optical components, photoelectromotive force elements, contact lenses, medical artificial tissues, and mold materials for light-emitting diodes (LEDs), etc.

Background technique

Glass, plastic, etc. have been used conventionally as materials for optical elements including lenses. There are many kinds of glass, and the variation of optical characteristics is abundant, so it is easy to perform optical design, and furthermore, since it is an inorganic material, it is highly reliable. In addition, high-precision optical elements can be obtained by grinding.

However, the cost is high, and aspherical shapes other than flat and spherical surfaces must use a special grinding device, or must be formed by the so-called mold method using an expensive mold with high heat resistance (such as ceramics, etc.). A glass material that can be formed at low temperatures. Therefore, very high price.

On the other hand, optical elements using synthetic resin materials (plastics) can be manufactured inexpensively by injection molding or casting (cast), but they have low heat resistance, large thermal expansion, narrow selection of optical properties such as refractive index, low reliability issues.

As a method of solving the above-mentioned problems, a composite optical element in which desired characteristics are obtained by laminating a resin layer on a glass substrate has been proposed. Patent Document 1 discloses a low-pass filter in which an organic polymer layer is formed on a flat glass substrate. In addition, Patent Document 2 and Patent Document 3 disclose a so-called composite aspheric lens in which a resin layer having an aspherical shape is formed on a glass lens substrate.

In recent years, the fields using the above-mentioned optical elements have expanded, and the reliability required for the optical elements has become increasingly strict. For example, durability for 500 to 1000 hours is sometimes required in an environment of 85° C. and 85% which is a high-temperature and high-humidity condition.

In these laminated optical elements, in order to improve the adhesion between the base material and the resin layer, a silane coupling agent diluted with a solvent is coated on the base material, and then a resin layer is formed thereon, but such a method is Sufficient adhesion cannot be maintained under the environment, and there is a problem that peeling tends to occur.

When the concentration of the coupling agent is increased in order to improve peelability, there are problems such as cloudiness of the surface after coating, inability to coat uniformly, and occurrence of spots.

In Patent Document 4, in high-refractive-index glass containing a large amount of high-refractive-index oxides and containing little silicon dioxide (SiO ₂ ), in order to prevent the A dielectric multilayer film such as SiO ₂ /ZrO ₂ /SiO ₂ is formed on the surface of the glass substrate due to reflection due to the difference in refractive index between the optical resin layers (refractive index = about 1.5).

In addition, in order to improve the adhesion between the glass and the optical resin layer, a silane coupling agent is usually applied on the glass surface. This silane coupling agent has the property of improving the adhesion to the silica component. In a high-refractive-index glass with a small component (SiO ₂ ), there is a problem that the adhesion between the glass and the optical resin layer cannot be improved by a silane coupling agent. In Patent Document 4, since the uppermost layer of the dielectric multilayer film is SiO ₂ , high adhesion can be obtained even with high refractive index glass. This dielectric multilayer film is formed by methods such as vacuum evaporation, ion plating, sputtering, etc. However, it is difficult to manufacture an optical element inexpensively and in a short time using such a method.

Patent Document 1: JP-A-54-6006

Patent Document 2: JP-A-52-25651

Patent Document 3: Japanese Unexamined Patent Publication No. 6-222201

Patent Document 4: Japanese Unexamined Patent Publication No. 5-100104

Contents of the invention

The first object of the present invention is to provide a laminated optical element, which is a composite optical element formed by laminating an optical resin layer on an optical substrate such as glass, and the optical resin layer is difficult to be damaged even under high temperature and high humidity. peeling, and excellent reliability.

The second object of the present invention is to provide a laminated optical element, which is a composite optical element formed by laminating an optical resin layer on an optical substrate such as glass, which can be used even on an optical substrate made of high refractive index glass. It is also possible to form an optical resin layer with good adhesion.

The first aspect of the present invention is a laminated optical element, which includes an optical substrate made of optical materials, an intermediate layer disposed on the optical substrate, and an optical resin layer disposed on the intermediate layer, characterized in that: The optical resin layer is composed of an organometallic polymer having an -M—O—M—bond (M is a metal atom), a metal alkoxide having only one hydrolyzable group and/or its hydrolyzate, and a carbamic acid A resin layer formed of an organic polymer having an ester bond and a methacryloxy group or a urethane bond and an acryloxy group. A layer formed in a matrix resin formed of a metal alkoxide and/or a hydrolyzate of a base and a hydrolyzable base.

In the first aspect of the present invention, it is characterized in that an intermediate layer is provided between the optical base material and the optical resin layer, and the intermediate layer includes fine particles composed of metal oxide dispersed in a material having radical polymerizable groups and A layer formed in a matrix resin formed of a hydrolyzed base metal alkoxide and/or its hydrolyzate. Since the intermediate layer is formed by dispersing fine particles of metal oxides in the matrix resin, the adhesion between the optical substrate and the optical resin layer can be improved, making it difficult to peel off the optical material even under high temperature and high humidity. resin layer. Therefore, a multilayer optical element excellent in reliability can be formed.

In the first aspect of the present invention, the intermediate layer may be formed of at least 2 layers. In this case, at least one of the layers may be formed by dispersing fine particles in a matrix resin.

In the first aspect of the present invention, both the matrix resin of the intermediate layer and the optical resin layer can use resins that can be cured by irradiation of energy rays. By using resins that are cured by irradiation with energy rays in this way, the adhesiveness between the intermediate layer and the optical resin layer can be further improved.

The irregularities on the surface of the intermediate layer according to the first aspect of the present invention can be formed, for example, by dissolving and removing fine particles near the surface of the intermediate layer.

The second aspect of the present invention is a laminated optical element, which includes an optical substrate made of optical materials, an intermediate layer disposed on the optical substrate, and an optical resin layer disposed on the intermediate layer, characterized in that: The optical resin layer is composed of an organometallic polymer having an -M—O—M—bond (M is a metal atom), a metal alkoxide having only one hydrolyzable group and/or its hydrolyzate, and a carbamic acid A resin layer formed of an ester bond and a methacryloxy group or an organic polymer having a urethane bond and an acryloxy group, and the intermediate layer includes a fine particle layer disposed on the optical substrate side and a fine particle layer disposed on the optical resin layer side In the coupling layer, the fine particle layer is a layer formed of a dispersion liquid of fine particles, and the coupling layer is a layer formed of a metal alkoxide and/or its hydrolyzate having a radically polymerizable group and a hydrolyzable group.

In the second aspect of the present invention, the intermediate layer includes a fine particle layer provided on the side of the optical substrate and a coupling layer provided on the side of the optical resin layer, and these layers are preferably formed by lamination.

According to the second aspect of the present invention, the fine particle layer is formed on the optical substrate, and the coupling layer is formed thereon, so even when high refractive index glass is used as the optical substrate, it can be obtained in good Adhesiveness forms an optical resin layer.

In the second aspect of the present invention, it is preferable that the fine particle layer is formed by applying a dispersion liquid of fine particles on the optical substrate followed by heat treatment, and the components of the optical substrate diffuse in the fine particle layer. The temperature of the heat treatment is preferably a temperature of 300 to 500°C.

In particular, after coating a dispersion of fine particles such as SiO ₂ on an optical substrate, and then baking at a temperature of, for example, 300 to 500° C., a layer in which fine particles such as SiO ₂ are aggregated can be formed on the optical substrate. . By forming a coupling layer on such a layer and then forming an optical resin layer, the optical resin layer can be provided with good adhesion.

By baking the microparticle layer at a specified temperature, for example, at a temperature of 300 to 500 ° C, components other than silicon dioxide such as _TiO2 in the optical substrate diffuse into the microparticle layer, and the adhesion between the optical substrate and the microparticle layer become good. In addition, in the fine particle layer, the silica component increased in the part on the side of the coupling layer. As a result, in the microparticle layer, an inclined structure in which there are many components other than silica on the optical substrate side of the microparticle layer and many silica components on the coupling layer side of the microparticle layer can be formed, and the optical substrate and microparticles can be simultaneously improved. The adhesion between the layers, and the adhesion between the micro particle layer and the coupling layer. In addition, the strength of the fine particle layer itself can also be increased by using the above-mentioned predetermined baking temperature.

In the second aspect of the present invention, the fine particle layer is formed of fine particles having an average particle diameter of 50 nm or more, whereby unevenness can be formed on the surface of the fine particle layer. By forming irregularities on the surface of the fine particle layer, the surface area of the interface with the coupling layer increases, and the adhesion with the coupling layer becomes good.

In the second aspect of the present invention, the fine particle layer may be composed of a first fine particle layer disposed on the optical substrate side consisting of fine particles having an average particle diameter of less than 50 nm, and a layer consisting of fine particles having an average particle diameter of 50 nm or more. The second fine particle layer disposed on the side of the coupling layer is formed by laminating layers. By forming such a structure, the area of the contact portion of the interface between the optical substrate and the microparticle layer can be increased, thereby improving the adhesion between the optical substrate and the microparticle layer, and, on the coupling layer side of the microparticle layer, By forming irregularities on the surface of the fine particle layer, the adhesion to the coupling layer can be improved.

In the second aspect of the present invention, the dispersion liquid of the fine particle layer may contain only fine particles as a solid component. That is, the dispersion of fine particles may contain only fine particles and a dispersion medium. Such a dispersion of fine particles can form a dense fine particle layer by baking as described above.

In addition, in the second aspect of the present invention, the dispersion of fine particles may contain a binder resin. By containing the binder resin, the strength of the fine particle layer can be increased without baking at a high temperature. In addition, depending on the type of binder resin to be added, it is also possible to improve the adhesiveness with the optical substrate. Examples of the binder resin include water-soluble acrylic monomers, water-soluble resins, silane coupling agents, and photosensitive resins. As the binder resin, a water-soluble resin is preferably used. By using a photosensitive binder resin such as a photosensitive resin, the fine particle layer can be provided with photosensitivity, and after forming the fine particle layer, it can be cured by irradiating ultraviolet rays or the like to pattern the fine particle layer.

In the second aspect of the present invention, minute particles can be patterned to have optical functions. For example, optical functions such as a diffraction grating can be provided. Thereby, the chromatic aberration compensating lens can also be used as a lens, and the number of parts of the optical system can be reduced.

In the second aspect of the present invention, the coupling layer may be formed to a thickness of 1 nm or less. By forming the coupling layer to have a thickness of 1 nm or less and a thickness of about several molecular layers to one molecular layer, the thickness unevenness of the coupling layer disappears, and the adhesion to the optical resin layer can be further improved.

In the second aspect of the present invention, the minute particle layer may be formed by spin coating or dipping a dispersion of minute particles. By spin coating or dipping, tiny particles are densely aggregated on the optical substrate to form a layer. Baking in this state or irradiating with energy rays such as ultraviolet rays causes the fine particles to bond or the resin between the fine particles to harden, whereby a dense fine particle layer can be formed.

In the second aspect of the present invention, the minute particle layer may be patterned. For example, when the fine particle layer is baked at a temperature of about 140° C., the film strength of the fine particle layer can be obtained to such an extent that the fine particles can be removed by a detergent solution. Therefore, after coating the dispersion of fine particles, bake at about 140°C to form a patterned resist film on the surface of the fine particle layer, immerse it in a cleaning solution and heat it, thereby removing The fine particles in the portion not covered by the resist film can thus be patterned.

In addition, when the dispersion liquid of fine particles contains a photosensitive resin, after the fine particle layer is formed, it is selectively exposed, and then immersed in a cleaning solution to remove the non-exposed part, thereby, the fine particle layer can be removed. patterned.

Hereinafter, matters common to the first aspect and the second aspect of the present invention may be described as "the present invention".

In the present invention, the outer surface of the optical resin layer may have an aspheric shape. By forming the outer surface of the optical resin layer into an aspheric shape, for example, a composite aspheric lens can be formed.

In the present invention, the fine particles dispersed in the intermediate layer can be dispersed in the optical resin layer.

In the present invention, for example, the refractive index of the intermediate layer may be equal to or higher than the refractive index of the optical resin layer and equal to or lower than the refractive index of the optical substrate. That is, the refractive index of the intermediate layer can be set to a range between the refractive index of the optical base material and the refractive index of the optical resin layer.

The fine particles contained in the intermediate layer include, for example, at least one selected from silicon oxide, niobium oxide, and zirconium oxide.

In the present invention, unevenness can be formed at the interface between the intermediate layer and the optical resin layer by forming unevenness on the surface of the intermediate layer. By forming irregularities at the interface between the intermediate layer and the optical resin layer, the adhesiveness between the intermediate layer and the optical resin layer can be further improved.

In the present invention, the intermediate layer may be provided so as to cover the periphery of the optical substrate. By providing the intermediate layer so as to cover the periphery of the optical base material, it is possible to more effectively prevent intrusion of moisture or the like, and further improve reliability.

In the present invention, an antireflection film may be provided on the outer surface of the optical resin layer. In addition, an antireflection film may be provided on the surface of the optical substrate opposite to the side on which the intermediate layer is provided.

In the present invention, the antireflection film is formed of, for example, the same material as the intermediate layer, and is a film in which irregularities are formed on the surface by dissolving and removing fine particles near the surface.

Hereinafter, the optical resin layer, intermediate layer, and optical substrate of the present invention will be described in detail.

<Optical resin layer>

The optical resin layer of the present invention is composed of an organometallic polymer having a -M—O—M—bond (M is a metal atom), a metal alkoxide having only one hydrolyzable group and/or its hydrolyzate, and an amino group having A formate bond and a methacryloxy group or an organic polymer having a urethane bond and an acryloxy group are formed.

The above-mentioned organic polymer is an organic polymer having a urethane bond and a methacryloxy group or an organic polymer having a urethane bond and an acryloxy group. Isocyanate, an organic polymer obtained by reacting a hydroxyl group with a compound having a methacryloyloxy group or an acryloyloxy group.

As a specific structure, when a part having a methacryloxy group or an acryloxy group (acrylate part or methacrylate part) is denoted as AC, and a part having a urethane bond (isocyanate part) is denoted as When it is IS and the polyol part is recorded as PO, there are

AC—IS—PO—IS—AC

The structure of the structure is usually called acrylate resin.

From the viewpoint of reducing water absorption, it is preferable to use an acrylate resin having a highly hydrophobic phenyl group or a bisphenol A structure.

In the above structure, at least one of AC-IS and IS-PO is bonded by a urethane bond. The existence of this urethane bond is important, and the cohesive force of the hydrogen bond derived from the urethane bond can make the optical resin layer have flexibility and toughness in the cured state, thereby preventing further damage to the optical resin layer. Cracks, etc., occur under high temperature and high humidity.

The above-mentioned AC moiety has a polymerizable group (double bond of carbon), and has the function of curing the optical resin layer by polymerizing the organic polymer itself or forming a bond with the above-mentioned organometallic polymer by energy such as light and heat.

In addition, by introducing a polymerizable group into the organometallic polymer in advance, it can be polymerized with the AC component in the organic polymer to form a stronger bond.

The above-mentioned PO part is a part that imparts properties such as flexibility to the organic polymer. For example, it is made of polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, silicone polyols etc.

Organic polymers having the above structures are generally called urethane acrylate resins and the like.

The above-mentioned metal alkoxide and/or its hydrolyzate are contained in the optical resin layer. The metal alkoxide and/or its hydrolyzate may be contained in a state not bonded to the organometallic polymer, or may be contained in a bonded state. In addition, the hydrolyzate of the metal alkoxide may be a polycondensate of the hydrolyzate.

In the optical resin layer, by containing a metal alkoxide and/or its hydrolyzate having only one hydrolyzable group, the metal alkoxide and/or its hydrolyzate react with the -OH group generated at the terminal of the organometallic polymer molecule , can eliminate -OH groups. Therefore, it is possible to reduce the light propagation loss and the water absorption rate generated in the wavelength range of 1450 to 1550 nm.

For example, when the metal atom M is Si, an alkoxy group represented by -Si-O-R may exist at the terminal of the organometallic polymer molecule. This alkoxy group absorbs water, hydrolyzes, and reacts as follows to generate a silanol group.

—Si—O—R+H ₂ O→—Si—OH+ROH↑

The ROH generated in the above reaction is volatilized. When the above-mentioned silanol groups exist, the transmittance decreases and the water absorption increases.

When a metal alkoxide having only one hydrolyzable group and/or a hydrolyzate thereof is contained, the silanol group generated as described above can be eliminated. For example, an alkoxysilane having only one alkoxy group represented by the following formula absorbs water and is hydrolyzed as follows.

R' ₃ Si—O—R”+H ₂ O→R' ₃ Si—OH+R”OH↑

In the above reaction, R"OH is volatilized. The hydrolyzate produced as above reacts with the terminal silanol group of the organometallic polymer as follows.

—Si—OH+R' ₃ Si—OH→—Si—O—SiR' ₃ +H ₂ O

Through the above reaction, the silanol group at the molecular terminal of the organometallic polymer is eliminated. Therefore, high transmittance can be maintained for a long time, and water absorption can be reduced.

As described above, the metal alkoxide is hydrolyzed and acts as a hydrolyzate, so it may be contained in the form of the metal alkoxide or in the form of a hydrolyzate. In addition, when the organometallic alkoxide or its hydrolyzate is contained in a state not bonded to the organometallic polymer, in the organometallic polymer, moisture is reabsorbed, and silanol groups are generated at its terminals. The metal alkoxide or its hydrolyzate in this state acts on the silanol group and the like to eliminate the silanol group and the like as described above.

The metal alkoxide or its hydrolyzate may contain fluorine atoms. That is, metal alkoxides in which hydrogen atoms in the hydrocarbon moiety are substituted by fluorine atoms and their hydrolyzates may be used.

M in the -M—O—M—bond of the organometallic polymer is preferably Si, Ti, Nb or Zr or a combination of these metals, particularly preferably Si. When it is Si, the organometallic polymer can be formed of, for example, a silicone resin.

It is preferable to further contain an organic acid anhydride and/or an organic acid in the optical resin layer.

Since the organic acid anhydride absorbs moisture and is hydrolyzed, the moisture in the organometallic polymer can be reduced by containing the organic acid anhydride. Thereby, the absorption caused by moisture is reduced, and even if only the organic acid anhydride is added, deterioration of the material due to moisture can be suppressed, and the transmittance can be improved. In addition, the organic acid contained in the organometallic polymer promotes the reaction of silanol groups and the like. Therefore, elimination of silanol groups and the like can be promoted. For example, it is also possible to promote the reaction between silanol groups at the molecular ends of the organometallic polymer.

It is preferable to contain an organic acid anhydride and/or an organic acid in the optical resin layer for the following reasons. That is, by containing a metal alkoxide having only one hydrolyzable group and/or its hydrolyzate and an organic acid anhydride and/or an organic acid at the same time, except for the removal of moisture generated by the organic acid anhydride, only one hydrolyzable group The hydrolyzate of the metal alkoxide reacts with the -OH group generated at the end of the organometallic polymer molecule, and promotes the reaction to eliminate the -OH group.

When the above-mentioned metal alkoxide or its hydrolyzate is an alkoxysilane or its hydrolyzate, the compound represented by the following general formula can be mentioned as an example.

(Here, R ₁ , R ₂ and R ₃ are an organic group having 1 to 15 carbon atoms, preferably an alkyl group. In addition, R ₄ is an alkyl group having 1 to 4 carbon atoms.)

Specific examples include trialkylalkoxysilanes such as trimethylalkoxysilane and triethylalkoxysilane. Examples of the alkoxy group include methoxy group, ethoxy group and the like.

Specific examples of the aforementioned organic acid anhydride include trifluoroacetic anhydride, acetic anhydride, propionic anhydride, and the like. Particular preference is given to using trifluoroacetic anhydride. Specific examples of the aforementioned organic acid include trifluoroacetic acid, acetic acid, propionic acid, and the like. Particular preference is given to using trifluoroacetic acid.

An organometallic polymer can be synthesized, for example, by hydrolysis and polycondensation of an organometallic compound having at least two hydrolyzable groups. As such an organometallic compound, an organic group-containing trialkoxysilane or dialkoxysilane is mentioned, for example. As an organic group, an alkyl group, an aryl group, a group containing an aryl group, etc. are mentioned. As the aryl group, phenyl is preferred. Furthermore, as preferable compounds, phenyltrialkoxysilane, diphenyldialkoxysilane, more preferably phenyltriethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane Silane, Diphenyldiethoxysilane.

In addition, as the above-mentioned organometallic compound, it is preferable to contain an organometallic compound having a functional group crosslinked by heating and/or irradiation with energy rays. Examples of energy rays include ultraviolet rays, electron rays, and the like. As such a crosslinking functional group, an acryloxy group, a methacryloxy group, a styryl group, an epoxy group, and a vinyl group are mentioned. Therefore, trialkoxysilanes having these functional groups are preferably used.

When radically polymerizable functional groups such as acryloyloxy groups, methacryloyloxy groups, styryl groups, and vinyl groups are contained, it is preferable to contain a radical-based polymerization initiator. As a radical polymerization initiator, for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-benzyl-2 -Dimethylamino-1-(4-morpholinophenyl)-butanone-1, oxygen (oxy)-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethyl Oxy]-ethyl-ester, oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl-ester, and mixtures thereof.

Moreover, when containing the organometallic compound which has an epoxy group, it is preferable to contain a hardening|curing agent. Examples of such curing agents include amine-based curing agents, imidazole-based curing agents, phosphorus-based curing agents, acid anhydride-based curing agents, and the like. Specifically, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, tetraethylenediamine, and the like are exemplified.

When an organometallic compound with a functional group and an organometallic compound without a functional group are used in combination, the mixing ratio is based on a weight ratio (organometallic compound with a functional group: organometallic compound without a functional group), preferably 5 to 5 95:95~5.

In the optical resin layer, the content of the above-mentioned organic polymer is preferably 5 to 95% by weight, more preferably 40 to 95% by weight. When the content of the above-mentioned organic polymer is too small, cracks are likely to be generated under high temperature and high humidity, which becomes a factor of light absorption and scattering. Conversely, when the content of the above-mentioned organic polymer is too large, heat resistance decreases, deterioration in a high-temperature environment progresses, and optical properties, particularly light transmittance, decrease.

As mentioned above, by making the content of the above-mentioned organic polymer in the range of 5 to 95% by weight, the optical resin layer can be made into a more transparent material. For example, at a wavelength of 630 nm, the transmittance of a sample with a thickness of , more than 80% can be obtained. Moreover, by making content of the said organic polymer into the range of 40 to 95 weight%, the transmittance becomes 90% or more.

In the optical resin layer, the content of the metal alkoxide or its hydrolyzate is preferably 0.1 to 15 parts by weight, more preferably 0.2 to 2.0 parts by weight, based on 100 parts by weight of the organometallic polymer. When the content of the above-mentioned metal alkoxide or its hydrolyzate is too small, OH groups remain, absorption in the wavelength range of 1450 to 1550 nm increases, water absorption becomes high, and deterioration is likely. Conversely, when the content of the above-mentioned metal alkoxide or its hydrolyzate is too large, the excess of the above-mentioned metal alkoxide or its hydrolyzate will detach from the material in a high-temperature environment and become a main cause of cracks.

In addition, the content of the organic acid anhydride or the organic acid is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the organometallic polymer. When the content of the organic acid anhydride or the organic acid is too small, the removal of the OH group by the metal alkoxide having only one hydrolyzable group is incomplete. The organic acid anhydride or organic acid itself will detach from the material and become the main cause of cracks.

In addition, in the optical resin layer, the difference between the refractive index of the cured product of the organometallic polymer and the refractive index of the cured product of the organic polymer is preferably 0.01 or less. By setting the difference in refractive index to 0.01 or less in this way, scattering of light due to the difference in refractive index at the interface between the organometallic polymer domain and the organic polymer domain in the material is suppressed, and a transmittance of 90% or more can be obtained.

In addition, in the optical resin layer, the difference between the refractive index in the liquid state before the organometallic polymer is cured and the refractive index before the organic polymer is cured is preferably 0.02 or less. By setting the difference in refractive index between the two in the liquid state before curing to 0.02 or less in this way, the transmittance of the material after curing can be made 90% or more.

The optical resin layer preferably has an absorption peak around 850 cm ⁻¹ caused by the above-mentioned metal alkoxide in an IR measurement chart. By having such an absorption peak, the trimethylsilyl group which is a metal alkoxide having only one hydrolyzable group is sufficiently contained in the material, and the OH group in the material is effectively removed.

<Middle layer of the first aspect>

The intermediate layer according to the first aspect of the present invention is formed by dispersing fine particles of a metal oxide in a matrix resin made of a metal alkoxide having a radically polymerizable group and a hydrolyzable group and/or its hydrolyzate. layer.

As said metal alkoxide, trialkoxysilane or dialkoxysilane etc. which have a radically polymerizable group are mentioned.

Moreover, as a radical polymerizable group, an acryloyloxy group, a methacryloyloxy group, a styryl group, a vinyl group, etc. are mentioned. As metal alkoxides, trialkoxysilanes having these groups are particularly preferably used.

Examples of microparticles composed of metal oxides dispersed in the matrix resin include silicon oxide, niobium oxide, zirconium oxide, titanium oxide, aluminum oxide, yttrium oxide, cerium oxide, and lanthanum oxide, among which silicon oxide is particularly preferably used. , Niobium oxide, Zirconia. The size of the fine particles in the present invention is preferably 100 nm or less, more preferably within a range of 5 to 50 nm, in terms of average particle diameter.

In the intermediate layer according to the first aspect of the present invention, the amount of fine particles contained in the matrix resin is appropriately selected so as to have a desired refractive index. Usually, the content of fine particles in the intermediate layer is preferably in the range of 0.5 to 50% by weight.

The intermediate layer according to the first aspect of the present invention is cured by polymerizing the radically polymerizable radical in the metal alkoxide and/or its hydrolyzate. For example, it can be cured by heating or irradiating energy rays such as ultraviolet rays.

The radical polymerization-based polymerization initiator described in the optical resin layer may also be contained in the intermediate layer.

In the intermediate layer, by adding fine particles with a low refractive index, it is possible to control the lowering of the refractive index of the intermediate layer. In addition, by containing fine particles having a high refractive index as the fine particles, it is possible to control the refractive index of the intermediate layer so that it becomes high. Examples of metal oxide particles capable of increasing the refractive index include niobium oxide (Nb ₂ O ₅ ) particles, zirconium oxide (ZrO ₂ ) particles, and titanium oxide (TiO ₂ ) particles. In addition, silicon oxide (SiO ₂ ) particles are exemplified as fine particles capable of lowering the refractive index.

In addition, as described above, fine particles may also be contained in the optical resin layer.

<Intermediate layer of the second aspect>

The intermediate layer of the second aspect of the present invention includes a fine particle layer provided on the side of the optical substrate and a coupling layer provided on the side of the optical resin layer.

As the fine particles in the second aspect of the present invention, the fine particles used in the first aspect of the present invention can be used.

In addition, as the metal alkoxide and/or its hydrolyzate forming the coupling layer in the second aspect of the present invention, the same metal alkoxide and/or its hydrolyzate in the first aspect can be used.

The fine particle layer in the first aspect of the present invention may be formed by laminating a plurality of layers. A plurality of layers may be formed by laminating layers of different fine particles.

As the binder resin used in the second aspect of the present invention, water-soluble acrylic monomers, water-soluble resins, silane coupling agents, and photosensitive resins can be cited as described above.

Examples of the water-soluble acrylic monomer include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 2-dimethylaminoethyl methacrylate.

Examples of water-soluble resins include epoxy resins such as polyethylene glycol glycidyl ether, acrylic resins such as polyacrylates and polymethacrylates, and polysiloxanes composed mainly of siloxane bonds. Silicone-based resins formed by adding hydrophilic groups to the chain, etc.

Examples of the silane coupling agent include methacryloxy-based silane coupling agents such as 3-methacryloxypropyltrimethoxysilane, cyclic silanes such as 3-glycidoxypropyltrimethoxysilane, etc. Styryl-based silane coupling agents such as oxygen-based silane coupling agents, hydrolyzates such as p-styryltrimethoxysilane or polymers of hydrolyzates, and the like.

As a photosensitive resin, the above-mentioned water-soluble acrylic monomer, water-soluble acrylic resin, etc. are mentioned.

In the second aspect of the present invention, as the cleaning solution for patterning the fine particle layer, a cleaning solution for cleaning optical components may be mentioned.

<Optical substrate>

Examples of the optical substrate in the present invention include members such as translucent glass, ceramics, and plastics. When forming a thin multilayer optical element, high-refractive-index glass, high-refractive-index translucent ceramics, etc. can be used as the optical substrate.

<Laminated Optical Components>

As the multilayer optical element of the present invention, a composite aspheric lens can be mentioned. A composite aspheric lens is formed by forming a light transmission region made of a translucent resin layer on a spherical lens made of glass or the like to form an aspheric lens. In the present invention, since an intermediate layer is provided between an optical substrate such as a spherical lens and an optical resin layer that is a translucent resin layer, an optical resin layer excellent in adhesion can be provided. In addition, in the present invention, a material excellent in hardness and heat resistance is used for the optical resin layer. Therefore, the multilayer optical element of the present invention is a multilayer optical element that has high reliability under high temperature and high humidity and is excellent in hardness and heat resistance.

The multilayer optical element of the present invention is excellent in reliability under high temperature and high humidity, and has high hardness and heat resistance, so it can be applied to various substrates for electrical wiring, materials for machine parts, antireflection films, and surface protection films. Coating materials, optical sending and receiving components, optical switches, optical modulators and other optical communication devices, optical waveguides, optical fibers, lens arrays and other optical propagation path structures, and optical devices including them such as beam splitters, integrator lenses ), microlens arrays, reflectors, light guide plates, projection screens and other display devices (displays or liquid crystal projectors, etc.) ) lenses, optical filters, diffraction gratings, interferometers, optical couplers, optical multiplexers, optical sensors, holographic optical elements, materials for other optical components, photoelectromotive force elements, contact lenses, medical artificial tissues, light-emitting diodes ( LED) mold materials, etc.

The imaging module of the present invention is characterized in that it has a combination lens composed of a plurality of lenses, an imaging element, and a holder for holding them, and at least one of the plurality of lenses is the multilayer optical element of the present invention. .

A mobile phone of the present invention is characterized by including the camera module of the present invention.

The liquid crystal projector of the present invention is characterized in that, comprises: light source; Illumination optical system; The liquid crystal part that is made of liquid crystal, semi-transparent mirror, reflecting mirror, and lens etc.; The projection optical system of the lens and the light source are arranged adjacent to each other.

In the present invention, between the optical substrate and the optical resin layer, fine particles made of metal oxide are dispersed in metal alkoxide and/or its hydrolyzate having a radically polymerizable group and a hydrolyzable group. The intermediate layer is formed in the matrix resin formed. Therefore, the laminated optical element of the present invention has excellent adhesion between the optical resin layer and the optical substrate, high reliability under high temperature and high humidity, and excellent hardness and heat resistance.

Description of drawings

Fig. 1 is a cross-sectional view showing a cross-sectional structure of a laminated optical element according to Embodiment 1 of the present invention.

Fig. 2 is a cross-sectional view showing a cross-sectional structure of a laminated optical element according to Example 2 of the present invention.

Fig. 3 is a cross-sectional view showing a cross-sectional structure of a laminated optical element according to Embodiment 3 of the present invention.

Fig. 4 is a cross-sectional view showing a cross-sectional structure of a laminated optical element according to Embodiment 5 of the present invention.

FIG. 5 is a diagram showing the structure of a matrix resin layer of the intermediate layer shown in FIG. 4 .

Fig. 6 is a cross-sectional view showing a cross-sectional structure of a laminated optical element according to Embodiment 6 of the present invention.

Fig. 7 is a cross-sectional view showing a cross-sectional structure of a laminated optical element according to Embodiment 7 of the present invention.

Fig. 8 is a cross-sectional view along line A-A shown in Fig. 7 .

Fig. 9 is a cross-sectional view showing a cross-sectional structure of a laminated optical element according to Embodiment 8 of the present invention.

FIG. 10 is a cross-sectional view showing the structure of the antireflection film 9 shown in FIG. 9 .

11 is a cross-sectional view showing a manufacturing process of a composite aspheric lens as a laminated optical element in each embodiment according to the present invention.

12 is a cross-sectional view showing a composite aspheric lens of a comparative example.

Fig. 13 is a cross-sectional view along line A-A shown in Fig. 12 .

FIG. 14 is a cross-sectional view showing a cross-sectional structure of Comparative Example 2. FIG.

FIG. 15 is a cross-sectional view showing a cross-sectional structure of Comparative Example 3. FIG.

FIG. 16 is a cross-sectional view showing a cross-sectional structure of Comparative Example 4. FIG.

FIG. 17 is a schematic diagram showing an apparatus for observing spherical aberration of a compound aspheric lens.

Fig. 18 is a diagram showing a mesh pattern when observed using a glass spherical lens and a composite aspheric lens.

Fig. 19 is a cross-sectional view showing a cross-sectional structure of a laminated optical element according to Embodiment 9 of the present invention.

Fig. 20 is an enlarged cross-sectional view showing a cross-sectional structure of a laminated optical element according to Embodiment 9 of the present invention.

Fig. 21 is a cross-sectional view showing a cross-sectional structure of a laminated optical element according to Embodiment 10 of the present invention.

Fig. 22 is an enlarged cross-sectional view showing a cross-sectional structure of a laminated optical element according to Embodiment 10 of the present invention.

Fig. 23 is a cross-sectional view showing a cross-sectional structure of a laminated optical element according to Embodiment 11 of the present invention.

Fig. 24 is an enlarged cross-sectional view showing a cross-sectional structure of a laminated optical element according to Embodiment 11 of the present invention.

Fig. 25 is a cross-sectional view showing a cross-sectional structure of a laminated optical element according to Embodiment 12 of the present invention.

Fig. 26 is a cross-sectional view showing a cross-sectional structure of a laminated optical element according to Embodiment 13 of the present invention.

Fig. 27 is a cross-sectional view showing the steps of manufacturing a laminated optical element according to Example 14 of the present invention.

Fig. 28 is a cross-sectional view showing the steps of manufacturing a laminated optical element according to Example 15 of the present invention.

Fig. 29 is a cross-sectional view showing a cross-sectional structure of a laminated optical element according to Embodiment 16 of the present invention.

Fig. 30 is a perspective view showing a state in which a plurality of optical elements are formed on a plate-like optical substrate according to the present invention.

Fig. 31 is a cross-sectional view showing a camera module having a laminated optical element according to the present invention.

FIG. 32 is a cross-sectional view showing a mobile phone equipped with a conventional camera module.

Fig. 33 is a cross-sectional view showing a cellular phone having a camera module using the laminated optical element according to the present invention.

Fig. 34 is a schematic sectional view showing a liquid crystal projector having a laminated optical element according to the present invention.

Fig. 35 is a schematic sectional view showing a liquid crystal projector having a laminated optical element according to the present invention.

Fig. 36 is a schematic sectional view showing a liquid crystal projector having a laminated optical element according to the present invention.

Fig. 37 is a cross-sectional view showing an optical waveguide according to the present invention.

Fig. 38 is a graph showing the relationship between the Nb ₂ O ₅ content in the mixed fine particle layer and the refractive index.

Fig. 39 is a graph showing the relationship between the refractive index of the substrate and the reflectance of the mixed fine particle layer.

Symbol Description

1 Optical substrate

2 middle layer

3 Optical resin layer

4 matrix resin layer

5 tiny particles

6 Coupling agent layer

7, 8 Anti-reflection film

9 matrix resin layer

21, 23～31, 32a, 32b, 33, 34, 35a, 35b, 36a, 36b tiny particle layer

22 coupling layer

40 camera module

41, 42, 43, 44 aspherical lens

45 camera components

50 portable phone

51 TV tuner

52 hard drives

53 display

54 keyboard

55 batteries

60 LCD projectors

61 Projection optical system

62 Illumination optical system

63 light source

64, 65 semi-transparent mirror (halfmirror)

66, 67, 68 Reflector (mirror)

69 Orthogonal Prisms

70, 71, 72 lens

73, 74, 75 LCD panel

80 substrate

81 middle layer

82 Tiny particle layer

83 coupling layer

84 optical resin layer

85 core layer

86 lower cladding

86a Slot for lower cladding

87 upper cladding

Detailed ways

Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example.

[Coupling agent solution 1]

3-Methacryloxypropyltrimethoxysilane (MPTMS) was diluted with ethanol to 2% by weight to prepare a coupling agent solution 1 .

This solution is applied on the surface of the substrate by spin coating or the like, and OH groups generated by hydrolyzing MPTMS with moisture in the atmosphere form hydrogen bonds with the substrate. In addition, since the organic group (methacryloxypropyl group moiety) in the MPTMS hydrolyzate has good compatibility with organic materials such as resin, the adhesion to the resin layer is improved.

[Coupling agent solution 2]

After adding 6.8g MPTMS in 13g ethanol and stirring, add 8g pure water, 1.6g 2N hydrochloric acid and stir, leave for 72 hours, make coupling agent solution 2.

In the coupling agent solution 2, by adding hydrochloric acid, hydrolysis and polycondensation can be actively and sufficiently performed, and thus a high-viscosity solution can be obtained. Therefore, compared with the coupling agent solution 1, a thicker coupling agent layer can be formed.

[Coupling agent solution 3]

Further dilute coupling agent solution 2 with 200 g of ethanol to prepare coupling agent solution 3.

〔Silicon oxide particle dispersion〕

A dispersion liquid in which silicon oxide particles (average particle diameter: 20 nm) was dispersed in ethanol to 10% by weight was prepared, and this dispersion liquid was mixed with the above-mentioned coupling agent solution 2 to prepare a silicon oxide particle dispersion liquid.

The mixing ratio is adjusted so that a predetermined refractive index can be obtained when the dispersion liquid is cured by heating and/or light irradiation. In the case of a silicon oxide particle dispersion, the higher the mixing ratio of the silicon oxide particles, the smaller the refractive index after curing. By adjusting the mixing ratio of the silicon oxide particles, the refractive index nD at a wavelength of 589 nm can be adjusted within a range of about 1.50 to 1.48.

Hereinafter, unless otherwise specified, a dispersion liquid whose refractive index was adjusted to 1.48 was used.

[Niobium Oxide Particle Dispersion]

Add 4.72g MPTMS and 2.08g diphenyldimethoxysilane (DPhDMS) in 13g ethanol, then add 8g pure water, 1.6g 2N hydrochloric acid and stir, stand for 72 hours. A dispersion liquid in which niobium oxide particles (average particle diameter: 10 nm) was dispersed in ethanol to 10% by weight was prepared, and the above-mentioned MPTMS and DPhDMS solutions were mixed with the dispersion liquid to prepare a niobium oxide particle dispersion liquid.

The mixing ratio of the aforementioned metal alkoxide and niobium oxide particles is adjusted so that the layer formed by applying the solution achieves a defined refractive index. In the case of the niobium oxide particle dispersion, the higher the content of the niobium oxide particles, the larger the refractive index after curing. By controlling the content of niobium oxide particles, the refractive index nD at a wavelength of 589 nm can be adjusted within the range of about 1.53-1.60.

Hereinafter, unless otherwise specified, a dispersion liquid having a refractive index of 1.59 was used.

[Solution for forming optical resin layer]

After mixing 10 ml (10.4 g) of MPTMS, 4.1 ml (4.4 g) of DPhDMS, and 1.65 ml (1.7 g) of 2N hydrochloric acid in 20.5 ml (16.2 g) of ethanol, the metal alkoxide was hydrolyzed and polycondensed by standing for 24 hours. Put 4ml of the obtained polycondensate liquid into a glass vessel with a cover, and dissolve 10mg of 1-hydroxy-cyclohexyl-phenyl-ketone as a polymerization initiator, and then heat at 100°C to evaporate ethanol Removal gave viscous liquid A. 3 ml (2.25 g) of trimethylethoxysilane and 0.8 ml (0.41 g) of trifluoroacetic anhydride were mixed in 1 g of this viscous liquid A, and after standing for 24 hours, they were heated and dried at 100° C. Trimethylethoxysilane and trifluoroacetic anhydride were evaporated to give B as a viscous liquid.

0.45 g of urethane acrylate photocurable resin was added to 0.55 g of this viscous liquid B, followed by stirring to obtain a solution for forming an optical resin layer containing 45% by weight of urethane acrylate photocurable resin.

(Example 1)

<Production of composite aspheric lens>

A composite aspheric lens was manufactured by the manufacturing process shown in FIG. 11 .

As shown in FIG. 11( a ), a spherical lens made of glass is used as the optical base 1 , and after the intermediate layer 2 is formed on the optical base 1 , the solution 3 for forming an optical resin layer is dropped thereon. As the optical substrate 1, a high-refractive-index glass spherical lens (refractive index nD of glass = about 1.8) having a diameter of 5 mm and a maximum thickness of 1 mm was used. The intermediate layer 2 was formed by spin-coating a silicon oxide particle dispersion and heating at 100° C. for 1 hour.

As shown in FIG. 11( b ), the mold 10 made of nickel with an aspheric surface shape on the inner surface is pressed on the solution 3 for forming an optical resin layer, and then, as shown in FIG. 11( c ), irradiates The ultraviolet rays cure the optical resin layer forming solution 3 to form the optical resin layer 3 . Specifically, the optical resin layer 3 was cured by irradiating ultraviolet light from the optical substrate 1 side for 6 minutes with a high-pressure mercury lamp (intensity about 40 mW/cm ² ), and the mold 10 was removed as shown in FIG. 11( d ). Next, ultraviolet rays were irradiated from the side of the optical resin layer 3 for 10 minutes with a high-pressure mercury lamp (intensity of about 40 mW/cm ² ) to further cure the optical resin layer 3 .

As described above, the composite aspheric lens shown in FIG. 11( e ) was obtained.

FIG. 1 is a cross-sectional view along line AA of FIG. 11( e ). As shown in FIG. 1 , an intermediate layer 2 is formed on an optical substrate 1 , and an optical resin layer 3 is formed on the intermediate layer 2 . In addition, although not shown in FIG. 11( e ), antireflection films 7 and 8 are formed on the outer surface of the optical resin layer 3 and the surface on the opposite side of the optical substrate 1 , respectively. The antireflection films 7 and 8 are formed by vacuum evaporation. The antireflection film 7 formed on the optical resin layer 3 is SiO ₂ layer (thickness 31nm)/Ti ₂ O ₃ layer (thickness 15nm)/SiO ₂ layer (thickness 24nm)/Ti ₂ in order from the optical resin layer 3 side. An anti-reflection film consisting of 5 layers of O ₃ layers (thickness 93nm)/SiO ₂ layers (thickness 83nm). Furthermore, the refractive index of the SiO ₂ layer is 1.46, and that of the Ti ₂ O ₃ layer is 2.35.

The antireflection film 8 formed on the optical substrate 1 is Ti ₂ O ₃ layers (thickness 11nm)/SiO ₂ layers (thickness 24nm)/Ti 2 O 3 layers (thickness 117nm)/Ti ₂ O ₃ layers (thickness 117nm)/ Anti-reflection coating consisting of 4 layers of SiO ₂ layers (thickness 89nm). In addition, the refractive index of the SiO ₂ layer and the refractive index of the Ti ₂ O ₃ layer are the same as above.

As shown in FIG. 1 , the intermediate layer 2 of the present embodiment is formed of a matrix resin layer 4 in which silicon oxide particles 5 are dispersed. The thickness of the intermediate layer 2 is 200 nm. In addition, the maximum thickness of the optical resin layer 3 is 140 μm.

(Example 2)

As shown in FIG. 2 , the intermediate layer 2 is formed by the coupling agent layer 6 provided on the optical substrate 1 and the matrix resin layer 4 in which the silicon oxide particles 5 are dispersed. In the same manner as in Example 1, a composite aspheric lens was produced.

The coupling agent layer 6 was formed by spin-coating the coupling agent solution 3 and heating at 140° C. for 1 hour. The thickness of the coupling agent layer 6 is 10 nm. The matrix resin layer 4 was formed in the same manner as in Example 1. Its maximum thickness is 200 nm.

Therefore, the thickness of the intermediate layer 2 in this embodiment is 210 nm.

(Example 3)

In this embodiment, niobium oxide particles are used as the fine particles 5 . A composite aspherical lens was produced in the same manner as in Example 2 above except that the niobium oxide particle dispersion liquid was used for forming the matrix resin layer 4 to thereby use the niobium oxide particles as the microparticles 5 .

(Example 4)

Niobium oxide particles (average particle diameter: 10 nm) were added to ethanol to make a ratio of 10% by weight to prepare a dispersion, and 1 g of the dispersion was added to 1 g of the optical resin layer forming solution and stirred to prepare a niobium oxide-dispersed A solution for forming an optical resin layer of particles. Except having used this solution to form the optical resin layer 3, it carried out similarly to Example 3, and produced the compound type aspherical lens.

(Example 5)

As shown in FIG. 4 , as the intermediate layer 2 , a coupling agent layer 6 is formed on the optical substrate 1 , a matrix resin layer 9 is formed on the coupling agent layer 6 , and the coupling agent layer 6 is formed on the matrix resin layer 9 . The matrix resin layer 9 has a structure in which four layers are laminated as shown in FIG. 5 . That is, the matrix resin layer 4a in which the silicon oxide particles 5a are dispersed is laminated on the matrix resin layer 4b in which the niobium oxide particles 5b are dispersed, and the two-layer laminated structure is repeated to form a matrix resin layer with a total of four layers. 9. Specifically, after the niobium oxide particle dispersion was spin-coated and heated at 140°C for 1 hour, the silicon oxide particle dispersion was spin-coated thereon and heated at 140°C for 1 hour. This step is repeated twice to form matrix resin layer 9 having a four-layer structure shown in FIG. 5 .

The coupling agent layer 6 on the optical substrate 1 was formed by spin-coating the coupling agent solution 3 and then heating at 140° C. for 1 hour. Its thickness is 10 nm.

The coupling agent layer 6 on the matrix resin layer 9 was formed by spin-coating the coupling agent solution 3 and then heating at 100° C. for 1 hour. Its thickness is 10 nm. The optical resin layer 3 was formed in the same manner as in Example 1.

Each layer of the matrix resin layer 9 shown in FIG. 5 has the following thicknesses from the side close to the optical resin layer, that is, from the top.

Matrix layer dispersed with silicon oxide particles: thickness 169nm

Matrix layer dispersed with niobium oxide particles: thickness 157nm

Matrix layer dispersed with silicon oxide particles: thickness 93nm

Matrix layer dispersed with niobium oxide particles: thickness 79nm

In addition, the refractive index of the matrix layer in which silicon oxide particles were dispersed was 1.48, and the refractive index of the matrix layer in which niobium oxide particles were dispersed was 1.59.

As a comparison, a composite aspheric lens without matrix layer 9 was produced, and the transmittance was compared with the composite aspheric lens of this embodiment. In the composite aspheric lens of this embodiment formed with matrix resin layer 9 , the transmittance increased by about 1.8%.

(Example 6)

The intermediate layer 2 shown in FIG. 6 is formed. The coupling agent layer 6 was formed by spin-coating the coupling agent solution 3 and then heating at 140° C. for 1 hour. Its thickness is 10 nm.

The matrix resin layer 4 in which the silicon oxide particles 5 are dispersed is formed by spin-coating a silicon oxide particle dispersion, heating at 140° C. for 1 hour, and irradiating ultraviolet light with a high-pressure mercury lamp to have a thickness of 0.9 μm. By bringing this layer into contact with a buffered hydrofluoric acid (BHF) solution, silicon oxide particles near the surface are dissolved and removed, pores 4c are formed on the surface, and the surface is made porous.

Thereafter, the optical resin layer 3 is formed in the same manner as in Example 1, whereby the optical resin layer 3 is formed in a state where the resin of the optical resin layer 3 is impregnated into the holes 4 c of the matrix resin layer 4 .

(Example 7)

In this embodiment, as shown in FIG. 7 , the intermediate layer 2 is formed on the entire periphery of the optical substrate 1 .

Fig. 8 is a cross-sectional view along line A-A shown in Fig. 7 . As shown in FIG. 8 , intermediate layer 2 is formed by forming coupling agent layer 6 and matrix resin layer 4 in which niobium oxide particles 5 are dispersed on optical substrate 1 . Specifically, after immersing the optical substrate 1 in the coupling agent solution 3, it was lifted up, and after the excess solution was blown away by air blowing, it was heated at 140° C. for 1 hour. A coupling agent layer 6 with a thickness of 10 nm was formed on the entire periphery of the optical substrate 1 .

Next, the optical substrate 1 on which the coupling agent layer 6 is formed is dipped in the niobium oxide particle dispersion, and after being lifted up, the excess dispersion is blown away by air blowing, and thereafter, heated at 100° C. for 1 hour, Thus, the matrix resin layer 4 with a thickness of 200 nm was formed on the entire surface around the optical substrate 1 .

Next, the optical resin layer 3 was formed in the same manner as in Example 1 so as to have a maximum thickness of 140 μm.

(Embodiment 8)

As shown in FIG. 9, in this embodiment, except that the antireflection film 13 formed on the optical resin layer 3 is formed as the antireflection film 13 shown in FIG. Compound aspheric lens. The antireflection film 13 in this embodiment is formed by the following method: after coating the silicon oxide dispersion liquid, it is contacted with the buffered hydrofluoric acid (BHF) solution in the same manner as in Example 5, and the silicon oxide particles near the surface are dissolved and removed, Pores 4c are formed to make them porous. The thickness of the antireflection film 13 was 4 μm.

As shown in FIG. 10 , it has a structure in which the volume of the porous hole 4 c increases from the side closer to the optical resin layer toward the outside. Therefore, the refractive index changes continuously, thereby giving it an anti-reflection function.

(comparative example 1)

FIG. 12 shows a composite aspheric lens of Comparative Example 1. FIG. As shown in FIG. 12 , an optical resin layer 3 is formed on an optical substrate 1 . Fig. 13 is a sectional view along line A-A of Fig. 12 . As shown in FIG. 13, after the coupling agent layer 11 is formed on the optical substrate 1, the optical resin layer 3 is formed thereon. As the optical substrate 1, the same high-refractive-index glass spherical lens as in Example 1 was used. The coupling agent layer 11 was formed by spin-coating the coupling agent solution 1 and then heating at 100° C. for 1 hour. The optical resin layer 3 was formed in the same manner as in Example 1 so that the maximum thickness thereof was 140 μm. In addition, the antireflection films 7 and 8 were also formed in the same manner as in the first embodiment.

Since the thickness of the coupling agent layer 11 cannot be measured with a stylus profiler, it is considered to be 10 nm or less.

(comparative example 2)

As shown in FIG. 14 , in this comparative example, the thickness of the coupling agent layer 11 was increased. The coupling agent layer 11 was formed by using the coupling agent solution 3 and heating it at 100° C. for 1 hour after spin-coating it. The thickness of the coupling agent layer 11 was measured with a stylus profiler and found to be 10 nm.

(comparative example 3)

As shown in FIG. 15 , in this comparative example, the thickness of the coupling agent layer 11 was further increased. Specifically, the coupling agent layer 11 was formed by using the coupling agent solution 2 and heating it at 100° C. for 1 hour after spin-coating. Measured with a stylus profiler, the thickness of the coupling agent layer 11 is 200 nm.

(comparative example 4)

As shown in FIG. 16 , in this comparative example, an epoxy-based photocurable resin was used as a matrix resin on the coupling agent layer 11 to form a matrix resin layer 12 in which silicon oxide particles 5 were dispersed. Therefore, it formed similarly to Example 2 except having used the epoxy-type photocurable resin as a matrix resin.

Specifically, after spin-coating the coupling agent solution 3, heating at 140° C. for 1 hour to form a coupling agent layer 11 with a thickness of 10 nm, and then spin-coating on it to disperse the silicon oxide particles in the epoxy-based photocuring The dispersion liquid formed in the resin was then heated at 100° C. for 1 hour to form a matrix resin layer 12 with a thickness of 200 nm. Dispersion liquid of epoxy resin in which silicon oxide particles are dispersed, using ethanol as a solvent, using a dispersion liquid containing about 5% by weight of silicon oxide particles (average particle diameter: 20nm) and about 20% by weight of epoxy-based photocurable resin .

〔Surface roughness of the surface of the intermediate layer〕

In each of the examples and comparative examples described above, the surface roughness of the intermediate layer was measured after the intermediate layer was formed. The measured surface roughness of the intermediate layer is the roughness of the surface to be the interface with the optical resin layer. The surface roughness was measured by AFM (Atomic Force Microscopy: atomic force microscope). Table 1 shows the measurement results.

〔High temperature and high humidity test〕

A high-temperature and high-humidity test was performed on the composite aspheric lenses of the above-mentioned examples and comparative examples. The 50 samples were left in an environment of 85° C. and 85% for 800 hours, and the number of samples in which the optical resin layer was not peeled off from the substrate was measured. Table 1 shows the results.

〔Measurement of reflectance〕

The reflectance on the side of the optical resin layer was measured. The method for measuring the reflectance is to measure with a lens reflectance measuring machine.

Table 1 shows the evaluation results.

〔Lattice pattern projection test〕

Using the apparatus shown in FIG. 17 , a lattice pattern projection test was performed on the composite aspheric lenses of the above-mentioned Examples and Comparative Examples.

The lens 17 to be measured is arranged between the screen 18 on which the mesh pattern is formed and the CCD camera 16, and the mesh pattern on the screen 18 is magnified by the CCD camera 16 for observation. The mesh pattern on the screen 18 is a mesh pattern 19 at intervals of 0.5 mm as shown in FIG. 17 .

When the glass spherical lens 10 is used as the lens 17, an image of a skewed mesh pattern as shown in FIG. 18(a) is observed due to spherical aberration peculiar to a spherical lens. On the other hand, when the composite aspherical lens produced as described above is used as the lens 17, an image in which the mesh pattern is faithfully enlarged as shown in FIG. 18(b) is obtained. The case where the mesh pattern as shown in FIG.18(b) was obtained was rated as "good". The case where the lines of grids were partially skewed slightly or fluctuated in thickness was described as "defective".

The measurement results are shown in Table 1.

Table 1

middle layer thickness Surface roughness of the interlayer surface High temperature and high humidity test (a) Reflectance on the resin side (wavelength 630nm) Lattice pattern projection test Example 1 200nm Below 50nm 40 0.3% or less good Example 2 210nm Below 50nm 45 0.3% or less good Example 3 210nm Below 50nm 43 0.3% or less good Example 4 210nm Below 50nm 48 0.3% or less good Example 5 518nm Below 50nm 50 0.3% or less good Example 6 1μm Below 50nm 50 0.3% or less good Example 7 210nm Below 50nm 50 0.3% or less good Example 8 210nm Below 50nm 45 about 0.7% good Comparative example 1 Below 10nm Below 10nm 7 0.3% or less good Comparative example 2 10nm Below 10nm 18 0.3% or less good Comparative example 3 200nm 100～150nm 40 0.3% or less bad Comparative example 4 210nm Below 50nm 38 0.3% or less good

From the results shown in Table 1, it can be seen that the composite aspheric lens according to the example of the present invention is excellent in durability under high temperature and high humidity. In addition, although Comparative Example 3 was excellent in durability under high temperature and high humidity, the lattice pattern was defective, and bleeding and distortion occurred.

In the above examples, silicon oxide particles and niobium oxide particles were used as fine particles, but the same results as above can be obtained when zirconia particles are used instead of them.

In addition, in the above-mentioned examples, urethane acrylate resin was used as the organic polymer of the optical resin layer, but acrylate resins such as epoxy acrylate resin, polyester acrylate resin, silicone urethane acrylate resin, etc. The same effects can also be obtained with UV-based or thermosetting resins and epoxy-based thermosetting or UV-curable resins.

Next, an embodiment according to the second aspect of the present invention will be described.

(Example 9)

Fig. 19 is a cross-sectional view showing the laminated optical element of this embodiment. An intermediate layer 2 is formed on the optical substrate 1 , and an optical resin layer 3 is formed on the intermediate layer 2 . The intermediate layer 2 is composed of a fine particle layer 21 formed on the optical substrate 1 and a coupling layer 22 formed on the fine particle layer 21 .

As the optical substrate 1 in this example, a substrate of high refractive index glass was used. High-refractive-index glass generally contains a large amount of high-refractive-index oxides such as TiO ₂ , ZrO ₂ , Nb ₂ O ₅ , and Ta ₂ O ₅ , and contains a small amount of silica. The high-refractive-index glass used in this example is a high-refractive-index glass with a trade name of "S-TIH6" (manufactured by Ohara Co., Ltd.), free of Pb and As, and containing a large amount of TiO ₂ .

The fine particle layer 21 is formed by applying a commercially available colloidal silica aqueous solution and then baking at 400° C. for 2 hours. The colloidal silica aqueous solution is usually an aqueous solution in which SiO ₂ microparticles with an average particle diameter of 5 nm to 500 nm are dispersed in water at a content of 10 to 40% by weight. In this example, an aqueous colloidal silica solution having an average particle diameter of 5 nm and a SiO ₂ content of 10% by weight was used. In addition, the average particle diameter can be measured with an electron microscope.

The above-mentioned colloidal silica aqueous solution was diluted with water so that the weight ratio (colloidal silica aqueous solution: water) became a ratio of 1:8, spin-coated at a rotation speed of 3000 rpm, and coated on the optical substrate 1. on high refractive index lenses. Before coating, the surface of the lens is pre-treated with dilute hydrofluoric acid in order to improve the wettability of the aqueous solution of colloidal silica. Instead of the hydrofluoric acid treatment, a treatment such as making the cleaning agent component adsorb on the glass surface in the cleaning agent may be performed. By performing such pretreatment, the uniformity of dispersion of fine particles in the fine particle layer can be improved. The thickness of the fine particle layer depends on the state of the surface treatment, and can be controlled by the concentration of the colloidal silica aqueous solution if the state of the surface treatment and application conditions such as spin coating are always constant. In this embodiment, the thickness of the fine particle layer 21 is set to 20 nm. In order to prevent cracks and the like, the thickness of the fine particle layer is preferably about 1000 nm or less. In addition, as a liquid containing _SiO2 fine particles, liquids using alcohols other than water, toluene, etc. as solvents are also commercially available, but when using an aqueous solution, the bonding force between the coated fine particles is strong, so it is preferable. In addition, when alcohol and toluene were compared, when an alcohol solution was used, a fine particle layer with a firm film quality was obtained. That is, as the solution for forming the fine particle layer, an aqueous solution is most preferable, and next, a solution of alcohols such as ethanol and isopropanol is preferable.

As described above, after coating the aqueous colloidal silica solution on the optical substrate 1, it baked at 400 degreeC for 2 hours. Thereby, in the interface between the optical substrate 1 and the fine particle layer 21 , mutual diffusion of the respective constituent substances occurs. Adhesiveness is improved by this interdiffusion. If the heat treatment temperature at this time is higher than 500°C, deformation of the base material will occur depending on the type of glass, so the temperature is preferably 500°C or lower, preferably about 400°C.

FIG. 20 is an enlarged view showing the fine particle layer 21 and the coupling agent layer 22 in FIG. 19 . As shown in FIG. 20 , in the fine particle layer 21 , due to the diffusion of Ti from the optical substrate 1 , a Ti diffusion region 21 a is formed. In addition, above the fine particle layer 21, a silicon dioxide high-concentration region 21b in which a large amount of silicon dioxide components are present is formed. The analysis of Ti concentration was performed by STEM-EDS analysis. STEM-EDS analysis is a method of analyzing the types and ratios (chemical composition) of contained elements based on the intensity of X-rays generated when electron beams are irradiated to the cross-section of a sample subjected to cross-sectional TEM observation. According to the analysis results, about 1 atomic % of Ti was detected in the silica high-concentration region 21 b, and about 9 atomic % of Ti was detected in the Ti-diffused region 21 a. Therefore, it is considered that about 99% is Si and about 1% is Ti in the silica high-concentration region 21b. In addition, it is considered that in the Ti diffusion region 21a, about 91% is Si and about 9% is Ti. Therefore, it is considered that in the Ti diffusion region 21a, Ti is present at a concentration approximately 9 times higher than that in the silicon dioxide high concentration region 21b.

After the above-mentioned baking treatment, the above-mentioned “coupling agent solution 2 ” is applied on the fine particle layer 21 to form a coupling layer 22 . After coating, heat treatment at 100° C. for 5 minutes, and then use isopropyl alcohol to remove excess coupling agent to form a coupling agent layer of 1 nm or less on the surface. This layer is so thin that it cannot be observed with a transmission electron microscope, and is considered to have a thickness of about 1 molecular layer to several molecular layers.

After applying the coupling agent solution in this way, it is preferable to perform heat treatment at about 100 to 120°C. In addition, after coating, it is preferable to remove excess coupling agent with alcohol such as ethanol or isopropanol to form a thickness of 1 nm or less. Thereby, a coupling layer with higher adhesiveness can be formed.

On the coupling layer 22 formed as described above, an optical resin layer is formed using the above-mentioned "solution for forming an optical resin layer".

In this embodiment, before the coupling agent solution is applied to form the coupling layer 22, a pretreatment for making the surface of the fine particle layer 21 hydrophobic is performed. Such pretreatment includes treatment using an organic solvent-based liquid. In this embodiment, a photoresist remover (trade name: "502A", produced by Tokyo Ohka Co., Ltd., 100% by weight of aromatic hydrocarbons) containing alkylbenzene and alkylbenzenesulfonic acid as main components was used. , 20% by weight of phenol, and 20% by weight of alkylbenzenesulfonic acid), the surface of the fine particle layer 21 is pretreated by immersing in this remover. After handling, wash with acetone.

In this example, "coupling agent solution 2" was used, but "coupling agent solution 1" or "coupling agent solution 3" may be used instead.

<Peel test>

On the optical substrate composed of the laminated optical element and the high-refractive index glass lens of the above-mentioned examples, a coupling layer was directly formed without forming a fine particle layer, and an optical resin layer was formed thereon to produce a laminate as a comparative sample. Optical element.

The samples of the examples and the samples of the comparative examples were left in an atmosphere of a temperature of 85° C. and a humidity of 85% for 500 hours as an accelerated test, and then the samples of the examples and the comparative examples were visually observed. In the sample of the comparative example, the approximately circular optical resin layer of several μm to several tens of μm peeled off, but in the sample of the present example, no peeling was observed at all. In addition, the same result was obtained also as other high-refractive-index glass "S-LAH79" (manufactured by Ohara Co., Ltd.) and high-refractive-index light-transmitting ceramics.

(Example 10)

Fig. 21 is a cross-sectional view showing the laminated optical element of this embodiment. As shown in FIG. 21, an intermediate layer 2 is formed on an optical substrate 1, and an optical resin layer 3 is formed thereon. The intermediate layer 2 is formed by laminating a fine particle layer and a coupling layer ₂₂ , and the fine particle layer includes a fine particle layer 23 composed of _Nb2O5 , a fine particle layer 24 composed of _SiO2 , a fine particle layer ₂₄ composed of _Nb2O5 The fine particle layer 25 made of SiO 2 and the fine particle layer 26 made of SiO ₂ .

As the optical substrate 1, the same high-refractive-index glass lens (refractive index: 1.8) as in Example 9 was used.

The thickness of the fine particle layer 23 is 20 nm, the thickness of the fine particle layer 24 is 20 nm, the thickness of the fine particle layer 25 is 140 nm, and the thickness of the fine particle layer 26 is 80 nm. The fine particle layers 24 and 26 made of SiO ₂ were formed by diluting an aqueous colloidal silica solution (average particle diameter 5 nm, SiO ₂ content 10% by weight) with water and spin-coating as in Example 10. The fine particle layers 23 and 25 composed of Nb ₂ O ₅ were diluted with water to 50 times and 1.6 times, respectively, a commercially available Nb ₂ O ₅ sol aqueous solution (average particle diameter: 5 nm, Nb ₂ O ₅ content: 10% by weight). fold and spin-coat it to form. However, since only a thickness of about 70 nm can be obtained by one spin coating, the fine particle layer 25 was spin coated twice. In addition, before the fine particle layer 23 was formed, pretreatment using a photoresist remover was performed in the same manner as in Example 10.

After spin-coating the colloidal silica aqueous solution, it baked at 140 degreeC for 1 minute. Also, after spin-coating an aqueous Nb ₂ O ₅ sol solution, it was baked at 140° C. for 1 minute. After forming the fine particle layer 26, it baked at 400 degreeC for 2 hours similarly to Example 10, and performed interdiffusion treatment by this. Through this interdiffusion treatment, the adhesion of the multilayer film is improved. Thereafter, a coupling agent is applied in the same manner as in Example 10 to form a coupling layer 22, on which the optical resin layer 3 is formed.

FIG. 22 is an enlarged view of the intermediate layer 2 . As shown in FIG. 22 , in the fine particle layers 23 , 24 and 25 , diffusion of Ti from the optical substrate 1 occurs.

In this embodiment, a fine particle layer composed of SiO ₂ is formed on a fine particle layer composed of Nb ₂ O ₅ , but a fine particle layer in which Nb ₂ O ₅ and SiO ₂ are mixed may be formed between these layers. , so that the composition changes stepwise. Thereby, a multilayer film with less stress during film formation can be formed.

<Peel test>

The sample of this example was also subjected to a peeling test in the same manner as in Example 9 above, and as a result, no peeling was observed at all. In addition, the same result was obtained also as other high-refractive-index glass "S-LAH79" (manufactured by Ohara Co., Ltd.) and high-refractive-index light-transmitting ceramics.

(Example 11)

Fig. 23 is a cross-sectional view showing the laminated optical element of this embodiment. As shown in FIG. 23 , an intermediate layer 2 is formed on an optical substrate 1 , and an optical resin layer 3 is formed on the intermediate layer 2 . The intermediate layer 2 is formed of the first fine particle layer 27 and the second fine particle layer 28 and the coupling layer 22 . The first fine particle layer 27 is formed using an aqueous colloidal silica solution in the same manner as in Example 9, and is formed by applying the aqueous colloidal silica solution and then baking at 400° C. for 2 hours. Its thickness is 5 nm. Next, the second fine particle layer 28 was formed by applying the same aqueous solution of colloidal silica, then lowering the temperature of the baking treatment to 280° C. and performing a baking treatment for 30 minutes. Its thickness is 5 nm.

FIG. 24 is an enlarged view of the intermediate layer 2 . The first fine particle layer 27 is baked at 400° C. as described above, and therefore Ti and the like are diffused from the optical substrate 1 . On the other hand, since the second fine particle layer 28 is baked at 280°C as described above, diffusion of Ti and the like hardly occurs, and it becomes a layer with a large silicon dioxide content. Therefore, the adhesion with the coupling layer 22 formed thereon becomes more favorable.

By providing a fine particle layer formed by baking at a lower temperature as in this example, even if the overall thickness of the fine particle layer is reduced, a layer rich in silica can be formed on the surface. Since the generation of peeling and cracks can be reduced by reducing the thickness of the fine particle layer, a multilayer optical element with higher reliability can be manufactured according to such a method.

In addition, the coupling layer 22 and the optical resin layer 3 were formed in the same manner as in Example 9.

(Example 12)

Fig. 25 is a cross-sectional view showing the laminated optical element of this embodiment. As shown in FIG. 25 , an intermediate layer 2 is formed on an optical substrate 1 , and an optical resin layer 3 is formed on the intermediate layer 2 . In this embodiment, the intermediate layer 2 is constituted by forming the coupling layer 22 on the fine particle layer 29 . In this example, the fine particle layer 29 was formed using an aqueous solution of colloidal silica having an average particle diameter of 80 nm. By setting the average particle diameter of the SiO ₂ fine particles to 80 nm, large irregularities were formed on the surface of the fine particle layer 29 . Therefore, the surface area of the fine particle layer 29 can be increased, and the coupling layer 22 and the optical resin layer 3 can be formed in an interface state in which they enter each other. Therefore, the mutual adhesion between the fine particle layer 29 , the coupling layer 22 and the optical resin layer 3 is improved.

In addition, the coupling layer 22 and the optical resin layer 3 were formed in the same manner as in Example 9.

(Example 13)

Fig. 26 is a cross-sectional view showing the laminated optical element of this embodiment. As shown in FIG. 26, in this embodiment, an intermediate layer 2 is formed on the optical substrate 1, an optical resin layer 3 is formed on the intermediate layer 2, and the intermediate layer 2 is composed of a first fine particle layer 30, a second fine particle layer The particle layer 31 and the coupling layer 22 are formed.

The first fine particle layer 30 is formed by applying an aqueous solution of colloidal silica with an average particle diameter of 5 nm, followed by baking at 400° C. for 2 hours, so that the thickness is about 20 nm. The second fine particle layer 31 is formed by applying an aqueous solution of colloidal silica having an average particle diameter of 80 nm and treating it at 280° C. for 30 minutes so as to have a thickness of about 300 nm. In this way, by forming the first fine particle layer 30 and the second fine particle layer 31, it is possible to manufacture a laminated optical element having good adhesion to the optical substrate 1 and good adhesion to the coupling layer 22 and the optical resin layer 3. .

That is, the first fine particle layer 30 is formed as an extremely flat layer with an average particle diameter of 5 nm even when observed by TEM, and the fine particles are airtightly aggregated to form a layer without forming gaps. Therefore, the optical substrate 1 is in contact with the entire interface, and the adhesiveness with the optical substrate 1 is in a good state. A dense layer can be formed by using colloidal particles having an average particle diameter of about 50 nm. As in Example 12, the second fine particle layer 31 has large irregularities formed on its surface, so that the adhesiveness with the coupling layer 22 and the optical resin layer 3 is good.

Although the interface between the first fine particle layer 30 and the second fine particle layer 31 has a small contact area, they are made of the same material, and thus sufficient adhesion can be obtained even by annealing at, for example, about 120°C.

In this embodiment, the fine particle layer is divided into two layers to form a hierarchical structure in which the particle diameter of the fine particle layer gradually increases, but it is also possible to further form multiple layers and form a hierarchical structure in which the particle diameter increases.

In addition, the coupling layer 22 and the optical resin layer 3 were formed in the same manner as in Example 9.

(Example 14)

In each of the above examples, the colloidal silica aqueous solution was used to form the fine particle layer, but it may also be used after adding a binder resin to the colloidal silica aqueous solution. By adding such a binder resin, the fine particle layer can be solidified and formed without performing a baking treatment at a high temperature of about 300 to 500°C. For example, it can be cured by heating to a temperature of about 120° C., or cured by irradiating ultraviolet rays.

The present example is an example using an aqueous solution of fine particles to which such a binder resin is added.

Fig. 27 is a cross-sectional view showing the manufacturing process of the multilayer optical element of this example. First, an optical substrate 1 composed of a high refractive index glass lens as shown in FIG. 27( a ) is prepared. Next, as shown in FIG. 27( b ), a first fine particle layer 32 a is formed on one surface of the optical substrate 1 . The first fine particle layer 32a is formed by _{interdiffusion} treatment at 400° C. , so that the thickness is 20 nm. Thereon, as shown in FIG. 27( b ), the coupling layer 22 and the optical resin layer 3 were formed in the same manner as in Example 9.

Next, as shown in FIG. 27(c), the second fine particle layer 32b is formed so as to cover the whole. Use 20 μl (microliter) of methacrylate-2-hydroxyethyl methacrylate in a mixture of 4ml of colloidal silicon dioxide aqueous solution (average particle diameter 5nm, _SiO content of 10% by weight) and 4ml of water as a resin binder. The aqueous solution formed from the mixture is applied to form the second fine particle layer 32b. Regarding the coating method, in the spin coating method, unevenness may occur in the coating, so it is preferable to blow nitrogen or air from above the coated liquid with an air gun or the like to dry it as quickly as possible. In this example, the coating was performed while drying by blowing air. After the coating film is dried, ultraviolet rays are irradiated to form the second fine particle layer 32b.

The reason why the resin binder is used in forming the second fine particle layer 32 b is that the first optical resin layer 3 a has already been formed and thus cannot be baked at a high temperature.

Next, as shown in FIG. 27( d), on the second fine particle layer 32b on the other surface of the optical substrate 1, the same operation as in Example 9 is performed to form the second coupling layer 22b and the second optical resin. Layer 3b.

In the laminated optical element shown in FIG. 27( d), the second fine particle layer 32b can function as a hard coat layer on one surface (upper surface) of the optical substrate 1, and can function as a hard coat layer on the other surface. One surface (lower surface) can function as a fine particle layer for improving adhesion.

As the resin binder, 2-hydroxyethyl methacrylate, which is a kind of water-soluble acrylic monomer, was used in this embodiment, but water-soluble acrylic resins, water-soluble epoxy resins, and the like may also be used. In addition, in the mixture of 4ml colloidal silica aqueous solution and 4ml water, add 20μl (microliter) of 2-hydroxyethyl methacrylate, and then add 20μl (microliter) of coupling agent solution 2 , thereby becoming a more stable liquid, which has the effect of reducing uneven coating.

As a binder resin, among water-soluble acrylic monomers, those having a hydroxyl group like the above-mentioned monomers are difficult to aggregate fine particles and are very easy to handle.

In addition, when forming a fine particle layer composed of Nb ₂ O ₅ , unevenness after coating is less likely to occur compared with a fine particle layer of SiO ₂ . For example, in a mixture of 4 ml of Nb ₂ O ₅ sol aqueous solution (average particle size 5 nm, Nb ₂ O ₅ content 10% by weight) and 4 ml of water, add 20 μl (microliter) of methacrylic acid-2-hydroxyethyl base ester, and spin-coated to form. In addition, a multilayer film can be easily formed by alternately laminating fine particle layers made of SiO ₂ and fine particle layers made of Nb ₂ O ₅ and simultaneously irradiating ultraviolet rays.

(Example 15)

Fig. 28 is a cross-sectional view showing the manufacturing process of the multilayer optical element of this embodiment.

As shown in FIG. 28( a ), a high-refractive-index lens with one surface flat is prepared as an optical substrate 1 . Next, as shown in FIG. 28(b), on the flat side of the optical substrate 1, Nb ₂ O ₅ sol aqueous solution (average particle diameter 5 nm, Nb ₂ O ₅ content 10% by weight) was applied without dilution, Patterning was performed as follows to form the first fine particle layer 33 to fabricate a Fresnel lens. There are the following two methods for producing a Fresnel lens.

<first method>

After coating the aqueous solution of Nb ₂ O ₅ sol (average particle diameter 5 nm, Nb ₂ O ₅ content 10% by weight), it was baked at 140° C. for 30 minutes to solidify the fine particle layer to a certain extent. Next, a photoresist is formed on the surface of the fine particle layer, and a resist pattern of a diffraction grating is formed using a photomask. Thereafter, by immersing for 5 to 10 minutes in a special cleaning agent for glass cleaning (trade name "SE10", manufactured by Sonic Fellow Co., Ltd.) heated to 80°C, the fine particles in the parts not covered by the resist film are partially eluted. to the cleaning agent and removed. Thereafter, the photoresist is removed using a resist stripper. The fine particle layer can be removed with hydrofluoric acid, but in this case, the underlying lens may be etched. However, by using this cleaning agent, only the fine particle layer can be selectively removed. This removal method can be used not only for Nb ₂ O ₅ but also for SiO ₂ and other oxide particles.

<second method>

After applying the same mixture of 4 ml of Nb ₂ O ₅ sol aqueous solution and 20 µl of 2-hydroxyethyl methacrylate as above, ultraviolet irradiation was performed using a photomask. As a result, 2-hydroxyethyl methacrylate, which is a photosensitive acrylic monomer, undergoes a crosslinking reaction, and only the photosensitive portion of the fine particle layer is cured. Next, by immersing for 5 to 10 minutes in a cleaning agent (SE10) heated to 80°C for glass cleaning, the fine particle layer of the unexposed part is eluted into the cleaning agent and removed.

After the first fine particle layer 33 composed of Nb ₂ O ₅ is patterned by the above method, as shown in FIG. 28( c ), the second fine particle layer 34 composed of SiO ₂ is applied. When a binder resin is added to the first fine particle layer, it is preferable to also add a binder resin to the second fine particle layer 34 . In addition, when the first fine particle layer 33 is patterned without adding a binder resin, it is preferable not to add a binder resin to the second fine particle layer 34 either. At this time, the second fine particle layer was baked at 400° C. for 2 hours after coating to be cured.

Next, after applying the coupling agent solution 2, the coupling agent on the surface was removed with alcohol in the same manner as in Example 9 to form a coupling layer 22 having a thickness of 1 nm or less.

Next, as shown in FIG. 28( d ), an optical resin layer 3 is formed on the coupling layer 22 in the same manner as in Example 9, whereby a Fresnel lens can be produced.

(Example 16)

Fig. 29 is a cross-sectional view showing the laminated optical element of this embodiment. In the laminated optical element of this embodiment, a plate-shaped optical element 1 is used, on both sides of which, a Fresnel lens formed by a diffraction grating and an aspheric lens formed by the optical resin layers 3a and 3b are formed, respectively. . On the upper surface and the lower surface, in the same manner as in Example 15, patterned first fine particle layers 35a and 35b are formed respectively, and second fine particle layers 36a and 36b are formed thereon, respectively. The layers 22a and 22b are coupled, and then the optical resin layers 3a and 3b are formed thereon.

In addition, when a plate-shaped base material is used as the optical base material, as shown in FIG. 30 , a plurality of optical elements 37 can be produced simultaneously on the same optical base material 1 .

In addition, as shown in FIG. 27 , when forming the fine particle layer as the outermost hard coat layer, a diffraction grating can be formed by patterning part of the hard coat layer.

In each of the above-mentioned embodiments, Ti, which is an optical base material component, is diffused into the fine particle layer by interdiffusion treatment, and even if it is, for example, Nb, Zr, Sn, Ce, Ta, etc., it can also be improved in the same way as Ti. The effect of the adhesion of the particle layer to the optical substrate.

In each of the above-mentioned embodiments, the spin coating method has been mainly described as the coating method for forming the fine particle layer, but the coating may be performed by the dipping method instead of the spin coating method. In this case, it is preferable to lift up the optical substrate at a constant speed after dipping the optical substrate in the coating solution for uniform coating.

In each of the above-mentioned examples, SiO ₂ and Nb ₂ O ₅ were described as fine particles, but the present invention is not limited to these fine particles, and ZrO ₂ , TiO ₂ , Al ₂ O ₃ , and SnO ₂ may also be used. , CeO ₂ , Ta ₂ O ₅ and other oxides; GaN, AlN, GaInN and other nitride-based fine particles with a higher refractive index than oxides; or diamond fine particles, etc. Since these fine particles have high physical hardness, they are preferably used when also serving as a hard coat layer. In addition, in the case of nitride-based fine particles, in oxides such as TiO ₂ and Nb ₂ O ₅ , due to photocatalytic reaction, when ultraviolet rays are irradiated on the part in contact with the optical resin, the resin may be discolored. However, such a problem can be solved by using nitride-based fine particles.

(Example 17)

Fig. 31 is a cross-sectional view showing an example of the camera module of the present invention. As shown in FIG. 31 , a combined lens composed of four aspherical lenses 41 , 42 , 43 , and 44 held by a holder 46 is provided on the imaging element 45 . The camera module 40 has four aspheric lenses 41 to 44 in this way, and can be used as a camera module of 2 to 5 megapixels for a mobile phone.

In the aspheric lenses 41 to 44 of this embodiment, the fine particle layer 21 shown in Embodiment 9 and the coupling layer 22 formed on the fine particle layer are formed on the optical substrate. Therefore, the optical resin layer 3 can be formed with good adhesion and reliability even on an optical substrate with a low silica content, and high-refractive-index glass with a low silica content can be used as an optical substrate. Therefore, in this example, as the aspherical lenses 41 to 44, the high refractive index glass (manufactured by Ohara Co., Ltd., trade name "S-LAH79", refractive index about 2.0) was used as the optical base material in Example 9. And formed aspheric lens. Since a high-refractive-index substrate with a refractive index of about 2.0 is used, the focal length can be shortened. Therefore, the length of the bracket 46 can be shortened, so the height of the camera module of this embodiment can be set to about 8 mm.

In addition, in this embodiment, all the aspheric lenses 41-44 are compound aspheric lenses, but according to the design of the camera module, it is not necessary to make all the lenses be compound aspheric lenses, as long as at least one lens It only needs to be a composite aspheric lens.

In a conventional camera module for a cellular phone that uses a composite aspheric lens that does not have a fine particle layer 21 as shown in Example 9 on an optical substrate, in order to maintain the adhesion between the optical substrate and the optical resin layer, it is necessary to The silica content of the optical substrate is increased, so the glass material that can be used is limited, and its refractive index reaches about 1.6. Therefore, the focal length cannot be shortened, so the height of the conventional camera module is about 10 mm.

32 is a cross-sectional view showing a foldable mobile phone in which a conventional camera module with a height of 10 mm is arranged.

In the half-folded state shown in Fig. 32(a) and (b), the height H is 25 mm. In the mobile phone shown in FIG. 32( a ), the height _h1 of the upper part and the height _h2 of the lower part are each 12.5 mm, which are the same height. There is a camera module 40 in the upper part, and a TV tuner 51, a hard disk drive 52, a display 53, and the like are built in. In FIG. 32( a ), the height _h1 of the upper part is 12.5 mm, which is low, so the presence of the camera module 40 becomes troublesome, and a small display 53 is provided. In the lower part, a keyboard 54, a battery 55, and the like are built in.

In the mobile phone shown in FIG. 32(b), the height _h1 of the upper part is 14.5 mm, and the height _h2 of the lower part is 10.5 mm. Since the height _h1 of the upper part is designed to be high, a large display 53 can be arranged. On the other hand, since the height _h2 of the lower part is 10.5 mm, the volume of the battery 55 becomes small, and there is a problem that the battery capacity becomes small.

Fig. 33 is a sectional view showing a portable telephone according to an embodiment of the present invention. The camera module 40 of the present invention is incorporated in the mobile phone shown in FIGS. 33( a ) and ( b ). The height of the camera module 40 of the present invention can be reduced to, for example, about 8mm. Therefore, as shown in _FIG . _h2 is 12.5mm which is the same as the height _h1 of the upper part. Therefore, a large-capacity battery 55 can be incorporated.

In addition, as shown in FIG. 33( b ), it is possible to arrange the camera modules 40 in the upper part and the lower part, respectively. Therefore, it is possible to capture a stereoscopic image, and it is also possible to capture one's own face with high image quality. In addition, applications such as panoramic photography using a plurality of cameras, electrical synthesis of output signals of a plurality of cameras to substantially improve sensitivity, and the like are also possible.

(Example 18)

In addition, the camera module shown in FIG. 31 can also be used as a camera module of a vehicle-mounted rear monitor. A vehicle-mounted camera module requires high heat resistance, and the aspheric lens used in Example 17 can be used. In addition, since the aspheric lens has a high refractive index, it is possible to widen the viewing angle.

(Example 19)

Fig. 34 is a schematic sectional view showing a liquid crystal projector. An illumination optical system 62 is provided on the light source 63, and the illumination optical system 62 is composed of lenses 62a and 62b. The light emitted from the light source 63 is irradiated on the half mirror 64 , and the light transmitted through the half mirror 64 is reflected by the mirror 68 , passes through the lens 70 and the liquid crystal panel 73 , and enters the cross prism 69 .

On the other hand, the light reflected by the half mirror 64 is irradiated on the half mirror 65 , and the light reflected by the half mirror 65 enters the cross prism 69 through the lens 71 and the liquid crystal panel 74 .

The light transmitted through the half mirror 65 is reflected by the mirror 66 and then reflected by the mirror 67 , passes through the lens 72 and the liquid crystal panel 74 , and enters the cross prism 69 .

The liquid crystal panel 75 is a liquid crystal panel for red (R), the liquid crystal panel 74 is a liquid crystal panel for green (G), and the liquid crystal panel 73 is a liquid crystal panel for blue (B). The light passing through these liquid crystal panels is synthesized by the cross prism 69, passes through the projection optical system 61, and is emitted to the outside. The projection optical system 61 is composed of composite aspheric lenses 61a, 61b, and 61c.

The light source 63 is constituted by, for example, a metal halide lamp, a mercury lamp, an LED, or the like.

Because the light source 63 is a heat source, in the conventional liquid crystal projector that does not use the fine particle layer 21 shown in Embodiment 9, due to the influence of repeated temperature changes caused by the on/off of the light source, there are glass substrates. In order to avoid the problem of delamination between the material and the optical resin layer, it is necessary to keep the lenses 61a to 61c of the projection optical system as far as possible from the light source 63 to a certain extent.

However, in this example, the composite aspheric lenses used in Example 17 are used for the lenses 61a to 61c, and the optical substrates of these composite aspheric lenses are formed with the The fine particle layer 21 and the coupling layer 22 formed on the fine particle layer. Therefore, regardless of the silica content of the optical base material, the optical resin layer 3 can be formed with good adhesion and reliability, even if the glass base material and the optical resin layer are separated due to repeated temperature changes caused by the on/off of the light source 63. The resin layer does not peel off either. In addition, the optical resin layer (resin lens layer) of the composite aspheric lens is formed of an organometallic polymer material having good heat resistance including an organometallic polymer and an organic polymer, so it has good heat resistance. sex. Therefore, the lenses 61 a to 61 c can be arranged near the light source 63 .

Fig. 35 is a schematic sectional view showing an embodiment of a liquid crystal projector according to the present invention.

In the embodiment shown in FIG. 35 , the lenses used in the seventeenth embodiment are used for the lenses 61 a to 61 c of the projection optical system 61 . Therefore, as shown in FIG. 35 , the position of the light source 63 can be arranged close to the projection optical system 61 . Therefore, the size of the liquid crystal projector 60 can be reduced.

In the liquid crystal projector shown in FIG. 35 , the light emitted from the light source 63 is irradiated on the half mirror 64 through the illumination optical system 62, and the light reflected by the half mirror 64 is incident through the lens 70 and the liquid crystal panel 73. to cross prism 69. The light transmitted through the half mirror 64 is reflected by the mirror 68 and goes to the half mirror 65 . The light reflected by the half mirror 65 passes through the lens 71 and the liquid crystal panel 74 and enters the cross prism 69 . The light transmitted through the half mirror 65 is reflected by the mirror 66 and then reflected by the mirror 67 , and enters the cross prism 69 through the lens 72 and the liquid crystal panel 75 . The light transmitted through the liquid crystal panels 73 , 74 , and 75 is synthesized by the cross prism 69 and emitted to the outside through the projection optical system 61 .

The liquid crystal projectors shown in Fig. 34 and Fig. 35 are 3-panel transmissive projectors that display RGB with independent liquid crystal panels. The same effect can also be obtained.

In the liquid crystal projector shown in FIG. 36 , a white LED is used as the light source 63 in order to achieve further miniaturization. As shown in FIG. 36 , the light emitted from the light source 63 passes through the illumination optical system 62 , passes through the lens 70 and the liquid crystal panel 73 , passes through the projection optical system 61 , and is emitted to the outside.

As shown in FIG. 36 , the light source 63 and the projection optical system 61 can be arranged on a straight line. In such a case, the lens 61a, 61b, and 61c of the projection optical system 61 use the composite aspheric lens used in Example 17, thereby shortening the focal length, so that the overall length of the liquid crystal projector can be shortened. .

(Example 20)

Fig. 37 is a cross-sectional view showing the optical waveguide of the present invention. As shown in FIG. 37 , an intermediate layer 81 is provided on a substrate 80 , and an optical resin layer 84 is formed on the intermediate layer 81 . The optical resin layer 84 is formed of a lower cladding layer 86 , a core layer 85 provided in a groove 86 a of the lower cladding layer 86 , and an upper cladding layer 87 , and constitutes an optical waveguide. The intermediate layer 81 is composed of a fine particle layer 82 and a coupling layer 83 .

As the substrate 80 , for example, a glass substrate, a Si substrate, a sapphire substrate, a GaN substrate, or the like can be used. In addition, a substrate having an Al ₂ O ₃ film, a SiN film, a metal film, or the like formed on the surface of these substrates may also be used. According to the present invention, even if a substrate containing no _SiO2 component is used on the substrate surface, by forming a fine particle layer substantially composed of _SiO2 , the effect of improving the adhesion of the coupling layer can be enhanced, and an optical resin layer can be formed with good adhesion.

The fine particle layer 82 can be formed using the colloidal silica aqueous solution similarly to Example 9, for example. In addition, the coupling layer 83 can also be formed in the same manner as in Example 9.

On the coupling layer 83 formed as described above, the lower cladding layer 86 , the core layer 85 , and the upper cladding layer 87 are formed to form the optical resin layer 84 as an optical waveguide. The lower cladding layer 86 and the upper cladding layer 87 can be formed using the "solution for forming an optical resin layer" in Example 1. In addition, for the core layer 85, the "solution for forming an optical resin layer" in Example 1 was also used, but the refractive index of the core layer needs to be about 0.005 higher than the refractive index of the cladding layer. Therefore, after preparing the "optical resin layer For "formation solution", add 0.1ml more PhDMS than for the coating layer, and add 4.2ml.

The lower cladding layer 86 is formed by dropping a solution for forming an optical resin layer on the coupling layer 83, then pressing a mold having a convex portion on the layer of the solution, and irradiating ultraviolet rays in this state to make the solution solidified. Thereby, the lower cladding layer 86 having the groove 86a can be formed. Next, the above-mentioned solution for forming a core layer is dropped into the groove 86a, the groove 86a is filled with the solution, and the solution is irradiated with ultraviolet rays to cure the solution, whereby the core layer 85 can be formed.

Next, the above-mentioned solution for forming an optical resin layer is dropped on the lower cladding layer 86 and the core layer 85 , and cured by irradiating with ultraviolet rays, whereby the upper cladding layer 87 can be formed.

According to the present invention, for example, a _SiO2 fine particle layer can be formed on a substrate by spin coating or dipping, and a coupling agent can be applied thereon to form a coupling layer, thereby forming an optical waveguide such as an optical waveguide with good adhesion. resin layer. Therefore, an optical waveguide or the like can be formed with good adhesion even on a substrate whose surface does not contain a SiO ₂ component. Therefore, since an optical waveguide can be formed with good adhesion also on a Si substrate, an optical device can be formed on an electronic device, and a large electronic/optical device can be easily produced. For example, an electronic device part such as a transceiver module and an optical waveguide part can be fabricated integrally.

(Example 21)

In this example, a composite aspheric lens was produced by sequentially stacking a mixed fine particle layer, a SiO ₂ fine particle layer, a coupling layer, and an optical resin layer on a glass substrate. In composite aspheric lenses, etc., when the refractive index of the glass substrate is high, the difference between the refractive index and the optical resin layer becomes large, so the reflection at the interface between the glass substrate and the optical resin layer becomes large. The problem. Generally, in a composite aspheric lens, the difference in reflectance between the glass substrate and the optical resin layer is required to be 1% or less as the average reflectance for light having a wavelength of 430 to 650 nm. Conventionally, for example, two types of oxide films having different refractive indices are combined to form a multilayer film of three or more layers, and used as an antireflection film. In order to form a multilayer film, it is necessary to perform film formation several times, and at the same time, it is necessary to strictly control the thickness of each layer. Therefore, it is difficult to suppress the average reflectance for light having a wavelength of 430 to 650 nm to 1% or less in consideration of fluctuations in thickness uniformity and reproducibility. According to this example, an antireflection film can be easily produced by laminating two oxide layers, and the average reflectance to light with a wavelength of 430 to 650 nm can be suppressed to 1% or less.

The structure of the laminated optical element of this embodiment is the same structure as that shown in FIG. In this embodiment, the first fine particle layer 27 is a mixed fine particle layer formed by mixing two kinds of fine particles having different refractive indices, and the second fine particle layer 28 is a fine particle layer composed of SiO ₂ .

In the mixed fine particle layer, the refractive index is adjusted to a predetermined value by mixing two types of fine particle dispersions having different refractive indices. Formation of the mixed fine particle layer can be performed by a spin coating method, a dipping method, or the like. The refractive index of the mixed fine particle layer is preferably the average value na _ave of the refractive index of the glass substrate and the refractive index of the optical resin layer. In addition, the thickness is preferably 1/4 of the wavelength. When used as an optical lens, since it is in the visible light region, the center wavelength is preferably about λ=540 nm. Therefore, the thickness of the mixed fine particle layer is preferably (1/4)·λ/n _ave .

The SiO ₂ fine particle layer is formed as a bottom layer of the coupling layer to improve adhesion with the optical resin layer. It is preferable to make the thickness as thin as about 10 to 15 nm so as not to affect the reflectance. In addition, when the adhesiveness with the optical resin layer can be ignored, this layer can also be omitted.

It is also preferable to make the thickness of the coupling layer as thin as about 10 to 15 nm so as not to affect the reflectance. When the adhesiveness with the optical resin layer can be ignored, this layer can also be omitted.

In this example, high-refractive index glass (manufactured by Ohara Co., Ltd., trade name "S-LAL7", refractive index about 1.8) was used as the glass substrate. In addition, the optical resin layer was formed using the "solution for forming an optical resin layer" in Example 1. The refractive index of the optical resin layer is 1.5.

The mixed fine particle layer is formed by mixing the SiO ₂ fine particle dispersion and the Nb ₂ O ₅ fine particle dispersion. As the SiO ₂ fine particle dispersion liquid, an aqueous colloidal silica solution (manufactured by Nissan Chemical Co., Ltd., trade name "Snow-Tex NXS", average particle diameter 5 nm, SiO ₂ content about 15.7% by weight) was used. As the Nb ₂ O ₅ fine particle dispersion liquid, an aqueous solution of niobium sol (manufactured by Taki Chemical Co., Ltd., trade name "Bairra-L Nb-X10", average particle diameter 5 nm, Nb 2 O ₅ content 10% by weight) was used.

Table 2 shows the refractive index of the microparticle layer formed by colloidal silica alone (sample A), niobium sol alone (sample C), and a mixed sol of colloidal silica sol and niobium sol (sample B) . In sample B in which the sol was mixed, it was mixed at a weight ratio of sample A:sample C=1:2. In addition, the fine particle layer was formed by applying each sol on a glass substrate by a spin coating method (3000 rpm, 30 seconds) and drying it.

Table 2

Fig. 38 is a graph showing the relationship between the Nb ₂ O ₅ content in the fine particle layer and the refractive index.

As shown in FIG. 38 , the refractive index becomes larger in proportion to the content of Nb ₂ O ₅ . Therefore, it can be seen that the refractive index can be adjusted within the range of 1.39 to 1.88 by adjusting the Nb ₂ O ₅ content.

In this example, sample B was used, and the refractive index of the mixed fine particle layer was set to 1.66. In addition, the thickness of the mixed fine particle layer was (1/4)·λ/n _ave =81 nm when the center wavelength was 540 nm.

Fig. 39 shows calculated reflectance values when the refractive index of the optical resin layer is 1.5 and the refractive index of the mixed fine particle layer is 1.66, and the refractive index of the glass substrate is changed from 1.7 to 1.9 around 1.8 diagram. As shown in FIG. 39 , it can be seen that the reflectance is the lowest when the refractive index of the glass substrate is 1.8. Therefore, it can be seen that the reflectance is the lowest when the refractive index of the mixed fine particle layer is the average value of the refractive indices of the glass substrate and the optical resin layer.

By using the mixed fine particle layer as in this example, an antireflection film can be easily formed. The refractive index of the mixed fine particle layer can be adjusted to any value as described above. Therefore, even if the materials of the glass substrate and the optical resin layer are changed, the mixed fine particle layer can be adjusted by adjusting the type and mixing ratio of the fine particles in the mixed fine particle layer. The index of refraction of the particle layer, resulting in the lowest reflectivity. Specifically, the refractive index of the mixed fine particle layer can be adjusted so as to be an intermediate value between the glass substrate and the optical resin layer.

In addition, by providing the SiO ₂ fine particle layer on the mixed fine particle layer, the adhesion effect of the coupling layer can be improved, thereby improving the adhesion of the optical resin layer.

Claims (23)

1. multilayer optical device comprises the optical element that is made of optical material, is arranged on the middle layer on the described optical element and is arranged on optical resin layer on the described middle layer, it is characterized in that:

Described optical resin layer be by have-organometallic polymer of M-O-M-key, only have 1 can hydrolysis base metal alkoxide and/or its hydrolysate and have amino-formate bond and methacryloxy or have amino-formate bond and resin bed that the organic polymer of acryloxy forms, wherein M is a metallic atom

Described middle layer comprise make the molecule that constitutes by metal oxide be dispersed in by in metal alkoxide with free-radical polymerised base and base that can hydrolysis and/or the matrix resin that its hydrolysate forms and form layer.

2. multilayer optical device as claimed in claim 1 is characterized in that:

Described middle layer has at least 2 layers rhythmo structure, and wherein at least 1 layer is molecule to be dispersed in the described matrix resin and the layer that forms.

3. multilayer optical device is characterized in that:

Comprise the optical element that constitutes by optical material, be arranged on the middle layer on the described optical element and be arranged on optical resin layer on the described middle layer, it is characterized in that:

Described optical resin layer be by have-organometallic polymer of M-O-M one key, only have 1 can hydrolysis base metal alkoxide and/or its hydrolysate and have amino-formate bond and methacryloxy or have amino-formate bond and resin bed that the organic polymer of acryloxy forms, wherein M is a metallic atom

Described middle layer comprises the molecule layer that is arranged on described optical element side and is arranged on the coupling layer of described optical resin layer side, described molecule layer is the layer that the dispersion liquid by molecule forms, described coupling layer be by the metal alkoxide with free-radical polymerised base and base that can hydrolysis and/or its hydrolysate forms layer.

4. multilayer optical device as claimed in claim 3 is characterized in that:

The composition of described optical element spreads in described molecule layer.

5. multilayer optical device as claimed in claim 3 is characterized in that:

Described molecule layer is formed by the molecule more than the mean grain size 50nm, forms concavo-convex on the surface of this molecule layer thus.

6. multilayer optical device as claimed in claim 3 is characterized in that:

Described molecule layer forms by the first molecule layer that is arranged on described optical element side that will be made of less than the molecule of 50nm mean grain size with by the second molecule layer laminate that is arranged on described coupling layer side that the molecule more than the mean grain size 50nm constitutes.

7. multilayer optical device as claimed in claim 3 is characterized in that:

Described molecule layer is the layer that the dispersion liquid by described molecule forms, and described dispersion liquid contains at least a kind that is selected from water soluble propene's acid monomers, water soluble resin, silane coupling agent.

8. multilayer optical device as claimed in claim 3 is characterized in that:

Described molecule layer is the layer that the dispersion liquid by described molecule forms, and described dispersion liquid contains photoresist.

9. multilayer optical device as claimed in claim 3 is characterized in that:

Described molecule layer is the layer that the dispersion liquid by described molecule forms, and described dispersion liquid contains adhesive resin.

10. multilayer optical device as claimed in claim 3 is characterized in that:

Described coupling layer is formed the following thickness of 1nm.

11. multilayer optical device as claimed in claim 3 is characterized in that:

Described molecule layer is patterned.

12., it is characterized in that as each described multilayer optical device in the claim 1～11:

Outer surface at described optical resin layer is provided with antireflection film.

13., it is characterized in that as each described multilayer optical device in the claim 1～11:

Also contain described molecule in the described optical resin layer.

14., it is characterized in that as each described multilayer optical device in the claim 1～11:

The refractive index in described middle layer is that the refractive index of described optical resin layer is above and for below the refractive index of described optical element.

15., it is characterized in that as each described multilayer optical device in the claim 1～11:

Described molecule is to be selected from least a in monox, niobium oxide and the zirconia.

16., it is characterized in that as each described multilayer optical device in the claim 1～11:

Form concavo-convexly by surface, form concavo-convex at the interface of described middle layer and described optical resin layer in described middle layer.

17., it is characterized in that as each described multilayer optical device in the claim 1～11:

Described middle layer be configured to cover described optical element around.

18., it is characterized in that as each described multilayer optical device in the claim 1～11:

With the face of the described optical element of the opposite side of a side that is provided with described middle layer on, be provided with antireflection film.

19. multilayer optical device as claimed in claim 12 is characterized in that:

Described antireflection film is by forming, form from the teeth outwards irregular film with described middle layer identical materials.

20. multilayer optical device as claimed in claim 18 is characterized in that:

Described antireflection film is by forming, form from the teeth outwards irregular film with described middle layer identical materials.

21., it is characterized in that as each described multilayer optical device in the claim 1～11:

Also contain organic acid anhydride and/or organic acid in the described optical resin layer.

22., it is characterized in that as each described multilayer optical device in the claim 1～11:

Described optical element is the lens that are made of glass or plastics, and the outer surface of described optical resin layer has aspherical shape.

23. a photographing module is characterized in that:

Have compound lens, imaging apparatus that is made of a plurality of lens and the support that is used to keep them, in described a plurality of lens, at least 1 is the described multilayer optical device of claim 22.

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