CN101019044A - Multilayer optical device - Google Patents

Multilayer optical device Download PDF

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Publication number
CN101019044A
CN101019044A CNA2006800007841A CN200680000784A CN101019044A CN 101019044 A CN101019044 A CN 101019044A CN A2006800007841 A CNA2006800007841 A CN A2006800007841A CN 200680000784 A CN200680000784 A CN 200680000784A CN 101019044 A CN101019044 A CN 101019044A
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layer
molecule
optical
optical device
resin layer
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CN100495077C (en
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藏本庆一
林伸彦
平野均
松本光晴
中井正也
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Sanyo Electric Co Ltd
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Sanyo Electric Co Ltd
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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

Multilayer optical device
Technical field
The present invention relates to a kind of multilayer optical device, this multilayer optical device is at electric distribution substrate; the mechanical part material; various coating materials such as antireflection film and surface protection film; light sends receiving unit; photoswitch; optic communication devices such as photomodulator; optical waveguide; optical fiber; propagation path of light structures such as lens arra and the optical devices such as light beam splitter that comprise them; integration lens (integrator lens); microlens array; reflecting plate; light guide plate; the optical element that display devices such as screen for projection (display or liquid crystal projector etc.) are relevant; glasses; the CCD optical system; lens; compound non-spherical lens; 2P (Photoreplication Process) lens; optical filter; diffraction grating; interferometer; photo-coupler; optical multiplexer/demultiplexer; optical sensor; holographic optical elements (HOE); other used for optical part material; photovoltaic cell; contact lens; medical artificial organ; useful in the mold materials of light emitting diode (LED) etc.
Background technology
Comprise lens, in the material of optical element, use glass or plastics etc. all the time.The kind of glass is a lot, and change of optical property (variation) is abundant, so, carry out optical design easily, further, owing to be inorganic based material, so the reliability height.In addition, can obtain high-precision optical element by grinding.
But, aspherical shape beyond the cost height, plane and sphere must be used special lapping device, so-called mold (mold) method that mould that maybe must be by utilizing the high high price of thermotolerance (for example pottery make etc.) forms, the glass material that shaping can be shaped at low temperatures.Therefore, very at high price.
On the other hand, use the optical element of synthetic resin material (plastics), can utilize injection moulding or casting (cast) method to make at an easy rate, but exist the selecting range of optical characteristics such as thermotolerance is low, thermal expansion big, refractive index narrow, problem such as reliability is low.
Method as eliminating the problems referred to above has proposed the composite optical element by the characteristic that obtains wishing at glass baseplate superimposed layer resin bed.In patent documentation 1, a kind of low-pass filter that is formed with organic polymer layer on the glass substrate on plane is disclosed.In addition, in patent documentation 2 and patent documentation 3, a kind of so-called compound non-spherical lens that forms the resin bed with aspherical shape on the glass lens base material is disclosed.
In recent years, use the field of optical element as described above to enlarge, also more and more stricter to the desired reliability of optical element.For example, require sometimes as 500～1000 hours permanance in 85 ℃ of hot and humid condition, 85% environment.
In these multilayer optical devices, in order to improve the adhesion of base material and resin bed, silane coupling agent after coating on the base material utilizes solvent dilution, form resin bed then thereon, but such method can not be kept sufficient adhesion under harsh environment, has the problem of peeling off easily.
When the concentration that improves coupling agent in order to improve fissility applies, have in the coating rear surface to produce gonorrhoea, can not apply, produce problem such as spot equably.
In patent documentation 4, containing the high oxide of a large amount of refractive indexes, silica composition (SiO 2) in the few glass of high refractive index, the reflection in order to prevent to produce owing to the refringence between glass of high refractive index substrate (about refractive index=1.8～2.0) and the optical resin layer (refractive index=about 1.5) is formed with SiO on glass baseplate surface 2/ ZrO 2/ SiO 2Deng the dielectric multilayer film.
In addition, in order to improve the adherence of glass and optical resin layer, apply silane coupling agent usually on glass surface, this silane coupling agent has the character of performance raising to the effect of the adherence of silica composition, at silica composition (SiO 2) in the few glass of high refractive index, existence can not utilize silane coupling agent to improve the problem of the adherence of glass and optical resin layer.In patent documentation 4, the superiors of dielectric multilayer film are SiO 2, therefore, even in glass of high refractive index, also can access high adherence.This dielectric multilayer film is formed by methods such as vacuum evaporation, ion plating, sputters, but when using such method, is difficult to make at an easy rate and at short notice optical element.
Patent documentation 1: the spy opens clear 54-6006 communique
Patent documentation 2: the spy opens clear 52-25651 communique
Patent documentation 3: the spy opens flat 6-222201 communique
Patent documentation 4: the spy opens flat 5-100104 communique
Summary of the invention
First purpose of the present invention is to provide a kind of multilayer optical device, and it is the composite optical element that forms at optical element superimposed layer optical resin layer such as glass, though hot and humid down, optical resin layer also is difficult to be stripped from, and the reliability excellence.
Second purpose of the present invention is to provide a kind of multilayer optical device, it is at optical element superimposed layer optical resin layers such as glass and the composite optical element that forms, even also can form optical resin layer with good adherence on the optical element that is made of glass of high refractive index.
A first aspect of the present invention is a kind of multilayer optical device, it comprises the optical element that is made of optical material, be arranged on the middle layer on the optical element, with the optical resin layer that is arranged on the middle layer, it is characterized in that: optical resin layer is by having-organometallic polymer of M-O-M-key (M is a metallic atom), only have 1 can hydrolysis metal alkoxide and/or its hydrolysate of base, and have amino-formate bond and methacryloxy or have amino-formate bond and resin bed that the organic polymer of acryloxy forms, the 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.
In a first aspect of the present invention, it is characterized in that, between optical element and optical resin layer, be provided with the middle layer, the 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.Because the middle layer is the molecule that is made of metal oxide to be dispersed in the matrix resin and the layer that forms, so, can improve the adherence of optical element and optical resin layer, also be difficult to peel off optical resin layer even can make at hot and humid time.Therefore, can form the multilayer optical device of reliability excellence.
In a first aspect of the present invention, the middle layer can form by at least 2 layers.In this case, as long as wherein at least 1 layer is molecule to be dispersed in the matrix resin and the layer that forms.
In a first aspect of the present invention, the matrix resin in middle layer and optical resin layer all can use the resin that can solidify by the irradiation energy line.By so all using the resin that utilizes the irradiation energy line to solidify, can further improve the adherence of middle layer and optical resin layer.
The surface in the middle layer of a first aspect of the present invention concavo-convex for example, can form by near the dissolving of the molecule the interlayer surfaces is removed.
A second aspect of the present invention is a kind of multilayer optical device, it comprises the optical element that is made of optical material, be arranged on the middle layer on the optical element, with the optical resin layer that is arranged on the middle layer, it is characterized in that: optical resin layer is by having-organometallic polymer of M-O-M-key (M is a metallic atom), only have 1 can hydrolysis metal alkoxide and/or its hydrolysate of base, and have amino-formate bond and methacryloxy or have amino-formate bond and the resin bed of the organic polymer of acryloxy formation, the middle layer comprises the molecule layer that is arranged on the optical element side and is arranged on the coupling layer of optical resin layer side, the molecule layer is the layer that the dispersion liquid by molecule forms, coupling layer be by the metal alkoxide with free-radical polymerised base and base that can hydrolysis and/or its hydrolysate forms layer.
In a second aspect of the present invention, the middle layer comprises the molecule layer that is arranged on the optical element side and is arranged on the coupling layer of optical resin layer side that preferably these layers form by lamination.
According to a second aspect of the invention, on optical element, be formed with the molecule layer, be formed with coupling layer thereon, therefore,, also can form optical resin layer with good adherence even under the situation that glass of high refractive index is used as optical element.
In a second aspect of the present invention, preferred: the molecule layer is by forming carrying out heat treated after the dispersed liquid coating of molecule is on optical element, and the composition of optical element spreads in the molecule layer.As the temperature of heat treated, preferred 300～500 ℃ temperature.
Especially, on optical element, apply SiO 2After the dispersion liquid Deng molecule,, can on optical element, form SiO thus for example curing under 300～500 ℃ the temperature 2Deng the molecule aggegation form the layer.By on such layer, forming coupling layer, forming optical resin layer again, can optical resin layer be set with good adherence.
By in the temperature of regulation, for example cure the molecule layer, the TiO in the optical element under 300～500 ℃ the temperature 2Be diffused in the molecule layer Deng the composition beyond the silicon dioxide, the adherence of optical element and molecule layer becomes good.In addition, in the molecule layer, in the part of coupling layer side, it is many that silica composition becomes.The result, form in the molecule layer that composition beyond the optical element side silicon dioxide of molecule layer is many, the incline structure more than the coupling layer side silica composition of molecule layer, can improve the adherence between optical element and the molecule layer and the adherence of molecule layer and coupling layer simultaneously.In addition, utilize the stoving temperature of afore mentioned rules, also can improve the intensity of molecule layer itself.
In a second aspect of the present invention, the molecule layer is formed by the molecule more than the mean grain size 50nm, can form concavo-convex thus on the surface of this molecule layer.Form concavo-convexly by surface, increase, become good with the adherence of coupling layer with the surface area at the interface of coupling layer at the molecule layer.
In a second aspect of the present invention, the molecule layer can form by the first molecule layer that is arranged on the 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 the coupling layer side that the molecule more than the mean grain size 50nm constitutes.By forming such structure, can increase the area of contact portion at the interface of optical element and molecule layer, thereby can improve the adherence of optical element and molecule layer, and, coupling layer side at the molecule layer, concavo-convex by forming at the molecule laminar surface, can improve adherence with coupling layer.
In a second aspect of the present invention, the dispersion liquid of molecule layer can only contain molecule as solid constituent.That is, the dispersion liquid of molecule can only contain molecule and dispersion medium.The dispersion liquid of such molecule by curing as described above, can form fine and close molecule layer.
In addition, in a second aspect of the present invention, the dispersion liquid of molecule can contain adhesive resin.By containing adhesive resin,, also can improve the intensity of molecule layer even under high temperature, do not cure.In addition, according to the kind of the adhesive resin that adds, also can improve adherence with optical element.As adhesive resin, can enumerate water soluble propene's acid monomers, water soluble resin, silane coupling agent and photoresist etc.As adhesive resin, preferably use water miscible resin.By using photosensitive adhesive resin such as photoresist, can make the molecule layer have photonasty, after forming the molecule layer, can harden by irradiation ultraviolet radiation etc., thus can be with the molecule layer patternization.
In a second aspect of the present invention, can make it have optical function the molecule patterning.For example, can make it have optical functions such as diffraction grating.Thus, Chromatically compensated lens that can the double as lens, thus can reduce the components number of optical system.
In a second aspect of the present invention, coupling layer can be formed the thickness below the 1nm.By coupling layer being formed the thickness below the 1nm and forming thickness about several molecule layer～1 molecular layer, the disappearance in uneven thickness of coupling layer can further improve the adherence with optical resin layer.
In a second aspect of the present invention, the molecule layer can form by the dispersion liquid of spin coating or dipping molecule.By spin coating or dipping, molecule is assembled on optical element thick and fast, forms stratiform.By under this state, curing or irradiation ultraviolet radiation homenergic line, combination between molecule, perhaps the resin solidification between molecule thus, can form fine and close molecule layer.
In a second aspect of the present invention, the molecule layer can patterning.For example, when curing the molecule layer under the temperature about 140 ℃, the film strength of the molecule layer of the degree that can obtain utilizing detergent solution to remove molecule.Therefore, after the dispersion liquid of coating molecule, carry out curing about 140 ℃, form the resist film of patterning on the surface of molecule layer, be immersed in the detergent solution and heating, thus, can remove not the molecule of the part that is covered by resist film, thus, can carry out patterning.
In addition, contain in the dispersion liquid of molecule under the situation of photoresist, form after the molecule layer, optionally exposure then, is immersed in the detergent solution, removes non-exposed portion, thus, and can be with the molecule layer patternization.
Below, about the common item of a first aspect of the present invention and second aspect, describe as " the present invention " sometimes.
In the present invention, the outer surface of optical resin layer can have aspherical shape.Form aspherical shape by outer surface, can form for example compound non-spherical lens optical resin layer.
In the present invention, the molecule that is dispersed in the middle layer can be distributed in the optical resin layer.
In the present invention, for example can make the refractive index in middle layer is that the refractive index of optical resin layer is above and for below the refractive index of optical element.That is, can make the refractive index in middle layer is the refractive index of the scope between the refractive index of the refractive index of optical element and optical resin layer.
As the molecule that contains in the middle layer, for example, can enumerate and be selected from least a in monox, niobium oxide and the zirconia.
In the present invention, can form by surface in the middle layer concavo-convex, thereby form concavo-convex at the interface of middle layer and optical resin layer.Form concavo-convexly by interface, can further improve the adherence of middle layer and optical resin layer at middle layer and optical resin layer.
In the present invention, the middle layer can be arranged to cover optical element around.By with cover optical element around mode the middle layer is set, can more effectively prevent the immersion of moisture etc., thereby can further improve reliability.
In the present invention, can antireflection film be set at the outer surface of optical resin layer.In addition, also can on optical element and the face opposite side of a side that is provided with the middle layer, antireflection film be set.
In the present invention, antireflection film is for example by form, form from the teeth outwards by the molecule dissolving of near surface is removed irregular film with the middle layer identical materials.
Below, optical resin layer of the present invention, middle layer and optical element are at length described.
＜optical resin layer 〉
Optical resin layer of the present invention by have-organometallic polymer of M-O-M-key (M is a metallic atom), 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 the organic polymer of acryloxy forms.
Above-mentioned organic polymer is to have amino-formate bond and methacryloxy or have amino-formate bond and the organic polymer of acryloxy, for example, can enumerate the polyisocyanates such as end use diisocyanate at polyvalent alcohol, the organic polymer that hydroxyl is obtained with the compound reaction with methacryloxy or acryloxy.
As concrete structure, the part (isocyanate moiety) that be designated as AC in the part that will have methacryloxy or acryloxy (acrylate part or methacrylic acid ester moiety), will have an amino-formate bond is designated as IS, when polyol moiety is designated as PO, can enumerates and have
AC-IS-PO-IS-AC
The structure of structure, be commonly referred to the acrylic ester resin.
From reducing absorptive viewpoint, the preferred acrylic ester resin that uses with the high phenyl of hydrophobicity or structure of bisphenol A.
In said structure, at least one between the AC-IS and between the IS-PO is by the amino-formate bond combination.The existence of this amino-formate bond is important, and the cohesive force by from the hydrogen bond of this amino-formate bond can make it have flexibility and obdurability under the solid state of optical resin layer, thereby can further prevent to crack etc. under hot and humid.
Above-mentioned AC partly have can polymerization base (two keys of charcoal), have by light, hot homenergic, organic polymer self carries out polymerization or forms key with above-mentioned organometallic polymer, thereby the effect that optical resin layer is solidified.
In addition, by in above-mentioned organometallic polymer, import in advance can polymerization base, can with the AC composition polymerization in the organic polymer, can form more strong key.
Above-mentioned PO portion is the part of giving the characteristics such as flexibility of organic polymer, for example, is that polyvalent alcohol, polyethers are that polyvalent alcohol, poly charcoal acid ester are that polyvalent alcohol, polycaprolactone are that polyvalent alcohol, silicon-type polyvalent alcohol etc. constitute by polyester.
The organic polymer of said structure, being commonly referred to as urethane acrylate is resin etc.
Contain above-mentioned metal alkoxide and/or its hydrolysate in the optical resin layer.Above-mentioned metal alkoxide and/or its hydrolysate can contain with the state that does not combine with organometallic polymer, also can contain with the state of combination.In addition, the hydrolysate of metal alkoxide can be the condensed polymer of hydrolysate.
In optical resin layer, by contain only have one can hydrolysis metal alkoxide and/or its hydrolysate of base, metal alkoxide and/or its hydrolysate produce-the OH radical reaction with end at the organometallic polymer molecule, can eliminate-the OH base.Therefore, the light propagation loss and the water-intake rate that produce in the wavelength coverage of 1450～1550nm are reduced.
For example, when metallic atom M is Si,, the situation of existence with the-alkoxy that Si-O-R represents arranged at the end of organometallic polymer molecule.This alkoxy absorbs moisture, hydrolysis, and reaction as described below produces silanol group.
-Si-O-R+H 2O→-Si-OH+ROH↑
The ROH volatilization that in above-mentioned reaction, produces.When above-mentioned silanol group existed, transmitance descended and water-intake rate increases.
When contain only have 1 can hydrolysis the metal alkoxide of base and/or during its hydrolysate, the silanol group that produces as described above can be eliminated.For example, the alkoxy silane that only has 1 alkoxy by following formula is represented absorbs moisture, hydrolysis as described below.
R’ 3Si-O-R”+H 2O→R’ 3Si-OH+R”OH↑
In above-mentioned reaction, R " the OH volatilization.The hydrolysate of Sheng Chenging as described above is as described below with the silanol group reaction of the end of organometallic polymer.
-Si-OH+R’ 3Si-OH→-Si-O-SiR’ 3+H 2O
By above-mentioned reaction, the silanol group of organometallic polymer molecular end is eliminated.Therefore, can keep high permeability for a long time, and can reduce water-intake rate.
As previously discussed, metal alkoxide is hydrolyzed, works as hydrolysate, therefore, can contain with the form of metal alkoxide, also can contain with the form of hydrolysate.In addition, when organic metal alkoxide or its hydrolysate are contained sometimes with the state that does not combine with organometallic polymer, in organometallic polymer, reuptake moisture, produce silanol group etc. at its end, at this moment, effects such as the metal alkoxide of unconjugated state or its hydrolysate and this silanol group can make eliminations such as silanol group as described above.
Above-mentioned metal alkoxide or its hydrolysate can contain fluorine atom.That is, can be metal alkoxide and the hydrolysate thereof that the hydrogen of hydrocarbon part is substituted by fluorine atom.
Organometallic polymer-M in the M-O-M-key, be preferably the combination of Si, Ti, Nb or Zr or these metals, be preferably Si especially.During for Si, organometallic polymer for example can be formed by organic siliconresin.
Preferably in optical resin layer, also contain organic acid anhydride and/or organic acid.
The hydrolysis because organic acid anhydride absorbs moisture, so, by containing organic acid anhydride, the moisture in the organometallic polymer is reduced.Thus, the absorption that moisture becomes reason will reduce, even only add organic acid anhydride, also can suppress the deterioration of the material that caused by moisture, improve transmitance.The reaction of the organic acid promotion silanol group that contains in the organometallic polymer in addition, etc.Therefore, can promote the elimination of silanol group etc.For example, also can promote reaction between the silanol group of organometallic polymer molecular end.
Because following reason contains organic acid anhydride and/or organic acid in the preferred optical resin layer.Promptly, by contain simultaneously only have 1 can hydrolysis metal alkoxide and/or its hydrolysate and the organic acid anhydride and/or the organic acid of base, except the moisture that is produced by organic acid anhydride is removed, only have 1 can hydrolysis base metal alkoxide hydrolysate with produce in the organometallic polymer molecular end-the OH radical reaction, promote to make-reaction that the OH base is eliminated.
When above-mentioned metal alkoxide or its hydrolysate were alkoxy silane or its hydrolysate, the compound of being represented by following general formula can be used as an example and enumerates.
Figure A20068000078400131
(at this, R 1, R 2And R 3Organic group for carbon number 1～15 is preferably alkyl.In addition, R 4Alkyl for carbon number 1～4.)
As object lesson, can enumerate trialkyl alkoxy silanes such as trimethyl alkoxy silane, triethyl alkoxy silane.As alkoxy, can enumerate methoxyl and ethoxy etc.
As the object lesson of above-mentioned organic acid anhydride, can enumerate trifluoroacetic anhydride, acetic anhydride, propionic andydride etc.Especially preferably use trifluoroacetic anhydride.As above-mentioned organic acid object lesson, can enumerate trifluoroacetic acid, acetate, propionic acid etc.Especially preferably use trifluoroacetic acid.
Organometallic polymer for example can by have at least 2 can hydrolysis the hydrolysis and the polycondensation reaction of organometallics of base synthesize.As such organometallics, for example, can enumerate the trialkoxy silane or the dialkoxy silicane that contain organic group.As organic group, can enumerate alkyl, aryl, contain the base of aryl etc.As aryl, preferred phenyl.And then, as preferred compound, can enumerate phenyl trialkoxy silane, diphenyl dialkoxy silicane, more preferably phenyl triethoxysilane, phenyltrimethoxysila,e, dimethoxydiphenylsilane, diphenyl diethoxy silane.
In addition, as above-mentioned organometallics, preferably contain and have by heating and/or irradiation energy line and crosslinked functional group's organometallics.As energy line, can enumerate ultraviolet ray, electronics line etc.Crosslinked functional group as such can enumerate acryloxy, methacryloxy, styryl, epoxy radicals and vinyl.Therefore, the preferred trialkoxy silane that uses with these functional groups.
When containing free-radical polymerised functional groups such as acryloxy, methacryloxy, styryl and vinyl, preferably contain the polymerization initiator of free base system.As free base system polymerization initiator, for example, can enumerate 1-hydroxyl-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1, oxygen (oxy)-phenyl-acetic acid 2-(2-oxo-2-phenyl-acetoxyl group-ethoxy)-ethyl-ester, oxygen (oxy)-phenyl-acetic acid 2-(2-hydroxyl-ethoxy)-ethyl-ester and their potpourri.
In addition, when containing organometallics, preferably contain hardening agent with epoxy radicals.As such hardening agent, can enumerate amine is that hardening agent, imidazoles are that hardening agent, phosphorus are that hardening agent, acid anhydrides are hardening agent etc.Specifically, can enumerate methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, tetraethylene pentamine etc.
In the time of will having functional group's organometallics and not have functional group's organometallics mixing use, blending ratio is in the weight ratio (organometallics with functional group: the organometallics that does not have the functional group), be preferably 5～95: 95～5.
In optical resin layer, the content of above-mentioned organic polymer is preferably 5～95 weight %, 40～95 weight % more preferably.When the content of above-mentioned organic polymer is very few, under hot and humid, be easy to generate crackle, become the main cause of the absorption and the scattering of light.In addition, on the contrary, when the content of above-mentioned organic polymer was too much, thermotolerance descended, and the deterioration under the hot environment is carried out, and optical characteristics, particularly light transmission descend.
As previously discussed, be in the scope of 5～95 weight % by the content that makes above-mentioned organic polymer, can make optical resin layer become more material transparent, for example, in wavelength 630nm, the transmitance as the sample of thickness 3mm can obtain more than 80%.In addition, be that transmitance reaches more than 90% in the scope of 40～95 weight % by the content that makes above-mentioned organic polymer.
In optical resin layer, the content of above-mentioned metal alkoxide or its hydrolysate with respect to the organometallic polymer of 100 weight portions, is preferably 0.1～15 weight portion, more preferably 0.2～2.0 weight portion.When the content of above-mentioned metal alkoxide or its hydrolysate was very few, the OH base can be residual, and the absorption in the wavelength coverage of 1450～1550nm increases, and water-intake rate uprises, easily deterioration.On the contrary, when the content of above-mentioned metal alkoxide or its hydrolysate was too much, in hot environment, superfluous above-mentioned metal alkoxide or its hydrolysate can break away from from material, become the main cause that cracks.
In addition, organic acid anhydride or organic acid content with respect to the organometallic polymer of 100 weight portions, are preferably 0.1～10 weight portion, more preferably 1～5 weight portion.When organic acid anhydride or organic acid content are very few, by only have 1 can hydrolysis the removing not exclusively of the OH base that carries out of the metal alkoxide of base, on the contrary, when organic acid anhydride or organic acid content are too much, in hot environment, superfluous organic acid anhydride or organic acid self can break away from from material, become the main cause that cracks.
In addition, in optical resin layer, the difference of the refractive index of the refractive index of the solidfied material of above-mentioned organometallic polymer and the solidfied material of above-mentioned organic polymer is preferably below 0.01.By the difference that makes refractive index like this is below 0.01, and the organometallic polymer zone in the material is suppressed with the scattering of light that is caused by refringence at the interface of organic polymer object area, can obtain the transmitance more than 90%.
In addition, in optical resin layer, make the refractive index under the liquid condition before above-mentioned organometallic polymer solidifies solidify the poor of preceding refractive index, be preferably below 0.02 with making above-mentioned organic polymer.Difference by making the refractive index under both liquid conditions before solidifying like this is below 0.02, and can make the transmitance of the material after the curing is more than 90%.
Preferred optical resin layer has the 850cm that is caused by above-mentioned metal alkoxide in IR mensuration figure -1Near absorption peak.By having such absorption peak, in material, contain fully as only have 1 can hydrolysis the trimethyl silyl of metal alkoxide of base, the OH base in the material is removed effectively.
The middle layer of＜first aspect 〉
The middle layer of a first aspect of the present invention be 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.
As above-mentioned metal alkoxide, can enumerate trialkoxy silane with free-radical polymerised base or dialkoxy silicane etc.
In addition, as free-radical polymerised base, can enumerate acryloxy, methacryloxy, styryl and vinyl etc.As metal alkoxide, preferred especially the use has these basic trialkoxy silanes.
As the microparticle that constitutes by metal oxide that is dispersed in the matrix resin, can enumerate monox, niobium oxide, zirconia, titanium dioxide, aluminium oxide, yttria, cerium oxide, lanthana etc., wherein, especially preferably use monox, niobium oxide, zirconia.The size of the molecule among the present invention in mean grain size, is preferably in the 100nm scope following, 5～50nm more preferably.
In the middle layer of a first aspect of the present invention, suitably select the amount of the molecule that contains in the matrix resin, making becomes the refractive index of expectation.Usually, the content of the molecule in the middle layer is preferably in the scope of 0.5～50 weight %.
Solidify by making the free-radical polymerised basic polymerization in metal alkoxide and/or its hydrolysate in the middle layer of a first aspect of the present invention.For example, can solidify by heating or irradiation ultraviolet radiation homenergic line.
The polymerization initiator that in the middle layer, also can contain the radical polymerization syzygy that in optical resin layer, has illustrated.
In the middle layer, make the refractive index in middle layer reduce by adding the low molecule of refractive index, can controlling.In addition, make the refractive index in middle layer uprise by containing the high molecule of refractive index as above-mentioned molecule, can controlling.As the metal oxide particle that can improve refractive index, can enumerate niobium oxide (Nb 2O 5) particle, zirconia (ZrO 2) particle and titanium dioxide (TiO 2) particle.In addition, as the molecule that can reduce refractive index, can enumerate monox (SiO 2) particle.
In addition, as mentioned above, in optical resin layer, also can contain molecule.
The middle layer of＜second aspect 〉
The middle layer of a second aspect of the present invention comprises the molecule layer that is arranged on the optical element side and is arranged on the coupling layer of optical resin layer side.
Molecule in a second aspect of the present invention can use the molecule that uses in a first aspect of the present invention.
In addition, form metal alkoxide and/or its hydrolysate of the coupling layer in a second aspect of the present invention, can use with first aspect in metal alkoxide and/or the same material of its hydrolysate.
Molecule layer in a first aspect of the present invention can form a plurality of layer laminate.A plurality of layers can form the layer laminate of different molecules.
As the adhesive resin that in a second aspect of the present invention, uses, can enumerate water soluble propene's acid monomers, water soluble resin, silane coupling agent and photoresist as mentioned above.
As water soluble propene's acid monomers, can enumerate methacrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxypropyl acrylate, methacrylic acid 2-dimethylamino ethyl ester etc.
As water soluble resin, can enumerate: epoxies such as Polyethylene Glycol Bisglycidyl Ether are resin, acrylic resin such as polyacrylate, polymethacrylate and on the main chain that the siloxane bond by polysiloxane constitutes addition water wettability base and silicon-type resin of forming etc.
As silane coupling agent, can to enumerate methacryloxies such as 3-methacryloxypropyl trimethoxy silane and be epoxies such as silane coupling agent, 3-glycidoxypropyltrime,hoxysilane be silane coupling agent, to styrene base system silane coupling agents such as the hydrolysate of styryl trimethoxy silane etc. or the polymkeric substance of hydrolysate etc.
As photoresist, can enumerate above-mentioned water soluble propene's acid monomers, water soluble acrylic resin etc.
In a second aspect of the present invention,, can enumerate and be used for detergent solution that optics is cleaned as the detergent solution that is used for the molecule layer patternization.
＜optical element 〉
As the optical element among the present invention, can enumerate the parts of glass, pottery and the plastics etc. of light transmission.When forming the multilayer optical device of thin thickness,, can use glass of high refractive index, high index of refraction light transparent ceramic etc. as optical element.
＜multilayer optical device 〉
As multilayer optical device of the present invention, can enumerate compound non-spherical lens.Compound non-spherical lens is to form the light transmissive region that is made of the translucent resin layer on the spherical lens that is made of glass etc., thereby forms non-spherical lens.In the present invention, between optical elements such as spherical lens and optical resin layer, be provided with the middle layer, therefore, the optical resin layer of adherence excellence can be set as the translucent resin layer.In addition, in the present invention, in optical resin layer, use the material of hardness and excellent heat resistance.Therefore, multilayer optical device of the present invention is the reliability height under hot and humid and the multilayer optical device of hardness and excellent heat resistance.
Multilayer optical device of the present invention; because the reliability excellence under hot and humid; hardness and thermotolerance height; so, can be applied to electric distribution substrate; the mechanical part material; various coating materials such as antireflection film and surface protection film; light sends receiving unit; photoswitch; optic communication devices such as photomodulator; optical waveguide; optical fiber; propagation path of light structures such as lens arra and the optical devices such as light beam splitter that comprise them; integration lens (integrator lens); microlens array; reflecting plate; light guide plate; the optical element that display devices such as screen for projection (display or liquid crystal projector etc.) are relevant; glasses; the CCD optical system; lens; compound non-spherical lens; 2P (Photoreplication Process) lens; optical filter; diffraction grating; interferometer; photo-coupler; optical multiplexer/demultiplexer; optical sensor; holographic optical elements (HOE); other used for optical part material; photovoltaic cell; contact lens; medical artificial organ; the mold materials of light emitting diode (LED) etc.
Photographing module of the present invention is characterised in that, the support (holder) that has compound lens, the imaging apparatus that constitutes by a plurality of lens and be used to keep them, and in above-mentioned a plurality of lens, at least 1 is multilayer optical device of the present invention.
Portable phone of the present invention is characterised in that, comprises photographing module of the present invention.
Liquid crystal projector of the present invention is characterised in that, comprising: light source; Lamp optical system; The liquid crystal portion that constitutes by liquid crystal, half-mirror, catoptron and lens etc.; And projection optical system, use the projection optical system of compound non-spherical lens of the present invention and light source to be set at position adjacent.
In the present invention, between optical element and optical resin layer, be provided with the molecule that is made of metal oxide is 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 the middle layer that forms.Therefore, multilayer optical device of the present invention, the adherence excellence between optical resin layer and the optical element, the reliability height under hot and humid, and hardness and excellent heat resistance.
Description of drawings
Fig. 1 is the sectional view of expression according to the cross section structure of the multilayer optical device of embodiments of the invention 1.
Fig. 2 is the sectional view of expression according to the cross section structure of the multilayer optical device of embodiments of the invention 2.
Fig. 3 is the sectional view of expression according to the cross section structure of the multilayer optical device of embodiments of the invention 3.
Fig. 4 is the sectional view of expression according to the cross section structure of the multilayer optical device of embodiments of the invention 5.
Fig. 5 is the figure of structure of the matrix resin layer in expression middle layer shown in Figure 4.
Fig. 6 is the sectional view of expression according to the cross section structure of the multilayer optical device of embodiments of the invention 6.
Fig. 7 is the sectional view of expression according to the cross section structure of the multilayer optical device of embodiments of the invention 7.
Fig. 8 is the sectional view along A-A line shown in Figure 7.
Fig. 9 is the sectional view of expression according to the cross section structure of the multilayer optical device of embodiments of the invention 8.
Figure 10 is the sectional view of the structure of expression antireflection film 9 shown in Figure 9.
Figure 11 is the sectional view of expression conduct according to the manufacturing process of the compound non-spherical lens of the multilayer optical device in the various embodiments of the present invention.
Figure 12 is the sectional view of the compound non-spherical lens of expression comparative example.
Figure 13 is the sectional view along A-A line shown in Figure 12.
Figure 14 is the sectional view of the cross section structure of expression comparative example 2.
Figure 15 is the sectional view of the cross section structure of expression comparative example 3.
Figure 16 is the sectional view of the cross section structure of expression comparative example 4.
Figure 17 is the schematic representation of apparatus that expression is used to observe the spherical aberration of compound non-spherical lens.
The figure of the mesh pattern when Figure 18 is expression use glass spherical lens and the observation of compound non-spherical lens.
Figure 19 is the sectional view of expression according to the cross section structure of the multilayer optical device of embodiments of the invention 9.
Figure 20 is the amplification sectional view of expression according to the cross section structure of the multilayer optical device of embodiments of the invention 9.
Figure 21 is the sectional view of expression according to the cross section structure of the multilayer optical device of embodiments of the invention 10.
Figure 22 is the amplification sectional view of expression according to the cross section structure of the multilayer optical device of embodiments of the invention 10.
Figure 23 is the sectional view of expression according to the cross section structure of the multilayer optical device of embodiments of the invention 11.
Figure 24 is the amplification sectional view of expression according to the cross section structure of the multilayer optical device of embodiments of the invention 11.
Figure 25 is the sectional view of expression according to the cross section structure of the multilayer optical device of embodiments of the invention 12.
Figure 26 is the sectional view of expression according to the cross section structure of the multilayer optical device of embodiments of the invention 13.
Figure 27 is the sectional view of expression manufacturing according to the operation of the multilayer optical device of embodiments of the invention 14.
Figure 28 is the sectional view of expression manufacturing according to the operation of the multilayer optical device of embodiments of the invention 15.
Figure 29 is the sectional view of expression according to the cross section structure of the multilayer optical device of embodiments of the invention 16.
Figure 30 represents according to the present invention, forms the stereographic map of the state of a plurality of optical elements on tabular optical element.
Figure 31 is that expression has the sectional view according to the photographing module of multilayer optical device of the present invention.
Figure 32 is the sectional view that the portable phone of photographing module is in the past disposed in expression.
Figure 33 is that expression has the sectional view of use according to the portable phone of the photographing module of multilayer optical device of the present invention.
Figure 34 is that expression has the schematic section according to the liquid crystal projector of multilayer optical device of the present invention.
Figure 35 is that expression has the schematic section according to the liquid crystal projector of multilayer optical device of the present invention.
Figure 36 is that expression has the schematic section according to the liquid crystal projector of multilayer optical device of the present invention.
Figure 37 is the sectional view of expression according to optical waveguide of the present invention.
Figure 38 is that expression mixes the Nb in the molecule layer 2O 5The figure of the relation of containing ratio and refractive index.
Figure 39 is the figure of refractive index with the relation of the reflectivity that mixes the molecule layer of expression substrate.
Symbol description
1 optical element
2 middle layers
3 optical resin layers
4 matrix resin layer
5 molecules
6 coupling agent layers
7,8 antireflection films
9 matrix resin layer
21,23～31,32a, 32b, 33,34,35a, 35b, 36a, 36b molecule layer
22 coupling layers
40 photographing modules
41,42,43,44 non-spherical lenses
45 imaging apparatuss
50 portable phones
51 TV tuners
52 hard disk drives
53 displays
54 keyboards
55 batteries
60 liquid crystal projectors
61 projection optical systems
62 lamp optical systems
63 light sources
64,65 half-mirrors (halfmirror)
66,67,68 catoptrons (mirror)
69 cross prisms
70,71,72 lens
73,74,75 liquid crystal panels
80 substrates
81 middle layers
82 molecule layers
83 coupling layers
84 optical resin layers
85 sandwich layers (core layer)
86 bottom clads
The groove of 86a bottom clad
87 top clads
Embodiment
Below, utilize embodiment to explain the present invention, but the present invention is not limited by following embodiment.
(coupling agent solution 1)
Is 2 weight % with ethanol with 3-methacryloxypropyl trimethoxy silane (MPTMS) dilution, makes coupling agent solution 1.
With spin-coating method etc. this solution is coated on the substrate surface, the OH base that utilizes the moisture in the atmosphere that the MPTMS hydrolysis is produced forms hydrogen bond with base material.In addition, the compatibility of organic materials such as organic group in the MPTMS hydrolysate (methacryloxypropyl part) and resin is good, therefore, and with the adherence raising of resin bed.
(coupling agent solution 2)
Add 6.8g MPTMS and stirring in 13g ethanol after, interpolation 8g pure water, 1.6g 2N hydrochloric acid also stir, and place 72 hours, make coupling agent solution 2.
In coupling agent solution 2, by adding hydrochloric acid, can be actively and hydrolysis and polycondensation fully, therefore, can make full-bodied solution.Therefore, compare, can form thicker coupling agent layer with coupling agent solution 1.
(coupling agent solution 3)
Further, make coupling agent solution 3 with 200g alcohol dilution coupling agent solution 2.
(silicon oxide particle dispersion liquid)
Making is dispersed in silicon oxide particle (mean grain size 20nm) in the ethanol and makes its dispersion liquid that becomes 10 weight %, and this dispersion liquid is mixed with above-mentioned coupling agent solution 2, prepares the silicon oxide particle dispersion liquid.
Adjust blending ratio, make when dispersion liquid being solidified the refractive index that can obtain stipulating by heating and/or rayed.Under the situation of silicon oxide particle dispersion liquid, the blending ratio of silicon oxide particle is many more, and the refractive index after the curing is more little.By adjusting the blending ratio of silicon oxide particle, can in about 1.50～1.48 scope, adjust the refractive index n D of wavelength 589nm.
Below, unless otherwise specified, just be to use refractive index to be adjusted into 1.48 dispersion liquid.
(niobium oxide particle dispersion)
In 13g ethanol, add 4.72g MPTMS and 2.08g dimethoxydiphenylsilane (DPhDMS), add 8g pure water, 1.6g 2N hydrochloric acid and stirring again, placed 72 hours.Preparation is dispersed in niobium oxide particle (mean grain size 10nm) in the ethanol and makes its dispersion liquid that becomes 10 weight %, and the solution of above-mentioned MPTMS and DPhDMS is mixed with this dispersion liquid, prepares the niobium oxide particle dispersion.
Adjust the mixing ratio of above-mentioned metal alkoxide and niobium oxide particle, make the layer that forms by coating solution reach definite refractive index.Under the situation of niobium oxide particle dispersion, the content of niobium oxide particle is many more, and the refractive index after the curing is big more.By the content of control niobium oxide particle, the refractive index n D of wavelength 589nm can adjust in about scope of about 1.53～1.60.
Below, unless otherwise specified, just be to use and refractive index be set at 1.59 dispersion liquid.
(optical resin layer forms and uses solution)
After in 20.5ml (16.2g) ethanol, mixing 10ml (10.4g) MPTMS, 4.1ml (4.4g) DPhDMS and 1.65ml (1.7g) 2N hydrochloric acid, placed 24 hours, thus, make metal alkoxide hydrolysis and polycondensation.The liquid of the condensed polymer that obtains is got 4ml put into water glass with cover,, behind 1-hydroxyl-cyclohexyl-phenyl-ketone of dissolving 10mg,, thus ethanol evaporation is removed, obtain viscous liquid A 100 ℃ of heating down as polymerization initiator.In this viscous liquid of 1g A, mix 3ml (2.25g) trimethylethoxysilane and 0.8ml (0.41g) trifluoroacetic anhydride, place after 24 hours, at 100 ℃ of following heat dryings, thus, the trimethylethoxysilane and the trifluoroacetic anhydride evaporation of surplus are removed, obtain viscous liquid B.
With respect to this viscous liquid of 0.55g B, adding the 0.45g urethane acrylate is to stir behind the light-cured resin, obtains containing the optical resin layer formation solution that 45 weight % urethane acrylates are light-cured resin.
(embodiment 1)
The making of＜compound non-spherical lens 〉
Utilize manufacturing process shown in Figure 11, make compound non-spherical lens.
Shown in Figure 11 (a), the spherical lens that uses glass, drips optical resin layer and forms with solution 3 after forming middle layer 2 on this optical element 1 as optical element 1.As optical element 1, use the glass of high refractive index spherical lens (the refractive index n D=about 1.8 of glass) of diameter 5mm, maximum ga(u)ge 1mm.Middle layer 2 by spin coating silicon oxide particle dispersion liquid after, 100 ℃ down heating formed in 1 hour.
Shown in Figure 11 (b), the mould 10 that inner face is had the nickel system of aspherical shape forms with on the solution 3, then by being pressed in optical resin layer, shown in Figure 11 (c), from optical element 1 side irradiation ultraviolet radiation, optical resin layer is formed with solution 3 solidify, form optical resin layer 3.Specifically, with high-pressure sodium lamp (the about 40mW/cm of intensity 2) from optical element 1 side irradiation ultraviolet ray in 6 minutes, optical resin layer 3 is solidified after, shown in Figure 11 (d), take apart a die 10.Then, with high-pressure sodium lamp (the about 40mW/cm of intensity 2) from optical resin layer 3 sides irradiation ultraviolet ray in 10 minutes, optical resin layer 3 is further solidified.
Operation obtains the compound non-spherical lens shown in Figure 11 (e) as described above.
Fig. 1 is the sectional view along the A-A line of Figure 11 (e).As shown in Figure 1, on optical element 1, be formed with middle layer 2, on middle layer 2, be formed with optical resin layer 3.In addition, though not expression in Figure 11 (e) is formed with antireflection film 7 and 8 respectively on the face of the opposition side of the outer surface of optical resin layer 3 and optical element 1. Antireflection film 7 and 8 is formed by vacuum vapour deposition.The antireflection film 7 that forms on optical resin layer 3 is to be followed successively by SiO from optical resin layer 3 sides 2Layer (thickness 31nm)/Ti 2O 3Layer (thickness 15nm)/SiO 2Layer (thickness 24nm)/Ti 2O 3Layer (thickness 93nm)/SiO 2Antireflection film layer (thickness 83nm), that constitute by 5 layers of structure.In addition, SiO 2The refractive index of layer is 1.46, Ti 2O 3The refractive index of layer is 2.35.
The antireflection film 8 that forms on optical element 1 is to be followed successively by Ti from optical element 1 side 2O 3Layer (thickness 11nm)/SiO 2Layer (thickness 24nm)/Ti 2O 3Layer (thickness 117nm)/SiO 2The antireflection film that constitutes by 4 layers of structure of layer (thickness 89nm).In addition, SiO 2The refractive index and the Ti of layer 2O 3The refractive index of layer is same as described above.
As shown in Figure 1, the middle layer 2 of present embodiment is formed by the matrix resin layer 4 that is dispersed with silicon oxide particle 5.The thickness in middle layer 2 is 200nm.In addition, the maximum ga(u)ge of optical resin layer 3 is 140 μ m.
(embodiment 2)
As shown in Figure 2, form middle layer 2 thereon, in addition, similarly operate, produce compound non-spherical lens with the foregoing description 1 by coupling agent layer 6 that on optical element 1, is provided with and the matrix resin layer that is dispersed with silicon oxide particle 54 that is provided with.
Coupling agent layer 6 heats down by spin coating coupling agent solution 3 and at 140 ℃ and formed in 1 hour.The thickness of coupling agent layer 6 is 10nm.Matrix resin layer 4 forms similarly to Example 1.Its maximum ga(u)ge is 200nm.
Therefore, the thickness in the middle layer in the present embodiment 2 is 210nm.
(embodiment 3)
In the present embodiment, use the niobium oxide particle as molecule 5.In forming matrix resin layer 4, use the niobium oxide particle dispersion, use the niobium oxide particle thus, in addition, similarly operate, produce compound non-spherical lens with the foregoing description 2 as molecule 5.
(embodiment 4)
Adding niobium oxide particle (mean grain size 10nm) in ethanol makes it become the ratio of 10 weight %, prepare dispersion liquid, also stir with adding this dispersion liquid of 1g in the solution in the formation of 1g optical resin layer, prepare the optical resin layer formation solution that is dispersed with the niobium oxide particle.Except using this solution formation optical resin layer 3, compound non-spherical lens is produced in operation similarly to Example 3.
(embodiment 5)
As shown in Figure 4,, on optical element 1, form coupling agent layer 6, on coupling agent layer 6, form matrix resin layer 9, on matrix resin layer 9, form coupling agent layer 6 as middle layer 2.Matrix resin layer 9 as shown in Figure 5, has the structure with 4 layer laminate.That is, be dispersed with the matrix resin layer 4a of silicon oxide particle 5a, repeat this rhythmo structure of 2 layers again, form the matrix resin layer 9 that adds up to 4 layers of structure thus at the matrix resin layer 4b superimposed layer that is dispersed with niobium oxide particle 5b.Specifically, at spin coating niobium oxide particle dispersion and 140 ℃ of down heating after 1 hour, spin coating silicon oxide particle dispersion liquid and 140 ℃ of heating 1 hour down thereon.Carry out this operation repeatedly 2 times, form the matrix resin layer 9 of 4 layers of structure shown in Figure 5.
Coupling agent layer 6 on the optical element 1 heats down by spin coating coupling agent solution 3 backs, at 140 ℃ and formed in 1 hour.Its thickness is 10nm.
Coupling agent layer 6 on the matrix resin layer 9 heats down by spin coating coupling agent solution 3 backs, at 100 ℃ and formed in 1 hour.Its thickness is 10nm.Optical resin layer 3 forms similarly to Example 1.
Each layer of matrix resin layer 9 shown in Figure 5 near one side of optical resin layer, promptly from the top, has following thickness.
Be dispersed with the parent terrain of silicon oxide particle: thickness 169nm
Be dispersed with the parent terrain of niobium oxide particle: thickness 157nm
Be dispersed with the parent terrain of silicon oxide particle: thickness 93nm
Be dispersed with the parent terrain of niobium oxide particle: thickness 79nm
In addition, the refractive index that is dispersed with the parent terrain of silicon oxide particle is 1.48, the refractive index that is dispersed with the parent terrain of niobium oxide particle is 1.59.
As a comparison, produce the compound non-spherical lens that does not form parent terrain 9, with the compound non-spherical lens comparison transmitance of present embodiment, in the compound non-spherical lens of the present embodiment that is formed with matrix resin layer 9, transmitance has improved about 1.8%.
(embodiment 6)
Form middle layer 2 shown in Figure 6.Coupling agent layer 6 heats down by spin coating coupling agent solution 3 backs, at 140 ℃ and formed in 1 hour.Its thickness is 10nm.
Be dispersed with the matrix resin layer 4 of silicon oxide particle 5,, and use the high voltage mercury lamp radiation ultraviolet ray, make thickness reach 0.9 μ m and form by behind the spin coating silicon oxide particle dispersion liquid, 140 ℃ of down heating 1 hour.By this layer is contacted with buffered hydrofluoric acid (BHF) liquid, the silicon oxide particle dissolving of near surface is removed, form hole 4c in its surface, with porous surfaceization.
After this, form optical resin layer 3 similarly to Example 1, thus, under the resin of optical resin layer 3 immerses state among the hole 4c of matrix resin layer 4, form optical resin layer 3.
(embodiment 7)
In the present embodiment, as shown in Figure 7, in the entire circumference formation middle layer 2 of optical element 1.
Fig. 8 is the sectional view along A-A line shown in Figure 7.As shown in Figure 8, form middle layer 2 by on optical element 1, forming coupling agent layer 6 with the matrix resin layer 4 that is dispersed with niobium oxide particle 5.Specifically, after optical element 1 flooded in coupling agent solution 3, it is mentioned, after by air blast (air blow) excessive solution being blown away, heated 1 hour down at 140 ℃, thus, on around the optical element 1 whole, form the coupling agent layer 6 of thickness 10nm.
Then, the optical element 1 that will be formed with coupling agent layer 6 is immersed in the niobium oxide particle dispersion, after it is mentioned, by air blast unnecessary dispersion liquid is blown away, after this, heated 1 hour down at 100 ℃, thus, on whole around the optical element 1, form the matrix resin layer 4 of thickness 200nm.
Then, form optical resin layer 3 similarly to Example 1, make that its maximum ga(u)ge is 140 μ m.
(embodiment 8)
As shown in Figure 9, in the present embodiment, except will forming antireflection film 13 as shown in figure 10 at the antireflection film 13 of formation on the optical resin layer 3, compound non-spherical lens is produced in operation similarly to Example 2.Antireflection film 13 in the present embodiment forms by the following method: behind coating monox dispersion liquid, contacts with buffered hydrofluoric acid (BHF) liquid similarly to Example 5, the silicon oxide particle dissolving of near surface removed, form hole 4c, thus porous materialization.The thickness of antireflection film 13 is 4 μ m.
As shown in figure 10, has the structure that increases from volume near the hole 4c of a side direction of the optical resin layer outside, porous matter.Therefore, refractive index changes continuously, makes it have anti-reflective function thus.
(comparative example 1)
Figure 12 represents the compound non-spherical lens of comparative example 1.As shown in figure 12, on optical element 1, be formed with optical resin layer 3.Figure 13 is the sectional view along the A-A line of Figure 12.As shown in figure 13, after forming coupling agent layer 11 on the optical element 1, form optical resin layer 3 thereon.As optical element 1, use glass of high refractive index spherical lens similarly to Example 1.Coupling agent layer 11 heats down by spin coating coupling agent solution 1 back, at 100 ℃ and formed in 1 hour.Optical resin layer 3 is operated similarly to Example 1 and is formed, and makes that its maximum ga(u)ge is 140 μ m.In addition, antireflection film 7 and 8 also forms similarly to Example 1.
The thickness of coupling agent layer 11 can't be measured with the contact pin type contourgraph, therefore, can think below the 10nm.
(comparative example 2)
As shown in figure 14, in this comparative example, with the thickness thickening of coupling agent layer 11.Coupling agent layer 11 is by using coupling agent solution 3, forming in 1 hour 100 ℃ of following heating after with its spin coating.The thickness of coupling agent layer 11 is measured with the contact pin type contourgraph, is 10nm.
(comparative example 3)
As shown in figure 15, in this comparative example, the thickness of coupling agent layer 11 is further thickeied.Specifically, use coupling agent solution 2, after with its spin coating, 100 ℃ of heating 1 hour down, form coupling agent layer 11 thus.Measure with the contact pin type contourgraph, the thickness of coupling agent layer 11 is 200nm.
(comparative example 4)
As shown in figure 16, in this comparative example, on coupling agent layer 11, use epoxy be light-cured resin as matrix resin, form the matrix resin layer 12 that is dispersed with silicon oxide particle 5.Therefore, except use epoxy be light-cured resin as the matrix resin, form similarly to Example 2.
Specifically, by heating behind the spin coating coupling agent solution 3, under 140 ℃ 1 hour, form the coupling agent layer 11 of thickness 10nm, then, it is in the light-cured resin and behind the dispersion liquid that forms that spin coating thereon makes silicon oxide particle be dispersed in epoxy, heated 1 hour down at 100 ℃, form the matrix resin layer 12 of thickness 200nm thus.The epoxy that is dispersed with silicon oxide particle is the dispersion liquid of resin, uses ethanol as solvent, and use contains the silicon oxide particle (mean grain size 20nm) of the 5 weight % that have an appointment, the epoxy of about 20 weight % is the dispersion liquid of light-cured resin.
(surfaceness of interlayer surfaces)
In each above-mentioned embodiment and each comparative example, after forming the middle layer, measure the surfaceness in middle layer.The surfaceness in the middle layer of measuring is the roughness that becomes with the surface at the interface of optical resin layer.Surfaceness is by AFM (Atomic Force Microscopy: atomic force microscope) measure.In table 1, represent measurement result.
(high temperature and humidity test)
Compound non-spherical lens to the various embodiments described above and each comparative example carries out high temperature and humidity test.Each 50 sample was placed 800 hours under 85 ℃, 85% environment, measured optical resin layer from the sample number of strippable substrate, its result of expression in table 1.
(mensuration of reflectivity)
Measure the reflectivity of optical resin layer side.The assay method of reflectivity utilizes reflection from lens rate mensuration machine to measure.
Evaluation result is shown in table 1.
(grid pattern projection test)
Use device shown in Figure 17, the compound non-spherical lens of the various embodiments described above and each comparative example is carried out grid pattern projection test.
The lens 17 of determination object are configured between the screen 18 and ccd video camera 16 that is formed with mesh pattern, utilize ccd video camera 16 that the mesh pattern on the screen 18 is amplified the back and observe.Mesh pattern on the screen 18 is the mesh pattern 19 of interval 0.5mm as shown in figure 17.
When using glass spherical lens 10, because the distinctive spherical aberration of spherical lens, observe the image of the crooked mesh pattern shown in Figure 18 (a) as lens 17.Relative therewith, when using the compound non-spherical lens made as described above as lens 17, obtain shown in Figure 18 (b), mesh pattern is by the image after verily amplifying.The situation that will obtain the mesh pattern shown in Figure 18 (b) is designated as " well ".The situation line of grid is partly crooked a little or thickness generation fluctuation is designated as " bad ".
Measurement result is shown in table 1.
Table 1
Intermediate layer thickness The surfaceness of interlayer surfaces High temperature and humidity test (individual) The reflectivity of resin face side (wavelength 630nm) Grid pattern projection test
Embodiment
1 200nm Below the 50nm 40 Below 0.3% Well
Embodiment
2 210nm Below the 50nm 45 Below 0.3% Well
Embodiment
3 210nm Below the 50nm 43 Below 0.3% Well
Embodiment
4 210nm Below the 50nm 48 Below 0.3% Well
Embodiment
5 518nm Below the 50nm 50 Below 0.3% Well
Embodiment
6 1μm Below the 50nm 50 Below 0.3% Well
Embodiment
7 210nm Below the 50nm 50 Below 0.3% Well
Embodiment
8 210nm Below the 50nm 45 About 0.7% Well
Comparative example 1 Below the 10nm Below the 10nm 7 Below 0.3% Well
Comparative example 2 10nm Below the 10nm 18 Below 0.3% Well
Comparative example 3 200nm 100～150nm 40 Below 0.3% Bad
Comparative example 4 210nm Below the 50nm 38 Below 0.3% Well
Can find out from the result shown in the table 1, according to the excellent in te pins of durability of compound non-spherical lens in hot and humid of embodiments of the invention.In addition, though the excellent in te pins of durability of comparative example 3 in hot and humid, grid pattern is bad, produces infiltration or crooked.
In the above-described embodiments,, used silicon oxide particle and niobium oxide particle, but when using zirconia particles to replace them, also can obtain and above-mentioned same result as molecule.
In addition, in the above-described embodiments, organic polymer as optical resin layer, having used urethane acrylate is resin, is that the ultra-violet solidified or heat-curing resin of acrylic esters such as resin, silicon-type polyurethane acrylate resin and the Thermocurable or the uv curing resin of epoxy system also can access same effect but epoxy acrylate is resin, polyester acrylate.
Below, the embodiment according to a second aspect of the present invention is described.
(embodiment 9)
Figure 19 is the sectional view of the multilayer optical device of expression present embodiment.On optical element 1, be formed with middle layer 2, on middle layer 2, be formed with optical resin layer 3.Middle layer 2 is by constituting at molecule layer 21 that forms on the optical element 1 and the coupling layer 22 that forms on molecule layer 21.
As the optical element in the present embodiment 1, use the base material of glass of high refractive index.Glass of high refractive index normally contains a large amount of TiO 2, ZrO 2, Nb 2O 5, Ta 2O 5Etc. the glass high index of refraction oxide, that silica composition is few.The glass of high refractive index that uses in the present embodiment is commodity " S-TIH6 " (Obara Corporation's production), no Pb and As by name, contains a large amount of TiO 2Glass of high refractive index.
Molecule layer 21 by after applying commercially available colloidal silica aqueous solution, under 400 ℃, cure and formed in 2 hours.The colloidal silica aqueous solution is the SiO of mean grain size 5nm～500nm normally 2Microparticle is dispersed in aqueous solution in the water with the content of 10～40 weight %.In the present embodiment, use mean grain size to be 5nm, SiO 2Content is the colloidal silica aqueous solution of 10 weight %.In addition, mean grain size can be used determination of electron microscopy.
The above-mentioned colloidal silica aqueous solution of dilute with water makes weight ratio (colloidal silica aqueous solution: water) become 1: 8 ratio, carry out spin coating with the rotational speed of 3000rpm, it is coated on the high refractive index lens as optical element 1.Before coating,, with the hydrofluorite of dilution lens surface is handled in advance in order to improve wetting state to the colloidal silica aqueous solution.Also can replace hydrofluoric acid treatment, carry out in clean-out system, making the clean-out system composition to be adsorbed on the first-class processing of glass surface.By carrying out such pre-treatment, can improve the molecule dispersed uniform in the molecule layer.The thickness of molecule layer depends on the surface-treated state, if make the condition of coatings such as surface-treated state and spin coating always certain, then can utilize the concentration of colloidal silica aqueous solution to control.In the present embodiment, making the thickness of molecule layer 21 is 20nm.In order to prevent to crack etc., the thickness that preferably makes the molecule layer be about 1000nm below.In addition, as containing SiO 2The liquid of molecule also has commercially availablely as the liquid of solvent with the pure and mild toluene beyond the water etc., but when using aqueous solution, the adhesion between the molecule after the coating is strong, and is therefore preferred.In addition, when pure and mild toluene is compared, when using alcoholic solution, can obtain membranous firm molecule layer.That is, as the solution that forms the molecule layer, aqueous solution most preferably, secondly, the solution of alcohols such as preferred alcohol, isopropyl alcohol.
As mentioned above, after coating colloidal silica aqueous solution on the optical element 1, under 400 ℃, cured 2 hours.Thus, in the interface of optical element 1 and molecule layer 21, constitute separately produces the phase counterdiffusion.By this phase counterdiffusion, adherence improves.If the heat treatment temperature of this moment is higher than 500 ℃, then according to the kind difference of glass, the distortion that can produce base material, therefore, preferred below 500 ℃ temperature, be preferably about 400 ℃.
Figure 20 amplifies the figure of expression with the molecule layer 21 of Figure 19 and coupling agent layer 22.As shown in figure 20, in molecule layer 21, owing to, be formed with Ti diffusion zone 21a from the diffusion of the Ti of optical element 1.In addition, above molecule layer 21, be formed with the silicon dioxide area with high mercury 21b that has a large amount of silica compositions.Utilize STEM-EDS to analyze and carry out the analysis of Ti concentration.It is intensity according at the X ray that has produced when having carried out the sample cross section irradiating electron beam of cross section tem observation that STEM-EDS analyzes, and analyzes the kind of contained element and the method for ratio (chemical composition).According to analysis result, in silicon dioxide area with high mercury 21b, detect the about 1 atom % of Ti, in Ti diffusion zone 21a, detect the about 9 atom % of Ti.Therefore, can think that in silicon dioxide area with high mercury 21b, about 99% is that Si, about 1% is Ti.In addition, can think that in Ti diffusion zone 21a, about 91% is that Si, about 9% is Ti.Therefore, can think that in Ti diffusion zone 21a, 21b compares with the silicon dioxide area with high mercury, has the Ti of about 9 times of high concentrations.
Above-mentioned cure processing after, above-mentioned " coupling agent solution 2 " of coating forms coupling layer 22 on molecule layer 21.After the coating, after 5 minutes, use isopropyl alcohol to remove unnecessary coupling agent, form the following coupling agent layer of 1nm from the teeth outwards 100 ℃ of following heat treated.This layer is the thin layer of the degree that can't observe with the infiltration type electron microscope, can think the thickness about 1 molecular layer～several molecular layers.
Behind the coating coupling agent solution, preferably about 100～120 ℃, heat-treat like this.In addition, after coating, preferably thickness below the 1nm is removed, formed to unnecessary coupling agent with alcohol such as ethanol or isopropyl alcohols.Thus, can form the higher coupling layer of adherence.
On above-mentioned such coupling layer that forms 22, use above-mentioned " optical resin layer forms and uses solution ", form optical resin layer.
In the present embodiment, with before forming coupling layer 22, carried out making the surface of molecule layer 21 to become hydrophobic pre-treatment at the coating coupling agent solution.As such pre-treatment, can enumerate the processing of the liquid that with an organic solvent is.In the present embodiment, use with alkyl benzene and alkyl benzene sulphonate remover (trade name: " 502A " as the photoresist of principal ingredient, Tokyo should be changed Co., Ltd. and produce, aromatic hydrocarbon 100 weight %, phenol 20 weight %, alkyl benzene sulphonate 20 weight %), by in this remover, flooding, pre-treatment is carried out on the surface of molecule layer 21.After the processing, clean with acetone.
In the present embodiment, use " coupling agent solution 2 ", but also can replace it and use " coupling agent solution 1 " or " coupling agent solution 3 ".
＜disbonded test 〉
On the optical element that multilayer optical device and glass of high refractive index lens by the foregoing description constitute, do not form the molecule layer, directly form coupling layer, form optical resin layer thereon, produce the multilayer optical device of sample as a comparison.
For the sample of embodiment and the sample of comparative example,, in the atmosphere of 85 ℃-humidity of temperature 85%, place after 500 hours the sample of detect by an unaided eye embodiment and comparative example as accelerated test.In the sample of comparative example, the optical resin layer of the circular about a few μ m～tens μ m is peeled off, but in the sample of present embodiment, can't see fully and peel off.In addition, trade name " S-LAH79 " (Obara Corporation's production), the high index of refraction light transparent ceramic of glass of high refractive index as other also can access same result.
(embodiment 10)
Figure 21 is the sectional view of the multilayer optical device of expression present embodiment.As shown in figure 21, on optical element 1, be formed with middle layer 2, be formed with optical resin layer 3 thereon.Middle layer 2 is by constituting molecule layer and coupling layer 22 laminations, and this molecule layer comprises by Nb 2O 5The molecule layer 23 that constitutes, by SiO 2The molecule layer 24 that constitutes, by Nb 2O 5The molecule layer 25 that constitutes and by SiO 2The molecule layer 26 that constitutes.
As optical element 1, use and glass of high refractive index lens (refractive index 1.8) that embodiment 9 is same.
The thickness of molecule layer 23 is that the thickness of 20nm, molecule layer 24 is that the thickness of 20nm, molecule layer 25 is that the thickness of 140nm, molecule layer 26 is 80nm.By SiO 2The molecule layer 24 and 26 that constitutes, similarly to Example 10, by dilute with water colloidal silica aqueous solution (mean grain size 5nm, SiO 2Content is 10 weight %) and carry out spin coating and form.By Nb 2O 5The molecule layer 23 and 25 that constitutes will be as the Nb of commercially available product by water 2O 5Colloidal sol aqueous solution (mean grain size 5nm, Nb 2O 5Content is 10 weight %) respectively dilution be 50 times, 1.6 times, and its spin coating is formed.But, because can only obtain the thickness of about 70nm, so molecule layer 25 has carried out 2 spin coatings with 1 spin coating.In addition, before forming molecule layer 23, use the pre-treatment of the remover of photoresist similarly to Example 10.
After the spin coating colloidal silica aqueous solution, under 140 ℃, cured 1 minute.In addition, spin coating Nb 2O 5After the colloidal sol aqueous solution, under 140 ℃, cured 1 minute.After forming molecule layer 26, under 400 ℃, cured 2 hours similarly to Example 10, carry out mutual DIFFUSION TREATMENT thus.By this mutual DIFFUSION TREATMENT, improved the adherence of multilayer film.After this, apply coupling agent similarly to Example 10, form optical resin layer 3 thereon to form coupling layer 22.
Figure 22 amplifies the figure of expression with middle layer 2.As shown in figure 22, in molecule layer 23,24 and 25, produce diffusion from the Ti of optical element 1.
In the present embodiment, by Nb 2O 5Form by SiO on the molecule layer that constitutes 2The molecule layer that constitutes, but also can between these layers, form Nb 2O 5And SiO 2The molecule layer that mixes makes the variation of composition be classified to change.Thus, the few multilayer film of stress in the time of can forming film formation.
＜disbonded test 〉
To the sample of present embodiment, also similarly carry out disbonded test with the foregoing description 9, the result can't see fully and peels off.In addition, trade name " S-LAH79 " (Obara Corporation's production), the high index of refraction light transparent ceramic of glass of high refractive index as other also can access same result.
(embodiment 11)
Figure 23 is the sectional view of the multilayer optical device of expression present embodiment.As shown in figure 23, on optical element 1, be formed with middle layer 2, on middle layer 2, be formed with optical resin layer 3.Middle layer 2 is formed by the first molecule layer 27 and the second molecule layer 28 and coupling layer 22.The first molecule layer 27 uses the colloidal silica aqueous solution to form similarly to Example 9, by after the coating colloidal silica aqueous solution, under 400 ℃, cure and formed in 2 hours.Its thickness is 5nm.Then, the second molecule layer 28 by after applying same colloidal silica aqueous solution, the temperature that will cure processing is reduced to 280 ℃ and carries out curing in 30 minutes handling and form.Its thickness is 5nm.
Figure 24 amplifies the figure of expression with middle layer 2.The first molecule layer 27 as mentioned above, cures processing under 400 ℃, therefore, produce the diffusion from the Ti of optical element 1 etc.Relative therewith, the second molecule layer 28 as mentioned above, cures processing under 280 ℃, therefore, produces the diffusion of Ti etc. hardly, becomes the many layers of dioxide-containing silica.Therefore, the adherence with the coupling layer 22 that forms thereon becomes better.
Handle the molecule layer that forms by as present embodiment, being provided with,, also can form the layer more than the silica composition in its surface even with the thickness attenuation of molecule layer integral body by curing of low temperature more.Thickness attenuation by with the molecule layer can reduce the generation of peeling off with crackle, therefore, according to such method, can the higher multilayer optical device of fabrication reliability.
In addition, coupling layer 22 and optical resin layer 3 form similarly to Example 9.
(embodiment 12)
Figure 25 is the sectional view of the multilayer optical device of expression present embodiment.As shown in figure 25, on optical element 1, be formed with middle layer 2, on middle layer 2, be formed with optical resin layer 3.In the present embodiment, middle layer 2 constitutes by form coupling layer 22 on molecule layer 29.In the present embodiment, molecule layer 29 uses the colloidal silica aqueous solution of mean grain size 80nm to form.By making SiO 2The mean grain size of molecule is 80nm, forms big concavo-convex on the surface of molecule layer 29.Therefore, the surface area of molecule layer 29 is increased, coupling layer 22 and optical resin layer 3 form with the interfacial state that enters mutually.Therefore, molecule layer 29, coupling layer 22 and optical resin layer 3 mutual adherences improve.
In addition, coupling layer 22 and optical resin layer 3 form similarly to Example 9.
(embodiment 13)
Figure 26 is the sectional view of the multilayer optical device of expression present embodiment.As shown in figure 26, in the present embodiment, be formed with middle layer 2 on optical element 1, be formed with optical resin layer 3 on middle layer 2, middle layer 2 is formed by the first molecule layer 30, the second molecule layer 31 and coupling layer 22.
The first molecule layer 30 is by using the colloidal silica aqueous solution of mean grain size 5nm, the coating back, carries out curing in 2 hours under 400 ℃ and handles and form, and makes that thickness is about 20nm.The second molecule layer 31 is handled down at 280 ℃ and was formed in 30 minutes by colloidal silica aqueous solution, the coating back of using mean grain size 80nm thereon, makes that thickness is about 300nm.Like this, by forming the first molecule layer 30 and the second molecule layer 31, can make with the adherence of optical element 1 good and also with the good multilayer optical device of adherence of coupling layer 22 and optical resin layer 3.
That is, the first molecule layer 30 forms mean grain size 5nm, promptly uses the also extremely smooth layer of tem observation, does not form the space between the molecule, assembles and cambium layer airtightly.Therefore, on whole interface, contact, become good state with the adherence of optical element 1 with optical element 1.By using mean grain size to reach the colloidal solid of size about 50nm, can form fine and close layer.The second molecule layer 31 forms big concavo-convexly similarly to Example 12 on its surface, therefore, become the adherence good state with coupling layer 22 and optical resin layer 3.
The interface of the first molecule layer 30 and the second molecule layer 31, though contact area is little, because form by same material, so, for example annealing about 120 ℃, also can access fully good adherence.
In the present embodiment, the molecule layer is divided into 2 layers, forms the hierarchy that the particle diameter make the molecule layer increases gradually, but also can further form multilayer, form the hierarchy that particle diameter increases.
In addition, coupling layer 22 and optical resin layer 3 form similarly to Example 9.
(embodiment 14)
In the various embodiments described above, use the colloidal silica aqueous solution to form the molecule layer, but use after also can in the colloidal silica aqueous solution, adding adhesive resin.By adding such adhesive resin,, the molecule layer is solidified to form even under the high temperature about 300～500 ℃, do not cure processing.For example, can make its curing or make its curing by the temperature that is heated to about 120 ℃ by irradiation ultraviolet radiation.
Present embodiment is to use the embodiment of the molecule aqueous solution that is added with such adhesive resin.
Figure 27 is the sectional view of manufacturing process of the multilayer optical device of expression present embodiment.At first, prepare the optical element 1 that constitutes by the glass of high refractive index lens shown in Figure 27 (a).Then, shown in Figure 27 (b), on a face of optical element 1, form the first molecule layer 32a.This first molecule layer 32a is by using colloidal silica aqueous solution (mean grain size 5nm, the SiO that does not contain adhesive resin 2Content is 10 weight %), coating back carries out mutual DIFFUSION TREATMENT and forms under 400 ℃, make that thickness is 20nm.Thereon, shown in Figure 27 (b), operation similarly to Example 9 forms coupling layer 22 and optical resin layer 3.
Then, shown in Figure 27 (c), form the second molecule layer 32b to cover all modes.Use is at 4ml colloidal silica aqueous solution (mean grain size 5nm, SiO 2Content is 10 weight %) and the mixed liquor of 4ml water in be added with 20 μ l (microlitre) aqueous solution that methacrylic acid-the 2-hydroxyethyl ester forms as resin binder, by applying this aqueous solution, form the second molecule layer 32b.With regard to coating method, in spin-coating method, in coating, might produce inhomogeneous, so, preferably utilize liquid top nitrogen blowing or the air from coating such as air gun, so that it is dry as early as possible.In the present embodiment, while blow air so that its dry coating.After making dried coating film, irradiation ultraviolet radiation forms the second molecule layer 32b.
In the formation of the second molecule layer 32b, use resin binder, so be because formed the cause that the first optical resin layer 3a can not at high temperature cure.
Then, shown in Figure 27 (d), on the second molecule layer 32b on another face of optical element 1, operation forms the second coupling layer 22b and the second optical resin layer 3b similarly to Example 9.
In the multilayer optical device shown in Figure 27 (d), the second molecule layer 32b is in a face (face of top) of optical element 1, can work as dura mater (hard coat) layer, in another face (face of below), can work as the molecule layer that is used to improve adherence.
As resin binder, use a kind of methacrylic acid-2-hydroxyethyl ester in the present embodiment, but also can use water soluble acrylic resin and water-soluble epoxy resin etc. as water miscible acrylic monomers.In addition, in the mixed liquor of 4ml colloidal silica aqueous solution and 4ml water, add methacrylic acid-2-hydroxyethyl ester of 20 μ l (microlitre), and add the coupling agent solution 2 of 20 μ l (microlitre) again, become more stable liquid thus, have and to reduce the uneven effect of coating.
As adhesive resin, in water soluble propene's acid monomers, the material that has hydroxyl as above-mentioned monomer is difficult to make the molecule aggegation, is very easy to handle.
In addition, forming by Nb 2O 5During the molecule layer that constitutes, with SiO 2The molecule layer compare, be difficult to produce inhomogeneous after the coating.For example, at the Nb of 4ml 2O 5Colloidal sol aqueous solution (mean grain size 5nm, Nb 2O 5Content is 10 weight %) and the mixed liquor of 4ml water in, add methacrylic acid-2-hydroxyethyl ester of 20 μ l (microlitre), and carry out spin coating and form.In addition, will be by SiO 2The molecule layer that constitutes and by Nb 2O 5Alternately behind the lamination, irradiation ultraviolet radiation can easily form multilayer film to the molecule layer that constitutes thus simultaneously.
(embodiment 15)
Figure 28 is the sectional view of manufacturing process of the multilayer optical device of expression present embodiment.
Shown in Figure 28 (a), prepare the high refractive index lens of the flat type of one side, as optical element 1.Then, shown in Figure 28 (b),, do not apply Nb dilutedly in the plane of optical element 1 side 2O 5Colloidal sol aqueous solution (mean grain size 5nm, Nb 2O 5Content is 10 weight %) after, carry out patterning as described below, form the first molecule layer 33, produce Fresnel lens (Fresnel lens).As the method for making of Fresnel lens, following 2 kinds of methods are arranged.
＜the first method 〉
Coating Nb 2O 5Colloidal sol aqueous solution (mean grain size 5nm, Nb 2O 5Content is 10 weight %) after, under 140 ℃, cured 30 minutes, make the molecule layer reach to a certain degree curing.Then, form photoresist, use photomask to form the resist pattern of diffraction grating on the surface of this molecule layer.After this, by cleaning in the special-purpose clean-out system (trade name " SE10 ", Sonic Fellow Co., Ltd. produce) immersion at the glass that is heated to 80 ℃ 5～10 minutes, the molecule part stripping of the part that is covered by resist film is not in clean-out system and be removed.After this, utilize resist stripper (resist stripper) to remove photoresist.The molecule layer can utilize hydrofluorite to remove, but at this moment, might etch into the lens of bottom.But,, can optionally only remove the molecule layer by using this clean-out system.This removes method not only at Nb 2O 5In time, can use, at SiO 2Also can use during with other oxide fine particle.
＜the second method 〉
At the Nb of coating with above-mentioned same 4ml 2O 5After the mixed liquor of the methacrylic acid of colloidal sol aqueous solution and 20 μ l-2-hydroxyethyl ester, use photomask, carry out the ultraviolet ray irradiation.Thus, as the methacrylic acid-2-hydroxyethyl ester generation cross-linking reaction of photonasty acrylic monomers, only the sensitization of molecule layer is partly solidified.Then, by cleaning in the special-purpose clean-out system (SE10) immersion at the glass that is heated to 80 ℃ 5～10 minutes, the molecule layer stripping of the part of sensitization be not in clean-out system and be removed.
Utilize above method, will be by Nb 2O 5Behind the first molecule layer, 33 patterning that constitute, shown in Figure 28 (c), coating is by SiO 2The second molecule layer 34 that constitutes.When in the first molecule layer, adding adhesive resin, preferably in the second molecule layer 34, also add adhesive resin.In addition, during with its patterning, preferably in the second molecule layer 34, do not add adhesive resin when in the first molecule layer 33, not adding adhesive resin yet.At this moment, the second molecule layer was curing under 400 ℃ 2 hours after the coating, so that its curing.
Then, behind coating coupling agent solution 2, with alcohol the coupling agent on surface is removed similarly to Example 9, formed the following coupling layer 22 of thickness 1nm.
Then, shown in Figure 28 (d), on coupling layer 22, operation similarly to Example 9 forms optical resin layer 3, can make Fresnel lens thus.
(embodiment 16)
Figure 29 is the sectional view of the multilayer optical device of expression present embodiment.In the multilayer optical device of present embodiment, use tabular optical element 1, on its two sides, be formed with Fresnel lens that produces by diffraction grating and the non-spherical lens that produces by optical resin layer 3a and 3b separately.In the face up and the face of below, operate similarly to Example 15, form first molecule layer 35a and the 35b of patterning respectively, form second molecule layer 36a and the 36b thereon, form coupling layer 22a and 22b thereon respectively, form optical resin layer 3a and 3b then thereon.
In addition, when using plate-like substrate, as shown in figure 30, can on same optical element 1, make a plurality of optical elements 37 simultaneously as optical element.
In addition, as shown in figure 27, when forming the molecule layer as outermost hard membrane layer, can be by the partially patterned diffraction grating that forms with this hard membrane layer.
In the various embodiments described above, by mutual DIFFUSION TREATMENT, Ti as the optical element composition is diffused in the molecule layer, even for example Nb, Zr, Sn, Ce, Ta etc., also with similarly can the be improved effect of adherence of molecule layer and optical element of Ti.
In the various embodiments described above, the coating method during as formation molecule layer is that the center is illustrated with the spin-coating method, applies but also can utilize infusion process to replace spin-coating method.In this case, for coating equably, preferably optical element is immersed in back in the coating solution, optical element mentioned with certain speed.
In the various embodiments described above, as molecule, to SiO 2And Nb 2O 5Be illustrated, but the present invention is not limited to these molecules, also can uses: ZrO 2, TiO 2, Al 2O 3, SnO 2, CeO 2, Ta 2O 5Deng oxide; The GaN higher, nitride based molecules such as AlN, GaInN than oxide refractive index; Or the adamas molecule etc.These molecules, because the physical hardness height, so, when double as is hard membrane layer, preferably use these particles.In addition, under the situation of nitride based molecule, at TiO 2, Nb 2O 5In oxide,, but, can solve such problem by using nitride based molecule because light-catalyzed reaction when at the part irradiation ultraviolet radiation that contacts with optical resin, has the situation that causes the resin variable color.
(embodiment 17)
Figure 31 is the sectional view of an embodiment of expression photographing module of the present invention.As shown in figure 31, imaging apparatus 45 is provided with the compound lens that is made of 4 non-spherical lenses 41,42,43 and 44 that kept by support 46.Photographing module 40 has 4 non-spherical lenses 41～44 like this, and the photographing module of 2～5,000,000 pixels that can use as portable phone uses.
In the non-spherical lens 41～44 of present embodiment, at the coupling layer 22 that is formed with the molecule layer 21 shown in the embodiment 9 on the optical element and on the molecule layer, forms.Therefore, even on the few optical element of silica composition, also can adherence, reliability forms optical resin layer 3 well, thereby can use the few glass of high refractive index of silica composition as optical element.Therefore, in the present embodiment,, use the non-spherical lens that in embodiment 9, uses glass of high refractive index (Obara Corporation's production, trade name " S-LAH79 ", refractive index about 2.0) to form as optical element as non-spherical lens 41～44.Because use the high index of refraction base material of refractive index about 2.0, so can shorten focal length.Therefore, can shorten the length of support 46, so the height that can make the photographing module of present embodiment is about 8mm.
In addition, in the present embodiment, making non-spherical lens 41～44 all is compound non-spherical lens, but according to the design of photographing module, not needing to make whole lens is compound non-spherical lens all, is compound non-spherical lens as long as make at least 1 lens.
Use in the photographing module at the portable phone compound non-spherical lens, in the past that uses the molecule layer 21 that does not have shown in embodiment 9 on the optical element, in order to keep the adherence of optical element and optical resin layer, need to improve the silica composition of optical element, therefore, the glass material that can use is limited, and its refractive index reaches about 1.6.Therefore, can not shorten focal length, so the height of photographing module in the past is for about about 10mm.
Figure 32 is that the highly sectional view of the portable phone of the folding type of the photographing module in the past of 10mm is disposed in expression.
At Figure 32 (a) with under the doubled state (b), height H is 25mm.In the portable phone shown in Figure 32 (a), the height h of upper portion 1Height h with following quadrate part 2The 12.5mm that respectively does for oneself is identical height.Have photographing module 40 up in the portion, be built-in with TV tuner 51, hard disk drive 52 and display 53 etc.In Figure 32 (a), the height h of upper portion 1Be 12.5mm, lower, so the existence of photographing module 40 becomes trouble, be provided with little display 53.In following quadrate part, be built-in with keyboard 54 and battery 55 etc.
In the portable phone shown in Figure 32 (b), the height h of upper portion 1Height h for 14.5mm, following quadrate part 2Be 10.5mm.Because be designed to the height h of upper portion 1Uprise, so, big display 53 can be disposed.On the other hand, because the height h of following quadrate part 2Be 10.5mm, so the volume of battery 55 diminishes, the problem that has battery capacity to diminish.
Figure 33 is the sectional view of expression according to the portable phone of one embodiment of the present of invention.At Figure 33 (a) with in the portable phone (b), be built-in with photographing module 40 of the present invention.The height of photographing module 40 of the present invention for example can be reduced to about 8mm, so, shown in Figure 33 (a),, do not need to improve the height h of upper portion even dispose big display 53 yet 1, can make down the height h of quadrate part 2For with the height h of upper portion 1Identical 12.5mm.Therefore, can built-in jumbo battery 55.
In addition, shown in Figure 33 (b), portion and below portion dispose photographing module 40 respectively up.Therefore, can carry out the photography of stereo-picture, and the face of oneself can be photographed also with high image quality.In addition, thus also can use the full shot of a plurality of video cameras, improve application such as sensitivity in fact with the output signal of a plurality of video cameras electricity is synthetic.
(embodiment 18)
In addition, the photographing module shown in Figure 31 photographing module that also can be used as the vehicle mounted back eye monitor uses.The photographing module of vehicle mounted needs the thermotolerance of height, can use the non-spherical lens that uses in embodiment 17.In addition, because this non-spherical lens has high index of refraction, so, can enlarge the visual angle.
(embodiment 19)
Figure 34 is the schematic section of expression liquid crystal projector.Light source 63 is provided with lamp optical system 62, and lamp optical system 62 is made of lens 62a and 62b.The rayed that penetrates from light source 63 on half-mirror 64, the light that sees through half-mirror 64 mirror 68 reflections that are reflected, scioptics 70 and liquid crystal panel 73 incide cross prisms 69.
On the other hand, the rayed that is reflected by half-mirror 64 is on half-mirror 65, and by the light that half-mirror 65 reflects, scioptics 71 and liquid crystal panel 74 incide cross prisms 69.
The light that sees through half-mirror 65 be reflected mirror 66 reflections, mirror 67 reflections that are reflected again, scioptics 72 and liquid crystal panel 74 incide cross prisms 69.
Liquid crystal panel 75 is liquid crystal panels of red (R) usefulness, and liquid crystal panel 74 is liquid crystal panels of green (G) usefulness, and liquid crystal panel 73 is liquid crystal panels of blue (B) usefulness.Light by these liquid crystal panels is synthetic by cross prisms 69, by projection optical system 61, penetrates to the outside.Projection optical system 61 is made of compound non-spherical lens 61a, 61b and 61c.
Light source 63 for example is made of metal halide lamp, mercury lamp, LED etc.
Because light source 63 is pyrotoxins, so, in the liquid crystal projector in the past that does not use the molecule layer 21 shown in the embodiment 9, the influence of temperature variation repeatedly that causes owing to ON/OFF by light source, the problem that exists glass baseplate and optical resin layer to peel off need make the lens 61a～61c of projection optical system leave light source 63 distance to a certain degree as far as possible.
But, in the present embodiment, in lens 61a～61c, use the compound non-spherical lens that uses among the embodiment 17, on the optical element of these compound non-spherical lenses, the coupling layer 22 that is formed with the molecule layer 21 shown in the embodiment 9 and on the molecule layer, forms.Therefore, no matter the dioxide-containing silica of optical element is how, can both adherence, reliability forms optical resin layer 3 well, even the temperature variation repeatedly that causes owing to the ON/OFF by light source 63, glass baseplate and optical resin layer can not peeled off yet.In addition, the optical resin layer of this compound non-spherical lens (resin lens layer) forms by comprising the good stable on heating Organometallic polymer material of having of organometallic polymer and organic polymer, so, have good thermotolerance.Therefore, lens 61a～61c can be configured in light source 63 near.
Figure 35 is the schematic section of expression according to an embodiment of liquid crystal projector of the present invention.
In embodiment shown in Figure 35, in the lens 61a～61c of projection optical system 61, use the lens that use among the embodiment 17.Therefore, as shown in figure 35, the position configuration of light source 63 can be become near projection optical system 61.Therefore, can make liquid crystal projector 60 miniaturizations.
In liquid crystal projector shown in Figure 35, the light that penetrates from light source 63 is radiated on the half-mirror 64 by lamp optical system 62, and by the light that half-mirror 64 reflects, scioptics 70 and liquid crystal panel 73 incide cross prisms 69.The light that sees through half-mirror 64 mirror 68 reflections that are reflected, directive half-mirror 65.By the light that half-mirror 65 reflects, scioptics 71 and liquid crystal panel 74 incide cross prisms 69.The light that sees through half-mirror 65 mirror 66 reflections that are reflected, mirror 67 reflections that are reflected again, scioptics 72 and liquid crystal panel 75 incide cross prisms 69.The light that sees through liquid crystal panel 73,74 and 75 is synthetic by cross prisms 69, injects to the outside by projection optical system 61.
Figure 34 and liquid crystal projector shown in Figure 35 are the 3 board-like infiltration type projectors that show RGB with liquid crystal panel independently, even but use 1 synthetic liquid crystal panel to show the one-board infiltration type projector of RGB, also can access same effect.
In liquid crystal projector shown in Figure 36,, use White LED as light source 63 in order further to realize miniaturization.As shown in figure 36, from the light that light source 63 penetrates, by lamp optical system 62, scioptics 70, liquid crystal panel 73 by projection optical system 61, inject to the outside again.
As shown in figure 36, can will 61 be configured on the straight line from light source 63 to projection optical system.Under these circumstances, in lens 61a, the 61b and 61c of projection optical system 61, use the compound non-spherical lens that uses among the embodiment 17, can shorten focal length thus, so, the length of liquid crystal projector integral body can be shortened.
(embodiment 20)
Figure 37 is the sectional view of expression optical waveguide of the present invention.As shown in figure 37, substrate 80 is provided with middle layer 81, is formed with optical resin layer 84 on middle layer 81.Optical resin layer 84 is formed by bottom clad 86, the sandwich layer 85 that is provided with in the groove 86a of bottom clad 86 and top clad 87, constitutes optical waveguide.Middle layer 81 is made of molecule layer 82 and coupling layer 83.
As substrate 80, can use for example glass substrate, Si substrate, sapphire substrate, GaN substrate etc.In addition, also can use on the surface of these substrates and be formed with Al 2O 3The substrate of film, SiN film, metal film etc.According to the present invention, even use substrate surface not contain SiO 2The substrate of composition is by forming almost by SiO 2The molecule layer that constitutes, the adherence that can improve coupling layer improves effect, thereby can adherence form optical resin layer well.
Molecule layer 82 for example can use the colloidal silica aqueous solution to form similarly to Example 9.In addition, coupling layer 83 also can be operated similarly to Example 9 and form.
On the coupling layer 83 that forms as described above, form bottom clad 86, sandwich layer 85 and top clad 87, thereby form optical resin layer 84 as optical waveguide.Bottom clad 86 and top clad 87 can use " optical resin layer forms and uses solution " among the embodiment 1 to form.In addition, for sandwich layer 85, also use " optical resin layer forms and uses solution " among the embodiment 1, but the refractive index of sandwich layer need be than the refractive index high about about 0.005 of clad, therefore, when preparing " optical resin layer forms and uses solution ", the PhDMS, the interpolation 4.2ml that add 0.1ml during than clad get final product.
Bottom clad 86 forms as follows: drip optical resin layer formation solution on coupling layer 83, then, the mold compresses that will have protuberance is on the layer of this solution, and irradiation ultraviolet radiation under this state solidifies solution.Thus, can form bottom clad 86 with groove 86a.Then, drip above-mentioned sandwich layer formation and use solution in groove 86a, be full of groove 86a with this solution, irradiation ultraviolet radiation solidifies this solution, can form sandwich layer 85.
Then, drip above-mentioned optical resin layer formation and use solution on bottom clad 86 and sandwich layer 85, irradiation ultraviolet radiation solidifies it, can form top clad 87 thus.
According to the present invention, for example can utilize spin coating or infusion process on substrate, to form SiO 2The molecule layer applies coupling agent thereon, forms coupling layer, thus, can adherence form optical resin layers such as optical waveguide well.Therefore, even substrate surface does not contain SiO 2The substrate of composition also can adherence form optical waveguide etc. well.Therefore, on the Si substrate, also can adherence form optical waveguide well, so, optical device can be on electron device, formed, thereby the large-scale device of electronic light can be easily made.For example, can integrally make electronics part and optical waveguide portions such as sending/receiving module.
(embodiment 21)
In the present embodiment, lamination mixing molecule layer, SiO successively on glass substrate 2Molecule layer, coupling layer and optical resin layer are produced compound non-spherical lens.In compound non-spherical lens etc., under the high situation of the refractive index of glass baseplate, become big with the difference of the refractive index of optical resin layer, so, the big problem of reflection change at the interface of glass baseplate and optical resin layer is arranged.Usually, in compound non-spherical lens, the reflectivity of glass baseplate and optical resin layer poor, as the average reflectance to the light of 430～650nm wavelength, requirement is below 1%.In the past, for example 2 kinds of oxide film combinations that refractive index is different constituted the multilayer film more than 3 layers usually, used as antireflection film.In order to form multilayer film, need carry out repeatedly film forming, need the thickness of strict each layer of control simultaneously.Therefore, consider the fluctuation of the homogeneity and the repeatability of thickness, being difficult to the average reflectance to the light of wavelength 430～650nm is suppressed is below 1%.According to present embodiment, by with 2 layers of oxide skin(coating) laminations, can easily make antireflection film, thereby the average reflectance to the light of wavelength 430～650nm can be suppressed be below 1%.
The structure of the multilayer optical device of present embodiment is and same structure shown in Figure 23 that middle layer 2 is formed by the first molecule layer 27, the second molecule layer 28 and coupling layer 22.In the present embodiment, the first molecule layer 27 is that 2 kinds of microparticles that refractive index is different mix the mixing molecule layer that forms, and the second molecule layer 28 is by SiO 2The molecule layer that constitutes.
Mix of the dispersion liquid mixing of molecule layer, refractive index is adjusted into setting by 2 kinds of microparticles that refractive index is different.Mix the formation of molecule layer, can utilize spin-coating method or infusion process etc. to carry out.Preferably making the refractive index of mixing the molecule layer is the mean value n of the refractive index of the refractive index of glass baseplate and optical resin layer AveIn addition, thickness is preferably 1/4 of wavelength.When using with lens as optics, because be the visible region, so, as centre wavelength, be preferably about λ=540nm.Therefore, the thickness of mixing molecule layer is preferably (1/4) λ/n Ave
SiO 2The molecule layer as the bottom of coupling layer, is used to make the adherence with optical resin layer well to form.Preferably make about its thin thickness to 10～15nm, making does not influence reflectivity.In addition, when the adherence that can not consider with optical resin layer, also this layer can be omitted.
For coupling layer, also preferably make about thin thickness to 10～15nm, making does not influence reflectivity.When the adherence that can not consider with optical resin layer, also this layer can be omitted.
In the present embodiment, as glass baseplate, use glass of high refractive index (Obara Corporation's production, trade name " S-LAL7 ", refractive index about 1.8).In addition, optical resin layer uses " optical resin layer forms and uses solution " among the embodiment 1 to form.The refractive index of optical resin layer is 1.5.
Mixing the molecule layer passes through SiO 2Microparticle dispersion liquid and Nb 2O 5The microparticle dispersion liquid mixes and forms.As SiO 2The microparticle dispersion liquid uses colloidal silica aqueous solution (Misao Kusano's production, trade name " ス ノ one テ Star Network ス NXS ", mean grain size 5nm, SiO 2About content 15.7 weight %).As Nb 2O 5The microparticle dispersion liquid uses niobium colloidal sol aqueous solution (Taki Chemical Co., Ltd's production, trade name " バ イ ラ one Le Nb-X10 ", mean grain size 5nm, Nb 2O 5Content 10 weight %).
Table 2 expression is by colloidal silica (Sample A), the niobium colloidal sol refractive index of the molecule layer that forms of the mixed sols (sample B) of (sample C) and colloidal silica sol and niobium colloidal sol separately separately.In the sample B that colloidal sol is mixed, with Sample A: sample C=1: 2 weight rate mixes.In addition, the molecule layer forms by utilizing spin-coating method (3000rpm, 30 seconds) each colloidal sol of coating and being dried on glass baseplate.
Table 2
Sample The ratio of microparticle dispersion liquid Oxide containing ratio in the dispersion liquid Mixture ratio in the molecule layer Refractive index
SiO 2Microparticle dispersion liquid (weight %) Nb 2O 5Microparticle dispersion liquid (weight %) SiO 2(weight %) Nb 2O 5(weight %) SiO 2(weight %) Nb 2O 5(weight %)
A 100 0 14.7 0.0 100 0 1.38
B 33 67 4.9 6.7 42.4 57.6 1.65
C 0 100 0.0 10.0 0 100 1.88
Figure 38 is the Nb in the expression molecule layer 2O 5The figure of the relation of containing ratio and refractive index.
As shown in figure 38, refractive index and Nb 2O 5Containing ratio become big pro rata.Therefore, as can be known, by adjusting Nb 2O 5Containing ratio can be adjusted refractive index in 1.39～1.88 scope.
In the present embodiment, use sample B, making the refractive index of mixing the molecule layer is 1.66.In addition, mixing the thickness of molecule layer, is 540nm with centre wavelength, becomes (1/4) λ/n Ave=81nm.
Figure 39 is that the refractive index that is illustrated in optical resin layer is 1.5, the refractive index of mixing the molecule layer is 1.66 o'clock, the refractive index that makes glass baseplate with 1.8 be the center, the figure of reflectivity calculating value when between 1.7～1.9, changing.As shown in figure 39, as can be known, when the refractive index of glass baseplate was 1.8, reflectivity was minimum.Therefore as can be known, when making the refractive index of mixing the molecule layer be the mean value of refractive index of glass baseplate and optical resin layer, reflectivity is minimum.
Mix the molecule layer by as present embodiment, using, can easily form antireflection film.The refractive index of mixing the molecule layer can be adjusted into arbitrary value as mentioned above, therefore, even the material of glass baseplate and optical resin layer changes, by adjusting the kind and the mixing ratio of mixing the microparticle in the molecule layer, can adjust the refractive index of mixing the molecule layer, make reflectivity minimum.Specifically, can adjust the refractive index of mixing the molecule layer, make it become the refractive index of the intermediate value of glass baseplate and optical resin layer.
In addition, by on mixing molecule layer, SiO being set 2The molecule layer can improve the adherence effect of coupling layer, thereby can improve the adherence of optical resin layer.

Claims (20)

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 comprises is 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 the molecule layer that forms the molecule that is made of metal oxide.
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 described molecule layer.
3. multilayer optical device as claimed in claim 1 or 2 is characterized in that:
Described middle layer comprise the described molecule layer that is arranged on described optical element side and the coupling layer that is arranged on described optical resin layer side, 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. as each described multilayer optical device in the claim 1～3, it is characterized in that:
The composition of described optical element spreads in described molecule layer.
5. as each described multilayer optical device in the claim 1～4, it 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. as each described multilayer optical device in the claim 1～5, it 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. as each described multilayer optical device in the claim 1～6, it 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 of adhesive resin that is selected from water soluble propene's acid monomers, water soluble resin, silane coupling agent and the photoresist.
8. as each described multilayer optical device in the claim 1～7, it is characterized in that:
Described coupling layer is formed the following thickness of 1nm.
9. as each described multilayer optical device in the claim 1～8, it is characterized in that:
Described molecule layer is patterned.
10. as each described multilayer optical device in the claim 1～9, it is characterized in that:
Outer surface at described optical resin layer is provided with antireflection film.
11., it is characterized in that as each described multilayer optical device in the claim 1～10:
Also contain described molecule in the described optical resin layer.
12., 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.
13., it is characterized in that as each described multilayer optical device in the claim 1～12:
Described molecule is to be selected from least a in monox, niobium oxide and the zirconia.
14., it is characterized in that as each described multilayer optical device in the claim 1～13:
Form concavo-convexly by surface, form concavo-convex at the interface of described middle layer and described optical resin layer in described middle layer.
15., it is characterized in that as each described multilayer optical device in the claim 1～14:
Described middle layer be configured to cover described optical element around.
16., it is characterized in that as each described multilayer optical device in the claim 1～15:
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.
17., it is characterized in that as claim 10 or 16 described multilayer optical devices:
Described antireflection film is by forming, form from the teeth outwards irregular film with described middle layer identical materials.
18., it is characterized in that as each described multilayer optical device in the claim 1～17:
Also contain organic acid anhydride and/or organic acid in the described optical resin layer.
19., it is characterized in that as each described multilayer optical device in the claim 1～18:
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.
20. 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 19.
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