CN101045788A - Curable organometallic composition, organometallic polymer material and optical component - Google Patents
Curable organometallic composition, organometallic polymer material and optical component Download PDFInfo
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- CN101045788A CN101045788A CN 200710091530 CN200710091530A CN101045788A CN 101045788 A CN101045788 A CN 101045788A CN 200710091530 CN200710091530 CN 200710091530 CN 200710091530 A CN200710091530 A CN 200710091530A CN 101045788 A CN101045788 A CN 101045788A
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Abstract
A curable organometallic composition containing an organometallic polymer having an -M-O-M- bond (M denotes a metal atom) and an aryl group, and a fluorene-based compound having an acryloyl or methacryloyl group, an organometallic polymer obtained by curing the composition and an optical component using the material.
Description
Technical field
The present invention relates to curable organometallic composition and, can be used in various coating materials such as electric distribution substrate, mechanical part material, antireflection film, surface protection film the Organometallic polymer material after its curing; Optical communication device such as optical transceiver module and photoswitch; Optical waveguide, optical fiber and lens array light conducting pathway structures such as (lens array); And the optical devices such as spectroscope that contain said structure; Integral lens, micro lens array (microlens array), reflector, light guiding plate, projection are with the related optics of display devices such as screen (indicating meter or liquid crystal projection apparatus etc.); Glasses, CCD optical system; Be used for digital camera or portable phone camera lens with photographic camera etc.; Optical filter, grating, interferometer, opticcoupler, optical multiplexer/demultiplexer, optical sensor, holographic optics parts, other used for optical part material; The molding material of photosensor, contact lense, medical artificial organ, photodiode (LED) etc.
Background technology
The material that contains the optical element of lens mainly uses glass and plastics all the time.Because the kind of glass is many, change of optical property is abundant, so optical design is easy, and because of it is inorganic based material, so the reliability height.And, can access high-precision optics by grinding.
But, the glass cost height, and the aspherical shape beyond plane or the sphere need be used special milling apparatus, perhaps the glass material that can be out of shape at low temperatures is shaped in the high mould of the thermotolerance of costliness (pottery system etc.), promptly must form, increase manufacturing cost by injection molding.
On the other hand, use synthetic resins material (plastic material) though optical element can make cheaply by injection forming or casting method, have that thermotolerance is low, thermal expansion greatly, problem such as the range of choice of optical characteristics such as specific refractory power is narrow, reliability is low.
Method as solving above-mentioned problem has proposed by obtain the composite optical element of desired characteristic at glass baseplate superimposed layer resin layer.In Japanese kokai publication sho 54-6006 communique, the low-pass filter that is formed with organic polymer layer on the planar glass substrate is disclosed.In Japanese kokai publication sho 52-25651 communique and Japanese kokai publication hei 6-222201 communique, the compound non-spherical lens that is formed with the resin layer with aspherical shape on the glass lens base material is disclosed.
Therefore compare with resin lens, the resin of compound non-spherical lens partly is as thin as about several 100 μ m, has the influence of temperature of being subjected to etc. and the little such characteristics of change of shape.For the compound non-spherical lens that uses in portable phone or the liquid crystal projector, require the thermotolerance about high environment resistant, 150 ℃ of works.
In addition, utilizing mould resin layer to be needed in the operation on the glass lens, in order to boost productivity, the material that forms resin layer is preferably light-cured resin.
And then, for miniaturization, the slimming that realizes machine, need to improve the specific refractory power of resin itself, simultaneously, for the shape of roller mould accurately, the volume cure shrinkage of photocuring front and back is less to be necessary.
As the method that improves the resin specific refractory power, the oxide compound microparticle that existence will have a high refractive index is mixed in the method in the resin.The resin combination that uses-oxyl silane, metal oxide particle and acrylic resin in disclosing No. 2002/088255 brochure, the world is disclosed.Having recorded and narrated in the world discloses No. 2002/088255 brochure with-oxyl silane is that the organic-inorganic mixing material of raw material is in excellence aspect the thermotolerance.But, do not have specifically to disclose cure shrinkage in the compound non-spherical lens and thermotolerance etc.
In Japanese kokai publication hei 4-325508 communique, disclosing the solid fluorenes is after acrylate is dissolved in the vinyl compound monomers such as acrylate monomer, makes it carry out radical polymerization by heat or light and solidify, the high refractive index resins of using as plastic lens.
But, be used for vinyl compounds such as dissolved acrylate monomer very big volume cure shrinkage about with 8～10% when polymerization.Therefore, cause that with die forming the time precision reduces, simultaneously, on mother metals such as glass, form in the compound non-spherical lens of resin layer, because the contraction of resin can produce resin layer and peel off such problem from mother metal.
In the disclosed lens that all constitute in Japanese kokai publication hei 4-325508 communique by plastics, the problem of not peeling off, the precision prescribed of disclosed eyeglass lens is about several 10 μ m in Japanese kokai publication hei 4-325508 communique, on form accuracy, compare with using the CCD and the portable phone of cmos sensor or the precision prescribed (about 1 μ m) that digital camera is used, also differ one more than the order of magnitude.
As mentioned above, at present, can't be satisfied the used for optical part resin of desired low cure shrinkage, high refractive index, thermotolerance, light solidified and transparency (preventing the scattering that gonorrhoea causes) etc. in the compound non-spherical lens of the uses such as portable phone that are used for having small-sized and slim camera simultaneously.
Summary of the invention
Though the object of the present invention is to provide a kind of volume cure shrinkage little and for cured article, but have the curable organometallic composition of high refractive index and good thermotolerance etc. and with its curing and Organometallic polymer material, and the optics that uses above-mentioned materials.
Curable organometallic composition of the present invention is characterised in that, comprises having-the M-O-M-key organometallic polymer of (M is an atoms metal) and aryl and has acryl or the fluorenes based compound of methacryloyl.
In organometallic polymer of the present invention, contain aryl, the overlapping generation bonding force of the πDian Zi cloud by constituting the aryl in this aryl and the fluorenes based compound, can improve affinity between organometallic polymer and the fluorenes based compound by this bonding force, therefore suppress separating of organometallic polymer and fluorenes based compound, obtain high transparent.
In the present invention, owing in the fluorenes based compound, mixed organometallic polymer, so can reduce the volume cure shrinkage.As mentioned above, because the affinity height between organometallic polymer and the fluorenes based compound, so can be with organometallic polymer of ratio mixing arbitrarily and fluorenes based compound, even change ratio of mixture, its volume cure shrinkage is also almost constant, is less value.
In addition, in the present invention,, therefore can make cured article with high refractive index because organometallic polymer and fluorenes based compound have aryl respectively.And, can make the cured article of excellent heat resistance.
In addition, in the present invention,, can control specific refractory power by changing the ratio of mixture of organometallic polymer and fluorenes based compound.Therefore, as mentioned above, even change the ratio of mixture of organometallic polymer and fluorenes based compound, also can reduce the volume cure shrinkage, though it is little and for cured article to make the volume cure shrinkage, the curable organometallic composition with high refractive index.
Organometallic polymer material of the present invention is the cured article of the curable organometallic composition of the invention described above, is to carry out the material that polymerization obtains by the curable organometallic composition with the invention described above.
In the present invention, organometallic polymer-M in the M-O-M-key is preferably at least a among Si, Nb, Ti and the Zi.M is preferably Si especially.When M was Si, organometallic polymer for example, can be formed by silicone resin.
Organometallic polymer among the present invention, for example, can by have at least two can hydrolysis the hydrolysis and the polycondensation of organometallic compound of base synthesize.When M is Si,, for example, can enumerate the three-oxyl silane or the two-oxyl silane that contain organic radical as such organometallic polymer.As organic radical, can enumerate alkyl, aryl, contain aryl etc.Contain aryl or contain the organometallic compound of aryl etc. by use, just aryl can be imported in the organometallic polymer.As aryl, be preferably phenyl.As the organometallic compound that contains phenyl, can enumerate phenyl three-oxyl silane, phenylbenzene two-oxyl silane, more particularly, can enumerate phenyl triethoxysilane, phenyltrimethoxysila,e, dimethoxydiphenylsilane, phenylbenzene diethoxy silane etc.
In addition, as above-mentioned organometallic compound, preferably include and have by heating and/or energy line irradiation and the organometallic compound of crosslinked functional group.Like this, by heating and/or energy line irradiation, just can form organometallic compound molecule key each other, form the key between organometallic compound and the fluorenes based compound simultaneously, Organometallic composition is solidified, make Organometallic polymer material of the present invention.
As energy line, can enumerate ultraviolet ray, electron rays etc.As carrying out so crosslinked functional group, can enumerate (methyl) acryl, styryl, epoxy group(ing), thiol group and vinyl.Therefore, preferred three-oxyl silane or the two-oxyl silane that contain above-mentioned functional group that use.As the-oxyl silane that contains (methyl) acryl; specifically, can enumerate 3-methacryloxypropyl methoxy silane, 3-methacryloxypropyl triethoxyl silane, to the styryl Trimethoxy silane, to styryl triethoxyl silane, 3-acryloxy propyl trimethoxy silicane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane etc.In addition, as the-oxyl silane that contains vinyl, can enumerate vinyltriethoxysilane.As the-oxyl silane that contains thiol group, can enumerate 3-sulfydryl propyl group methyl dimethoxysilane, 3-sulfydryl propyl trimethoxy silicane etc.
In addition, when using under the situation of styryl as crosslinked functional group, contain the organometallic compound of styryl, just aryl can be imported in the organometallic polymer by use.
When containing free-radical polymerised functional groups such as (methyl) acryl, styryl and vinyl, preferably in Organometallic composition of the present invention, contain free base system polymerization starter.
Polymerization starter as free base system, for example, can enumerate 1-hydroxyl-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholine and phenyl)-butanone-1, hydroxyl-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetic acid base-oxyethyl group]-ethyl-ester, hydroxyl-phenyl-acetic acid 2-[2-hydroxyl-oxyethyl group]-ethyl-ester, and composition thereof.
In the present invention, when the mixing use contains the organometallic compound of crosslinked functional group and does not contain the organometallic compound of functional group, blending ratio is in the weight ratio (organometallic compound that contains functional group: the organometallic compound that does not contain functional group), be preferably 5～95: 95～5.
Fluorenes based compound as using in the present invention can use the fluorenes based compound that contains acryl or methacryloyl.As such fluorenes based compound, can enumerate and have 9, fluorenes system (methyl) acrylate of 9-phenylbenzene fluorenyl skeleton.As such fluorenes is the object lesson of acrylate, and can enumerate the fluorenes of representing with following general formula is acrylate.
(in the formula, m and n are 0～5 integer)
In addition, in the present invention, so-called (methyl) acrylate is the general name of acrylate and methacrylic ester; (methyl) acryl is the general name of acryl and methacryloyl.In addition, acryloxy is identical with the implication of acryl, methacryloxy and methacryloyl.
In the curable organometallic composition in the present invention, as required, making it solidify optical characteristics such as mechanical characteristics, specific refractory power, Abbe number such as liquid viscosity before, the hardness of cured article with adjusting by heat, the irradiation of light homenergic is purpose, also can adds 1 official energy, be (methyl) acrylate of simple function.In addition, also can add multifunctional (methyl) acrylate that contains a plurality of functional groups.
Example as simple function (methyl) acrylate, for example, can enumerate (methyl) benzyl acrylate, (methyl) ethyl propenoate, (methyl) methyl acrylate, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid two ring pentyl esters, (methyl) vinylformic acid α-Nai Zhi, (methyl) propenoic acid beta-naphthalene ester, dicyclopentenyl hydroxyethyl (methyl) acrylate, (methyl) vinylformic acid norbornene ester, (methyl) phenyl acrylate etc.
Example as multifunctional (methyl) acrylate, for example, can enumerate two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid propylene glycol ester, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, two (methyl) vinylformic acid glyceryl ester, 2,2-dimethyl-3-hydroxypropyl-2, two (methyl) acrylate of 2-dimethyl-3-propionic ester, two (methyl) vinylformic acid 1, the 4-butanediol ester, two (methyl) vinylformic acid DOPCP, two (methyl) acrylate of hydroxyl trimethylacetic acid neopentyl glycol, two (methyl) acrylate of the propylene oxide adduct of dihydroxyphenyl propane, 2, two (methyl) acrylate of 2 '-two (hydroxyl propoxy-phenyl) propane, 2, two (methyl) acrylate of 2 '-two (hydroxyl-oxethyl phenyl) propane, two (methyl) acrylate of the ethylene oxide adduct of dihydroxyphenyl propane, two (methyl) acrylate of tristane dihydroxymethyl, 2,2 officials such as two (methyl) vinylformic acid affixture of 2 '-two (Racemic glycidol hydroxy phenyl) propane energy (methyl) acrylate, and then, for example, three (methyl) vinylformic acid, five tetrahydroxybutane esters, four (methyl) vinylformic acid, five tetrahydroxybutane esters, three (methyl) vinylformic acid trishydroxymethyl propyl ester, six (methyl) vinylformic acid, two-five tetrahydroxybutane esters, three (methyl) acrylate of trimellitic acid, the triallyl trimellitic acid, three (methyl) acrylate of cyanacrylate three (2-hydroxyethyl) isocyanuric acid ester, three (methyl) acrylate of three (hydroxypropyl) isocyanuric acid ester, three (methyl) vinylformic acid tetra methylol methyl esters, four (methyl) vinylformic acid tetra methylol methyl esters etc.
In curable organometallic constituent of the present invention, as required, also may further include (methyl) acrylate with an above aryl.As (methyl) acrylate with an above aryl, can enumerate (methyl) benzyl acrylate, (methyl) vinylformic acid phenoxy ethyl, (methyl) vinylformic acid phenoxy group propyl ester, acryloxy ethyl phthalic ester, (methyl) vinylformic acid cresols ester, to cumyl phenoxy group ethylene glycol (methyl) acrylate, tribromo phenyl (methyl) acrylate, dihydroxyphenyl propane two (methyl) acrylate, Bisphenol F two (methyl) acrylate, phthalic acid two (methyl) acrylate, TriMethylolPropane(TMP) benzoic ether (methyl) acrylate, (methyl) vinylformic acid naphthalene ester etc., and oxyethane addition (EO modification) thing, propylene oxide addition (PO modification) thing, ethylcyclohexane addition (ECH modification) thing etc.
In addition, in curable organometallic composition of the present invention, also may further include the aromatic urethane origoester acrylate.As the aromatic urethane origoester acrylate, can enumerate commodity " Ebecryl 210 ", " Ebecryl 220 " by name that ダ イ セ Le サ イ テ Star Network company produces, commodity " Uvithanc 782 ", " Uvithanc 783 " by name that wild village company of business quarters produces, commodity " Laromer LR8983 " by name that BASF AG produces and with its material (commodity that ダ イ セ Le サ イ テ Star Network company produces " Ebecryl 205 " by name etc.) after with the dilution of (methyl) acrylate such as tripropylene glycol diacrylate.
In curable organometallic composition of the present invention, also can further contain only have one can hydrolysis metal alkoxide and/or its hydrolyzate of base.This metal alkoxide and/or its hydrolyzate can not contained with organometallic polymer bonded state, and also the bonded state is contained with it.In addition, the hydrolyzate of metal alkoxide also can be the polycondensate of hydrolyzate.
By contain above-mentioned have one can hydrolysis metal alkoxide and/or its hydrolyzate of base, the OH base that the end of above-mentioned alkoxide and/or its hydrolyzate and organometallic polymer molecule produces reacts, and can remove-the OH base.So just can suppress-water-intake rate that the OH base causes reduces, the reduction of the photoabsorption in the wavelength region of 1450～1550nm, because of under the condition of high temperature-volumetric shrinkage that the OH base contracts gradually and produces each other.Such volumetric shrinkage is to cause that resin layer peels off the reason that reduces with precision, by suppressing volumetric shrinkage, just can suppress resin layer and peel off with precision and reduce.
As among the present invention only have one can hydrolysis the metal alkoxide of base, can enumerate trimethylammonium methoxy silane, trimethylethoxysilane, triethyl methoxy silane, triethyl-ethoxy-silicane alkane, tripropyl methoxy silane, tripropyl Ethoxysilane, benzyl dimethyl methoxy silane, benzyl dimethyl Ethoxysilane, phenylbenzene methoxy ylmethyl silane, phenylbenzene (ethoxymethyl) base silane, acetyltriphenylsilane, oxyethyl group tri-phenyl-silane etc.
In curable organometallic composition of the present invention, preferably further comprise anhydrous organic acid and/or organic acid.Because anhydrous organic acid absorbs moisture, is hydrolyzed, so by containing anhydrous organic acid, just can reduce the moisture in the organometallic polymer.The change of shape that like this, just can suppress that photoabsorption that moisture causes reduces and cause because of moisture evaporation.
The reaction of the organic acid promotion silanol group that in organometallic polymer, contains in addition, etc.Therefore, can promote removing of silanol group.For example, also can promote the silanol group reaction each other of the molecular end in the organometallic polymer.In addition, only have one can hydrolysis hydrolyzate and the molecular end of metal alkoxide of base at organometallic polymer produce-the OH base reacts, and promote to remove-reaction of OH base.
As above-mentioned anhydrous organic acid object lesson, can enumerate anhydrous trifluoroacetic acid, anhydrous acetic acid, anhydrous propionic acid etc.The anhydrous trifluoroacetic acid of preferred especially use.As above-mentioned organic acid object lesson, can enumerate trifluoroacetic acid, acetate, propionic acid etc.Especially preferably use trifluoroacetic acid.
In curable organometallic composition of the present invention, the content of organometallic polymer is preferably 5～95 weight %, more preferably 20～75 weight %, more preferably 20～50 weight %.If the content of organometallic polymer is very few, then owing to characteristic near the fluorenes based compound, so the temperature dependency of specific refractory power increases, simultaneously, change of shape under hot environment also increases, and then the viscosity height before curing, particularly shape high precision for the needed 100 μ m left and right thicknesses of optics of compound non-spherical lens etc. the difficulty that becomes with mould etc.In addition, otherwise, if the content of organometallic polymer is too much, then specific refractory power reduction.
In curable organometallic composition of the present invention, the content of fluorenes based compound is preferably 5～95 weight %, more preferably 30～80 weight %.If the content of fluorenes based compound is very few, the tendency that then has specific refractory power to reduce.Particularly be made as more than the 25 weight %, just easily specific refractory power be controlled at more than 1.58, further, just easily specific refractory power is controlled at more than 1.59 by its lower value being made as more than the 35 weight % by lower value with the content of fluorenes based compound.In addition, otherwise, if fluorenes based compound content is too much, then owing to characteristic near the fluorenes based compound, so the temperature dependency of specific refractory power increases, simultaneously, the change of shape under hot environment also increases, and then the viscosity height before curing, particularly shape high precision for the needed 100 μ m left and right thicknesses of optics of compound non-spherical lens etc. the difficulty that becomes with mould etc.Particularly in order to reach the low viscosity of processing ease at room temperature, the content of fluorenes based compound is preferably below 70 weight %, further preferably below 50 weight %.
In curable organometallic composition of the present invention, the higher limit of the content of above-mentioned simple function or multifunctional (methyl) acrylate is preferably below 40 weight %, further preferably below 30 weight %, further preferably below 25 weight %.In addition, lower value is preferably more than 5 weight %, further preferably more than 10 weight %, further preferably more than 15 weight %.Owing to these (methyl) acrylate are that the purpose that is adjusted into of the hardness etc. with viscosity adjustment, cured article is added, so if its content is very few, the adjustment of the hardness of viscosity adjustment sometimes and cured article etc. will become insufficient.In addition, if the content of these (methyl) acrylate is too much, then because the shrinking percentage of these (methyl) acrylate when solidifying is big, so worry that the volume cure shrinkage of curable organometallic composition is excessive.
In curable organometallic composition of the present invention, only have one can hydrolysis the metal alkoxide of base and/or the content of its hydrolyzate with respect to 100 weight parts of organometallic polymer, be preferably 0.1～15 weight part, more preferably 0.2～2.0 weight part.If the content of above-mentioned metal alkoxide or its hydrolyzate is very few, then because the OH base is residual, the absorption increase in the wavelength region of 1450～1550nm, water-intake rate raise, and deterioration takes place easily.Otherwise, if the content of above-mentioned metal alkoxide or its hydrolyzate is too much, then because in hot environment, superfluous above-mentioned metal alkoxide or its hydrolyzate spin off, and become the disruptive major cause takes place from material.
In addition, anhydrous organic acid or organic acid content are preferably 0.1～10 weight part with respect to organometallic polymer 100 weight parts, more preferably 1～5 weight part.If anhydrous organic acid or organic acid content are very few, then can not fully promote the hydrolysis of metal alkoxide, otherwise, if anhydrous organic acid or organic acid content are too much, then because in hot environment, superfluous anhydrous organic acid or organic acid self spin off from material, and become the disruptive major cause take place.
In addition, in curable organometallic composition of the present invention, preferably include by at least a microparticle that constitutes in metal, metal oxide and the metal nitride.The gravel size decision of microparticle is below 100nm.
As metallic particles, can enumerate gold and silver, iron etc.
As metal oxide particle, can enumerate silicon oxide, niobium oxides, zirconium white, titanium oxide, aluminum oxide, iridium oxide, cerium oxide, lanthanum trioxide etc.Wherein, especially preferably use silicon oxide, niobium oxides, zirconium white and titanium oxide.
As the nitride metal composition granule, can enumerate aluminium nitride, zirconium nitride, titanium nitride etc.
By adding the low material of specific refractory power as above-mentioned microparticle, just can control Organometallic polymer material, its specific refractory power is reduced.In addition,, just can control Organometallic polymer material, its specific refractory power is raise by containing the high microparticle of specific refractory power as above-mentioned microparticle.As the metal oxide particle that can improve specific refractory power, can enumerate niobium oxides (Nb
2O
3) particle, zirconium white (ZrO
2) particle, titanium oxide (TiO
2) particle.In addition, as the microparticle that can reduce specific refractory power, can enumerate silicon oxide (SiO
2) particle.
As the content of microparticle, with respect to whole Organometallic compositions, preferably in the scope of 5～50 weight %.
Hindered Amine Light Stabilizer) in the curable organometallic composition of the present invention, also can add antioxidant, HALS (hindered amine as light stabilizer: photostabilizer, UV light absorber etc. such as.
Organometallic polymer material of the present invention is the cured article of the curable organometallic composition of the invention described above, can obtain by above-mentioned curable organometallic composition is carried out polymerization.
Optics of the present invention is characterised in that, uses the Organometallic polymer material of the invention described above to form light transmissive region.
As the object lesson of optics of the present invention, for example, can enumerate and use Organometallic polymer material of the present invention, on the mother metals such as glass, pottery or plastics of light transmission, form the parts of light transmissive region.When making the optics of thin thickness, preferably use glass of high refractive index or high refractive index light transparent ceramic etc. as mother metal.
As optics 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 translucent resin on the spherical lens that is made of glass etc., and the non-spherical lens of making.
Owing to Organometallic polymer material of the present invention is that curable organometallic composition with the invention described above is cured and obtains, so the volume cure shrinkage when solidifying is little.Therefore, by on the mother metal that constitutes by glass etc., the curable organometallic composition layer being set, and with its curing, when forming light transmissive region, can prevent that light transmissive region from peeling off from mother metal, the good light transmissive region of stickiness can be set.And Organometallic polymer material of the present invention as mentioned above, owing to have high refractive index and excellent heat resistance, has high refractive index and has good stable on heating compound non-spherical lens so can make.
Optical devices of the present invention are characterised in that to possess the optics of the invention described above.As Optical devices of the present invention, can enumerate the camera module that possesses above-mentioned compound non-spherical lens.Such camera module can be used in portable phone and vehicle mounted rear watch-dog etc.
As Optical devices of the present invention, the optical waveguide that constitutes by core layer and/or tectum that further can enumerate projector such as liquid crystal projection apparatus, uses that Organometallic polymer material forms etc.
In addition, as Optical devices of the present invention, can enumerate optical communication devices such as photoswitch, optical transceiver module, opticcoupler; Display unit such as liquid crystal device, plasma display, OLED display, projector; Camera modules such as camera heads such as photographic cameras such as digital camera, video recorder, CCD camera module, CMOS camera module; Opticinstruments such as visual telescope, microscope, magnifying glass.
Curable organometallic composition of the present invention comprises and has-organometallic polymer of M-O-M-key and aryl and have acryl or the fluorenes based compound of methacryloyl.Little and the cured article of volume cure shrinkage has high refractive index and good thermotolerance.In addition, because when accessing high transparent, therefore the ratio of mixture that can make organometallic polymer and fluorenes based compound can control optical characteristics such as specific refractory power and Abbe number with ratio vary arbitrarily.
Because the volume cure shrinkage is little, so when curable organometallic composition is solidified to form Organometallic polymer material, can suppress peeling off of Organometallic polymer material, can carry out high-precision shaping.
Description of drawings
Fig. 1 is the schematic cross-section of expression manufacturing as an example of operation of the compound non-spherical lens of optics of the present invention.
Fig. 2 is used to observe the schematic representation of apparatus of the spherical aberration of compound non-spherical lens for expression.
The figure of reticulate pattern figure when Fig. 3 uses glass spherical lens and compound non-spherical lens to observe for expression.
Fig. 4 is the addition of expression organometallic polymer in an embodiment of the present invention and the figure of the relation between the volume cure shrinkage.
Fig. 5 is the addition of expression organometallic polymer in an embodiment of the present invention and the figure of the relation between the specific refractory power behind the photocuring.
Fig. 6 for the expression in an embodiment of the present invention Abbe number and the figure of the relation between the specific refractory power under the wavelength 589nm.
Fig. 7 is the expression addition of organometallic polymer in an embodiment of the present invention and the figure of the relation between the temperature factor of specific refractory power.
Fig. 8 is the schematic cross-section of an example of the existing camera module of expression.
Fig. 9 is the schematic cross-section of the camera module of expression embodiments of the invention.
Figure 10 is the schematic cross-section of expression folding portable telephone.
Figure 11 is the sectional view of the optical waveguide of expression one embodiment of the present of invention.
Figure 12 is the sectional view of the optical waveguide of expression an alternative embodiment of the invention.
Figure 13 is the sectional view of the optical waveguide of expression another embodiment of the present invention.
Figure 14 is the schematic cross-section of the embodiment of expression liquid crystal projection apparatus.
Figure 15 is the schematic cross-section of an embodiment of expression liquid crystal projection apparatus of the present invention.
Figure 16 is the schematic cross-section of another embodiment of expression liquid crystal projection apparatus of the present invention.
Figure 17 is the sectional view of the compound non-spherical lens of expression embodiments of the invention.
Figure 18 is the schematic cross-section of the device that uses in the expression thermal shock test of carrying out in an embodiment of the present invention.
Figure 19 is the figure in the timed interval that is illustrated in the thermostatic bath of 85 ℃ of thermostatic baths in the thermal shock test and-40 ℃.
Figure 20 is the sectional view of an embodiment of expression optical transceiver module of the present invention.
Embodiment
Below, the present invention will be described in detail according to embodiment, but the invention is not restricted to following examples.
(embodiment 1)
Use have structure shown in the above-mentioned Chemical formula 1, m and n be that 1 vinylformic acid fluorenes ester is as the fluorenes based compound.
＜viscous liquid A 〉
By mixing following substances while heating down, obtain viscous liquid A at 60 ℃:
Vinylformic acid fluorenes ester: 10g;
1-hydroxyl-cyclohexyl-benzophenone: 0.2g;
HALS (Tinuvin292 that Ciba Speciality Chemicals company produces): 0.05g;
UV light absorber (Tinuvin400 that Ciba Speciality Chemicals company produces): 0.15g; With
Benzyl methacrylate: 1.43g.
＜viscous liquid B 〉
Placed 24 hours by following substances is mixed the back, organometallic compound A and organometallic compound B be hydrolyzed, make it that polycondensation take place:
Organometallic compound A:3-methacryloxypropyl triethoxyl silane: 15.3ml;
Organometallic compound B: dimethoxydiphenylsilane: 6.3ml;
Contain the aqueous solution of hydrochloric acid (hydrochloric acid of concentration 2N: 3.8ml) as catalysts; With
Ethanol: 40ml.
Be heated to 100 ℃ by the liquid that contains polycondensate that will obtain under nitrogen atmosphere, ethanol is removed in evaporation, obtains viscous liquid.Get the viscous liquid that 1g obtains, with
Metal alkoxide X: trimethylethoxysilane: 3ml,
Organic acid Y: anhydrous trifluoroacetic acid: 0.8ml
Mix, place after 24 hours, by carry out heat drying under nitrogen atmosphere, under 110 ℃, excessive metal alkoxide X and organic acid Y are removed in evaporation, obtain viscous liquid B.
＜viscous liquid C 〉
By above-mentioned viscous liquid A and viscous liquid B are stirred while heating down at 60 ℃ with the ratio of stipulating, obtain viscous liquid C.
Viscous liquid C is clipped between the quartz glass plate of thickness 1mm, is about 30mW/cm with the UV-lamp exposure intensity of centre wavelength 365nm
2Ultraviolet ray 15 minutes, make its curing.
The volume cure shrinkage when measuring curing and the specific refractory power and the Abbe number of cured article.
According to the 4.6.2 of JIS K 5400, measure the proportion dL of the liquid composition before solidifying, according to 4 of JIS Z 8807, measure the proportion dS after solidifying, volume cure shrinkage r calculates by following formula:
r＝1-dL/dS。
About specific refractory power and Abbe number, use the DR-M2 type Abb of the ATAGO of Co., Ltd. to measure.In addition, short of special qualification, specific refractory power is with the measured value of D ray (589nm) under 25 ℃.
In addition, specific refractory power and Abbe number also can use MODEL2010 prism-coupled instrument that Metricon company produces etc. to measure.
(comparative example 1)
Use the viscous liquid B that contains organometallic polymer of three vinylformic acid, five tetrahydroxybutane esters replacement embodiment 1, with embodiment 1 identical its curing, mensuration volume cure shrinkage, specific refractory power and the Abbe number of making.
In embodiment 1 and comparative example 1, the content of organometallic polymer or three vinylformic acid, five tetrahydroxybutane esters is made as 0 weight %, 20 weight %, 29 weight %, 50 weight %, 70 weight % and 100 weight %.
Fig. 4 is expression organometallic polymer or the addition of three vinylformic acid, five tetrahydroxybutane esters and the figure of the relation between the volume cure shrinkage.In embodiment 1, the volume cure shrinkage is all lower when any addition, is 5～6%, even the addition of organometallic polymer changes (transverse axis), the volume cure shrinkage does not have big variation yet.
Relative therewith, in comparative example 1, when the addition of three vinylformic acid, five tetrahydroxybutane esters was 20 weight %, the volume cure shrinkage just surpassed 7%, and the volume cure shrinkage increases along with the increase of addition as can be known.
Fig. 5 is the figure of the relation between the specific refractory power of addition and the cured article behind the photocuring of expression organometallic polymer, and as shown in Figure 5 as can be known, by the addition of adjustment organometallic polymer, specific refractory power can roughly be controlled in about about 1.53～1.61.Particularly when the addition of organic metal-containing polymer was 20 weight % and 29 weight %, specific refractory power was 1.59～1.60, and Abbe number can access such high refractive index of polycarbonate resin and low Abbe number below 30.Because Abbe number hour, the wavelength dependency of specific refractory power just increases, so by constituting optical system with optical materials such as big glass of Abbe number or resins, just can the revisal aberration.
Fig. 6 is that the expression curable organometallic composition that will prepare in embodiment 1 is cured and the Abbe number of the Organometallic polymer material that obtains and the figure of the relation between the specific refractory power under the wavelength 589nm.As shown in Figure 6, adopt the material of embodiment 1, Abbe number is identical with specific refractory power, also can change in a big way.Therefore, the curable organometallic constituent of the application of the invention, the very big degree of freedom of design that just can give the optics such as design of the camera module that makes up a plurality of lens.
Fig. 7 is the figure that is illustrated in the relation between the temperature factor of specific refractory power of the addition of the organometallic polymer among the embodiment 1 and cured article.
As shown in Figure 7 as can be known, the temperature factor of specific refractory power reduces along with the increase of the addition of organometallic polymer.
Think that this is that promptly the temperature factor of specific refractory power is about-0.8 * 10 because the temperature factor of the specific refractory power of organometallic polymer is little
-4In addition, in comparative example 1, replace organometallic polymer and use the temperature factor of specific refractory power of the cured article of three vinylformic acid, five tetrahydroxybutane esters to be about-2.8 * 10
-4
[high temperature is placed test]
The stability of the shape of composition under hot environment that evaluation is made in embodiment 1 and comparative example 1.Make the sample of the tablet shape of thick about 2mm, the about 6mm of diameter respectively, after 48 hours, measure the reduction of thickness with 120 ℃ oven heat.Because material shrinks under 120 ℃ high temperature, thereby the thickness minimizing, so in this test, measure the reduction of this thickness.Evaluation result is shown in table 1.In addition, in table 1, the measurement result when also having represented only to use the viscous liquid A of embodiment 1 as a comparison.
Table 1
| Addition (weight %) | 20 | 29 | 50 | 70 | 100 |
| | 3μm | 1μm | 1μm | 1μm | 0.8μm |
| Comparative example 1 | 6μm | 8μm | 12μm | 15μm | 20μm |
| The viscous liquid A of | 5μm | ||||
As shown in Table 1, in embodiment 1, if increase the addition of organometallic polymer, shrinkage just reduces.On the other hand, in comparative example 1, if increase the addition of three vinylformic acid, five tetrahydroxybutane esters, then shrinking percentage increases, and shape stability at high temperature worsens.
(embodiment 2)
In embodiment 1, the addition of organometallic polymer is made as 29 weight %, in viscous liquid A, do not contain benzyl methacrylate, in addition with embodiment 1 identical preparation curable organometallic composition, measure temperature factor with volume cure shrinkage, specific refractory power, Abbe number and the specific refractory power of the cured article after its curing.
The volume cure shrinkage is about 5.1%, and specific refractory power is about 1.60, and Abbe number is about 28, and the temperature factor of specific refractory power is approximately-1.6 * 10
-4
(comparative example 2)
In embodiment 1, use three vinylformic acid trishydroxymethyl propyl ester to replace organometallic polymer.Its result is, and is identical with comparative example 1, and along with increasing of the addition of three vinylformic acid trishydroxymethyl propyl ester, the volume cure shrinkage raises.
(comparative example 3)
In the preparation of the viscous liquid B of embodiment 1, except not using the organometallic compound B that contains phenyl, only using the 20.8ml organometallic compound A, identical with embodiment 1, mixing cohesive liquid A and viscous liquid B, preparation curable organometallic composition.
But, on the time point of mixing cohesive liquid A and viscous liquid B, gonorrhoea takes place, can't obtain clear composition.Think that this is because organometallic polymer in viscous liquid B does not contain aryl, so and the avidity between the vinylformic acid fluorenes ester insufficient, gonorrhoea takes place.
(embodiment 3)
In embodiment 1, use 3-sulfydryl propyl trimethoxy silicane as making the organometallic compound A that viscous liquid B uses, preparation viscous liquid B.9.8ml is measured in containing of organometallic compound A, and 6.3ml is measured in containing of organometallic compound B, and the hydrochloric acid of concentration 2N is got 3.8ml, and ethanol is measured 40ml.By above-mentioned substance is mixed, placed 24 hours, with organometallic compound A and organometallic compound B hydrolysis, make it that polycondensation take place.
Under nitrogen atmosphere, be heated to 100 ℃ by the liquid that contains polycondensate that will obtain, the methyl alcohol of ethanol and reaction generation is removed in evaporation, the liquid that obtains is used as viscous liquid B, A mixes with viscous liquid, make that the addition of organometallic polymer is 29 weight %, the preparation Organometallic composition.
With the curable organometallic polymkeric substance and above-mentioned identical being cured that obtains, measure the temperature factor of volume cure shrinkage, specific refractory power, Abbe number and the specific refractory power of cured article.
The volume cure shrinkage is about 6.4%, and specific refractory power is about 1.61, and Abbe number is about 28, and the temperature factor of specific refractory power is approximately-1.7 * 10
-4
(embodiment 4)
The material that will not use benzyl methacrylate in the viscous liquid A of embodiment 1 and prepare uses as viscous liquid A, and this viscous liquid A, viscous liquid B and three vinylformic acid trishydroxymethyl propyl ester are mixed.At this moment, mix making that the addition of organometallic polymer is 20 weight %, the amount of three vinylformic acid trishydroxymethyl propyl ester is 20 weight %, the preparation curable organometallic composition.
The Organometallic composition that obtains is cured, measures the temperature factor of volume cure shrinkage, specific refractory power, Abbe number and the specific refractory power of cured article.
The volume cure shrinkage is about 7%, and specific refractory power is about 1.59, and Abbe number is about 30, and the temperature factor of specific refractory power is approximately-1.5 * 10
-4
(embodiment 5)
The microparticle (median size is 6nm) of titanium oxide is scattered in the Virahol with about 10 weight %, the preparation particle dispersion, make an addition among the viscous liquid B of embodiment 1 after, by carry out heat drying under 100 ℃, Virahol is removed in evaporation, obtains viscous liquid D.
Viscous liquid D is mixed with various ratios with the viscous liquid A of embodiment 1, make its photocuring make cured article, measure the specific refractory power and the Abbe number of cured article.
By adjusting the addition of above-mentioned particle dispersion, it is about 26 that the specific refractory power of cured article is adjusted to about Abbe number at 1.62 o'clock, and the volume cure shrinkage is about 6.5%.
(embodiment 6)
The microparticle (median size is 10nm) of the niobium oxides of about 10 weight % is scattered in the ethanol, the preparation particle dispersion, in the viscous liquid B of the 1g embodiment 1 that is added with 0.2g three vinylformic acid five tetrahydroxybutane esters, add this particle dispersion, after the stirring, by carry out heat drying under 100 ℃, ethanol is removed in evaporation, obtains viscous liquid E.
Identical with embodiment 1, viscous liquid E is mixed with various ratios with viscous liquid A, make its photocuring, measure the specific refractory power and the Abbe number of cured article.
By adjusting the addition of above-mentioned particle dispersion, it is 24 that the specific refractory power of cured article is adjusted to about Abbe number at 1.64 o'clock, and the volume cure shrinkage is about 7%.
(embodiment 7)
Use the viscous liquid C among the embodiment 1, make compound non-spherical lens.So-called compound non-spherical lens is to use glass or resinous spherical lens or dull and stereotyped as mother metal, by form aspheric resin layer, the non-spherical lens of making on the optical surface of this mother metal.
Shown in Fig. 1 (a), on the glass spherical lens 10 (base glass material) of diameter 5mm, maximum ga(u)ge 1mm, viscous liquid 11 drips.Viscous liquid 11 is the viscous liquid C among the embodiment 1.Then, shown in Fig. 1 (b), the nickel molding jig 12 that inner face is had aspherical shape is by on the viscous liquid 11 that is pressed on the spherical lens 10, then, shown in Fig. 1 (c), from glass spherical lens 10 side irradiation ultraviolet radiations 14, viscous liquid 11 is solidified, form the resin layer 13 that constitutes by Organometallic polymer material.
Next, shown in Fig. 1 (d), mould 12 is taken off, shown in Fig. 1 (e), obtain the compound non-spherical lens 15 that constitutes by glass spherical lens 10 and resin layer 13.
Next, at compound non-spherical lens that obtains and the spherical lens that does not form resin layer, use device shown in Figure 2 to observe spherical aberration, between screen 18 that is formed with the reticulate pattern pattern and CCD photographic camera 16, configuration lens 17 amplify observation by CCD photographic camera 16 with the reticulate pattern pattern on the screen 18.Reticulate pattern pattern on the screen 18 is the reticulate pattern pattern 19 of interval 0.5nm as shown in Figure 2.
When using glass spherical lens 10, because the distinctive spherical aberration of spherical lens, observe the image of the reticulate pattern pattern of the distortion shown in Fig. 3 (b) as lens 17.Relative therewith, when the compound non-spherical lens 15 that uses above-mentioned making during as lens 17, obtain shown in Fig. 3 (a) like that with the loyal enlarged image of reticulate pattern pattern.
When using, during the compound non-spherical lens of making same as described above, also can access structure same as described above with other the viscous liquid of embodiment gained beyond the embodiment 1.
(embodiment 8)
＜use as mother metal with high refractive index perviousness pottery
Except using high refractive index infiltration type pottery (specific refractory power about 2.1) as the mother metal, other are identical with embodiment 7, make compound non-spherical lens.
When resulting compound aspheric lens is estimated, identical with embodiment 7, can access reticulate pattern pattern enlarged image verily.
(embodiment 9)
As beyond the mother metal, other are identical with embodiment 7, make compound non-spherical lens except using glass of high refractive index (HARA company of Co., Ltd. O produces, and commodity are called " S-LAH79 ", and specific refractory power is about 2.0).
When resulting compound aspheric surface neck is estimated, identical with embodiment 7, can access reticulate pattern pattern enlarged image verily.
In addition, use that HARA company of Co., Ltd. O produces commodity " S-NPH1 " (specific refractory power is about 1.81) by name, " S-NPH2 " (specific refractory power is about 1.92), " S-TIH53 " (specific refractory power is about 1.85), " S-TIH6 " (specific refractory power is about 1.80), " S-LAL7 " (specific refractory power is about 1.65) during as glass of high refractive index, also can access identical result.
(embodiment 10)
Fig. 8 is the sectional view of an example of the existing camera module of expression.As shown in Figure 8, on imaging apparatus 25, be provided with 2 plastic aspherical element lens 21 and 22,2 glass spherical lenses 23 and 24, these lens are held by automatic focusing structure 26.Camera module 20 has 4 lens 22～24, and the camera module of 2～5 megapixels that can use as portable phone uses.By making up a plurality of lens, just can be when guaranteeing required multiplying power, the various aberrations of the necessary aberration of camera lens that comprises the usefulness of photographing are carried out revisal.For example, in example shown in Figure 8, make the Abbe number of a slice at least in spherical lens 23 and 24 increase by setting, the Abbe number of at least one in the plastic aspherical element lens 21 and 22 reduces, and just can carry out the design that aberration is cancelled out each other.
Fig. 9 is the sectional view of the camera module of expression embodiments of the invention.In Fig. 9, by with the compound non-spherical lens (specific refractory power of resin layer: be about 1.59 of the present invention, Abbe number: be about 30) is used in the lens 23 and 24 of Fig. 8 any one, by the little resin layer of Abbe number and at least one in plastic aspherical element lens 21 and 22, can the revisal aberration, can cut down lens thus.As its result, the height of camera module can be reduced about 1mm.The height of existing camera module shown in Figure 8 is 10mm, and the height of the camera module of present embodiment shown in Figure 9 is 9mm.
Figure 10 disposes the sectional view of the folder-type portable phone of camera module for expression.In the portion, be provided with camera module 20 up, in be provided with TV tuner 31, hard disk drive 32 and indicating meter 33 etc.Be provided with keyboard 34 and battery 35 etc. in the quadrate part down.
When using existing camera module as camera module 20, the height h of upper portion
1Height h with following quadrate part
2Be respectively 12.5mm, the height H of whole portable phone is 25mm.But, according to the present invention, use camera module embodiment illustrated in fig. 9 as camera module 20, just can be with height h
1The about 1mm of attenuate, like this, just can be with the about 1mm of height H attenuate of integral body.
Though in the present embodiment, be the compound non-spherical lens that glass lens is provided with resin layer, among the present invention, also can be the compound non-spherical lens that plastic lens is provided with resin layer.Material as in this case plastic lens, for example, can enumerate the fluorenes that commodity " ZEONEX resin " by name that Japanese ZEON company produces, polyolefin-based resins that commodity " ARTON resin " by name that JSR company produces wait, commodity that Osaka Gas Chemicals company produces are called " OKP4 " etc. is vibrin etc.In addition, as other resin, can use resins such as acrylic acid series, epoxy system, silicon system, polycarbonate, polyethylene terephthalate (polyethylene terephthalate), PEN (Polyethylenenaphtahalate), fluoro-resin, polymethylpentene, polystyrene, polyarylester (polyarylate), polysulfones, polyethersulfone, polyetherimide.
(embodiment 11)
In addition, camera module shown in Figure 9 also can be as the camera module of vehicle mounted rear watch-dog and is used.In the watch-dog of vehicle mounted rear, need the thermotolerance of height, can use the non-spherical lens of embodiment 9.In addition, the non-spherical lens of embodiment 9 is owing to having high refractive index, so can enlarge the visual angle.
(embodiment 12)
Organometallic polymer material of the present invention can be used in the substrate of various electronic machines distribution between distribution and substrate, and can be applied to optical waveguide component.
Figure 11 is the sectional view of an embodiment of expression optical waveguide of the present invention.As shown in figure 11, on glass substrate 43, be provided with tectum 42, in tectum 42, be formed with core layer 41.The height of core layer 41 is about 70 μ m, and the distance that core layer is 41 is about 500 μ m.Above core layer 41, have the tectum 42 of about 100 μ m thickness, below core layer 41, also have the tectum 42 of about 100 μ m thickness.
In the present embodiment, use the solid specific refractory power behind the photocuring is adjusted into about 1.53 material, form core layer 41.In addition, use specific refractory power is adjusted into about 1.51 material, form tectum 42.The cross section of core layer 41 is the square of about 70 μ m.In addition, used thickness is that the TENPAX glass substrate of 1mm is as glass substrate 43.
After injecting the light of wavelength 650nm, 830nm and 850nm from a side end face of optical waveguide, confirm to penetrate light respectively, by returning result that (cutback) method of cutting carries out the light conduction loss for below the 0.5dB/cm from other end face.
Figure 12 (a) is expression with the thickness as flexible substrate is the figure of optical waveguide of the structure of the Kapton 44 of the 70 μ m both sides of clamping core layer shown in Figure 11 41 and tectum 42.
In addition, Figure 12 (b) be expression with polyimide to carrying out mold around the tectum 42, make thickness reach 70 μ m, form the sectional view of the optical waveguide of mold layer 45.
Using under the situation of flexible substrate as Figure 12 (a) and Figure 12 (b), for example, can bending reaching radius-of-curvature is about 10mm.
Figure 13 is the sectional view of the optical waveguide of expression other embodiment of the present invention.
In Figure 13 (a), be provided with the electric power copper wiring 46 of diameter 150 μ m in the side of core layer 41.The thickness that the both sides of tectum 42 are used as flexible substrate is that the Kapton 44 of 70 μ m is clamped.
In the embodiment of Figure 13 (b), dispose electric power copper wiring 46 in the Kapton 44 up.
As shown in figure 13, in light-guide wave path of the present invention, also can be provided with the electric power distribution.By the electric power distribution is set like this, just can carry out the supply of information signal and electric power with an element.
Electric power can have the orthogonal cross-sectional shape with copper wiring 46.
(embodiment 13)
Figure 14 is the schematic cross-section of expression liquid crystal projection apparatus.Be provided with lamp optical system 52 above light source 53, lamp optical system 52 is made of lens 52a and 52b.Hit half-mirror 54 from the light that light source 53 penetrates, the light that sees through half-mirror 54 is by speculum 58 reflections, and scioptics 60 and liquid crystal panel 63 are injected cross prisms 59.
On the other hand, the light that reflects with half-mirror 54 shines to half-mirror 55, injects cross prisms 59 with the light scioptics 61 and the liquid crystal panel 64 of half-mirror 55 reflections.
The light that sees through half-mirror 55 mirror 56 reflections that are reflected, and then mirror 57 reflections that are reflected, scioptics 62 and liquid crystal panel 64 are injected cross prisms 59.
Because light source 53 is pyrotoxins, so need be 51 lens 51a～51c and light source 53 isolation distance to a certain degree at present with projection optics.
But, because optics of the present invention is to be formed by the above-mentioned Organometallic polymer material with good heat resistance energy, so can be configured near the light source 53.
Figure 15 is the schematic cross-section of an embodiment of expression liquid crystal projection apparatus of the present invention.
In the embodiment shown in fig. 15, be the lens that use embodiment 9 among lens 51a～51c of 51 at projection optics.Therefore, as shown in figure 15, can be near projection optical system 51 with the position configuration of light source 53.Therefore, can be with liquid crystal projection apparatus 50 miniaturizations.
In liquid crystal projection apparatus shown in Figure 15, the light that penetrates from light source 53 passes through lamp optical system 52, and directive half-mirror 54 by light scioptics 60 and the liquid crystal panel 63 that half-mirror 54 reflects, is injected cross prisms 59.The light that sees through half-mirror 54 mirror 58 reflections that are reflected, directive half-mirror 55.By light scioptics 61 and the liquid crystal panel 64 that half-mirror 55 reflects, inject cross prisms 59.The light that sees through half-mirror 55 mirror 56 reflections that are reflected, and then mirror 57 reflections that are reflected, scioptics 62 and liquid crystal panel 650 are injected cross prisms 59.The light that sees through liquid crystal panel 63,64 and 65 is synthesized at cross prisms 59, is 51 by projection optics, penetrates to the outside.
Though Figure 14 and liquid crystal projection apparatus shown in Figure 15 are the independently three-plate type infiltration type projector represented of liquid crystal panel of RGB, be to use one syntheticly to have the one-board infiltration type projector of the liquid crystal panel of RGB also can obtain same effect.
In liquid crystal projection apparatus shown in Figure 16,, use White LED as light source 53 in order to realize further miniaturization.As shown in figure 16, the light that penetrates from light source 53 passes through lamp optical system 52, and scioptics 60, liquid crystal panel 63 further penetrate to the outside by projection optical system 51.
As shown in figure 16, can on straight line, dispose from light source 53 to projection optical system 51.At this moment,, can shorten focal length, therefore can shorten the length of whole liquid crystal projection apparatus by being the lens that use embodiment 9 among 51 lens 51a, 51b and the 51c at projection optics.
(embodiment 14)
Make compound non-spherical lens shown in Figure 17.Compound non-spherical lens 5 shown in Figure 17 is, on the 2nd 1b of the lens mother metal 1 of diameter 3mm, maximum ga(u)ge 1.5mm, forms the resin layer 2 that is formed by Organometallic polymer material of the present invention, on resin layer 2, and formation AR film (antireflection film) 3.On the 1st 1a of the opposition side of lens mother metal 1, form AR film 4.The radius-of-curvature of the 1st 1a of lens mother metal 1 is 4mm, and the radius-of-curvature of the 2nd 1b is 1.7mm.
The Organometallic polymer material that forms resin layer 2 is formed by the following curable organometallic composition that constitutes.
Vinylformic acid fluorenes ester: 40 weight %
Organometallic polymer: 40 weight %
Phenoxyethyl acrylate (PhEA): 20 weight %
Organometallic polymer is formed with 50: 50 mixed in molar ratio by 3-methacryloxypropyl triethoxyl silane (MPTES) and dimethoxydiphenylsilane (DPhDMS).
Specifically, heat down at 60 ℃, mix by viscous liquid A and the viscous liquid B that will be prepared as follows, the preparation curable organometallic composition.
＜viscous liquid A 〉
By mixing following substances while heating down, obtain viscous liquid A at 60 ℃:
Vinylformic acid fluorenes ester: 6.4g;
1-hydroxyl-cyclohexyl-benzophenone: 0.2g;
HALS (Tinuvin292 that Ciba Speciality Chemicals company produces): 0.05g;
UV light absorber (Tinuvin400 that Ciba Speciality Chemicals company produces): 0.15g; With
PhEA：3.2g。
＜viscous liquid B 〉
By with MPTES:12.3ml, DPhDMS:10.3ml, as catalysts contain aqueous solution of hydrochloric acid (hydrochloric acid of concentration 2N: 3.8ml) and ethanol: 40ml mix the back and placed 24 hours, be hydrolyzed, make it that polycondensation take place.
Be heated to 100 ℃ by the liquid that contains polycondensate that will obtain under nitrogen atmosphere, ethanol is removed in evaporation, obtains viscous liquid.Get the viscous liquid that 1g obtains, with
Metal alkoxide X: trimethylethoxysilane: 3ml,
Organic acid Y: anhydrous trifluoroacetic acid: 0.8ml
Mix, place after 24 hours, by carry out heat drying under nitrogen atmosphere, under 110 ℃, excessive metal alkoxide X and organic acid Y are removed in evaporation, obtain viscous liquid B.
In following embodiment, use this viscous liquid B.
The above-mentioned curable organometallic composition that obtains is dripped on the lens mother metal, form resin layer 2.
Next, on the resin layer 2 and on the 1st 1a of mother metal 1, form AR film 3 and 4 respectively.The AR film is made silicon oxide film and oxidation titanium film alternative stacked by the electron beam evaporation plating method.Design wavelength lambda is made as 500nm, at first on mother metal, form silicon oxide film as basic unit with thickness λ, then, disclosed as Japanese kokai publication hei 6-11601 communique, from mother metal side lamination oxidation titanium film 0.04 λ successively, silicon oxide film 0.1 λ, oxidation titanium film 0.5 λ, silicon oxide film 0.24 λ.
As compound non-spherical lens, two kinds of lens that use base glass material and use the plastics mother metal have been made.
As base glass material, the S-FPL51 that uses OHARA company to produce.In addition, as the plastics mother metal, the lens mother metal that uses the ZEONEX resin produced by Japanese ZEON company to constitute.
The radius-of-curvature of the resin layer 2 when using base glass material as lens mother metal 1 is 3.01mm, and the radius-of-curvature of the resin layer 2 when using the plastics mother metal is 4.43mm.
[thermal shock test]
Two kinds of compound non-spherical lenses at above-mentioned making carry out thermal shock test.Figure 18 carries out the schematic cross-section of the device of thermal shock test for expression.To put into container 7 as the sample 8 of determination object, container 7 with the cycle shown in Figure 19 between the thermostatic bath 6 of-40 ℃ thermostatic bath 5 and 85 ℃ back and forth, give sample 8 thermal shockings thus.
The result who carries out above-mentioned thermal shock test is in the compound non-spherical lens that uses base glass material, after 500 circulations, not have not peel off or break on resin layer and AR film.But, in the compound non-spherical lens that uses the plastics mother metal, after 100 circulations, on the AR film, break.
Use the curable organometallic composition (the Organometallic composition addition is 20 weight %) of embodiment 1, the compound non-spherical lens with above-mentioned identical making base glass material and plastics mother metal carries out thermal shock test.Its result is that after 100 circulations, any of base glass material and plastics mother metal all taken place to break on resin layer and AR film.Therefore as can be known, be compared to the benzyl methacrylate (BzMA) that uses in embodiment 1, the phenoxyethyl acrylate of Shi Yonging (PhEA) has the disruptive of preventing effect in the present embodiment.When using under the situation of PhEA as acrylate, the content of PhEA is preferably in the scope of 10～30 weight %.
(embodiment 15)
Use three vinylformic acid, five tetrahydroxybutane esters (PETA) as acrylate, the following curable organometallic composition of forming of preparation.
Vinylformic acid fluorenes ester: 55 weight %
Organometallic polymer: 25 weight %
PETA:15 weight %
Viscous liquid B by the viscous liquid A that will be prepared as follows and embodiment 14 mixes simultaneously and stirs, the preparation curable organometallic composition 60 ℃ of heating down.
＜viscous liquid A 〉
By mixing following substances while heating down, obtain viscous liquid A at 60 ℃:
Vinylformic acid fluorenes ester: 8.8g;
1-hydroxyl-cyclohexyl-benzophenone: 0.2g;
HALS (Tinuvin292 that Ciba Speciality Chemicals company produces): 0.05g;
UV light absorber (Tinuvin400 that Ciba Speciality Chemicals company produces): 0.15g; With
PETA：4g。
The curable organometallic composition that use prepares, the compound non-spherical lens with the foregoing description 14 identical making base glass materials and plastics mother metal carries out thermal shock test.
In the compound non-spherical lens that uses the plastics mother metal, after 500 circulations, on resin layer and AR film, do not have not peel off or break.But, in the compound non-spherical lens that uses base glass material, within 100 circulations, on the AR film, break.When using PETA as acrylate, the content of PETA is preferably in the scope of 5～25 weight %.
(embodiment 16)
Use above-mentioned PETA and urethane acrylate (commodity that ダ イ セ Le サ イ テ Star Network company produces " Ebecry1210 " by name) as acrylate, the following curable organometallic composition of forming of preparation.
Vinylformic acid fluorenes ester: 45 weight %
Organometallic polymer: 30 weight %
PETA:10 weight %
Urethane: 15 weight %
Viscous liquid A is prepared as follows.
＜viscous liquid A 〉
By mixing following substances while heating down, obtain viscous liquid A at 60 ℃:
Vinylformic acid fluorenes ester: 7.2;
1-hydroxyl-cyclohexyl-benzophenone: 0.2g;
HALS (Tinuvin292 that Ciba Speciality Chemicals company produces): 0.05g;
UV light absorber (Tinuvin400 that Ciba Speciality Chemicals company produces): 0.15g;
PETA:1.6g; With
Urethane acrylate: 2.4g.
Use the curable organometallic composition as above-mentioned preparation, identical with the foregoing description 14, the compound non-spherical lens of making base glass material and plastics mother metal carries out thermal shock test.
Use plastics mother metal and plastics mother metal any in, after 100 circulations, on resin layer and AR film, do not peel off or break.
But the viscosity of curable organometallic composition is high slightly.In addition, in the compound non-spherical lens that uses base glass material, after 250 circulations, on resin layer, break.When using urethane acrylate as acrylate, the content of urethane acrylate is preferably in the scope of 5～10 weight %.
(embodiment 17)
The EO modification diacrylate (commodity that East Asia Synesis Company produces " M-210 " by name) that uses above-mentioned PETA and dihydroxyphenyl propane prepares the following curable organometallic composition of forming as acrylate.
Vinylformic acid fluorenes ester: 45 weight %
Organometallic polymer: 35 weight %
PETA:10 weight %
Bis-phenol diacrylate: 10 weight %
Viscous liquid A is prepared as follows.
＜viscous liquid A 〉
By mixing following substances while heating down, obtain viscous liquid A at 60 ℃:
Vinylformic acid fluorenes ester: 7.2g;
1-hydroxyl-cyclohexyl-benzophenone: 0.2g;
HALS (Tinuvin292 that Ciba Speciality Chemicals company produces): 0.05g;
UV light absorber (Tinuvin400 that Ciba Speciality Chemicals company produces): 0.15g;
PETA:1.6g; With
Bis-phenol diacrylate: 1.6g.
The curable organometallic composition that use obtains, the compound non-spherical lens with the foregoing description 14 identical making base glass materials and plastics mother metal carries out thermal shock test.
In the compound non-spherical lens that uses the plastics mother metal, after 500 circulations, on resin layer and AR film, do not have not peel off or break.Relative therewith, in the compound non-spherical lens that uses base glass material, within 100 circulations, on resin layer and AR film, break.In addition, the viscosity of the curable organometallic composition of the viscosity ratio embodiment 16 of curable organometallic composition is low in the present embodiment.
In the present embodiment, though use the bis-phenol diacrylate of EO modification, outside this, also can use the bis-phenol diacrylate of PO modification, tetrahydrofuran (THF) modification.In addition, also can use other (methyl) acrylate that contain bis-phenol base and (methyl) acryl of Bisphenol F diacrylate etc.When using the bis-phenol diacrylate as acrylate, the content of bis-phenol diacrylate is preferably in the scope of 15～40 weight %.
(embodiment 18)
Use above-mentioned PETA and hydroxyethylated orthoxenol methacrylic ester (trade(brand)name " NK ester L-4 " that Xin Zhong village chemical company produces) (PhPhMA) as acrylate, the following curable organometallic composition of forming of preparation.
Vinylformic acid fluorenes ester: 40 weight %
Organometallic polymer: 20 weight %
PETA:10 weight %
PhPhMA:30 weight %
Viscous liquid A is prepared as follows.
＜viscous liquid A 〉
By mixing following substances while heating down, obtain viscous liquid A at 60 ℃:
Vinylformic acid fluorenes ester: 7.2g;
1-hydroxyl-cyclohexyl-benzophenone: 0.2g;
HALS (Tinuvin292 that Ciba Speciality Chemicals company produces): 0.05g;
UV light absorber (Tinuvin400 that Ciba Speciality Chemicals company produces): 0.15g;
PETA:1.6g and
PhPhMA：4.8g。
The curable organometallic composition that use obtains, the compound non-spherical lens with the foregoing description 14 identical making base glass materials and plastics mother metal carries out thermal shock test.
In the compound non-spherical lens of plastics mother metal, after 500 circulations, on resin layer and AR film, do not have not peel off or break.But, in the compound non-spherical lens that uses base glass material, after 100 circulations, on resin layer and AR film, break.
In addition, the viscosity of the curable organometallic composition of the viscosity ratio embodiment 16 of curable organometallic composition is low in the present embodiment.
In the present embodiment; though use hydroxyethylated orthoxenol methacrylic ester, (methyl) acrylate that contains phenyl phenol and (methyl) acryl that also can use orthoxenol glyceryl ether acrylate (Xin Zhong village chemical company produce trade(brand)name " NK ester 401B ") to wait.When using phenylphenol (methyl) acrylate as acrylate, the content of phenylphenol (methyl) acrylate is preferably in the scope of 10～40 weight %.
As known from the above, by as embodiment 17 and embodiment 18, use as (methyl) acrylate that bis-phenol base or phenyl phenol etc. contain the phenyl more than 2 dilutes curable organometallic composition, just can keep high refractive index, reduction viscosity.
The viscosity of the curable organometallic composition of preparation and the specific refractory power and the Abbe number of cured article are shown in table 2 in embodiment 1 and embodiment 14～18.
Table 2
| Organometallic polymer | The fluorenes based compound | First acrylate | Second acrylate | Viscosity | Specific refractory power | | |
| Embodiment | |||||||
| 1 | MPTES +DPhDMS | Vinylformic acid fluorenes ester | BzMA | Do not have | Low | 1.600 | 28 |
| | PhEA | Do not have | Low | 1.589 | 30 | ||
| | PETA | Do not have | In | 1.582 | 32 | ||
| | PETA | Urethane acrylate | High | 1.591 | 29 | ||
| | PETA | The bis-phenol acrylate | Low | 1.588 | 30 | ||
| | PETA | PhPhMA | Low | 1.594 | 29 |
BzMA, PhEA, PhPhMA are 1 functional acrylate, and urethane acrylate and bis-phenol acrylate are 2 functional acrylates, and PETA is 3 functional acrylates.
(embodiment 19)
At the compound non-spherical lens of the base glass material of in embodiment 14, making, measure focal length, in arbitrary wavelength of wavelength 486nm and wavelength 656nm, focal length is 3.79mm.
(embodiment 20)
At the compound non-spherical lens of the plastics mother metal among the embodiment 17, measure focal length.In arbitrary wavelength of wavelength 486nm and wavelength 656nm, focal length is 4.92mm.
In the foregoing description 19 and embodiment 20, though just realized the aberration elimination with 1 compound non-spherical lens, but the lens more than 1 in the lens combination that is made of a plurality of lens adopt the compound type lens with resin layer that curable organometallic composition of the present invention constitutes, and also one realize color difference eliminating surely.
(embodiment 21)
Figure 20 is the cross section mode chart of expression use as an embodiment of the optical transceiver module of the compound non-spherical lens 5 of optics of the present invention.
In optical transceiver module 70, be inserted with an end 71a of optical fiber 71, on the position relative, be provided with luminous element 73 with an end 71a of optical fiber 71.In the place ahead of luminous element 73, be provided with compound non-spherical lens 5 of the present invention.Between the end 71a of compound non-spherical lens 5 and optical fiber 71, the wavelength that is provided with 45 ° of inclinations is selected spectral filter 72.Below wavelength selection spectral filter 72, be provided with photo detector 75 across lens 74.
The light that is penetrated by luminous element 73 is selected spectral filter 72 by compound non-spherical lens 5 by wavelength, enters in the optical fiber 71 and is transmitted from end 71a.
In addition, the light of sending from optical fiber 71 passes through end 71a, is selected spectral filter 72 reflections by wavelength, and scioptics 74 make light receiving component 75 accept light.
In the optical transceiver module of present embodiment,,, can realize miniaturization so can shorten focal length owing to used compound non-spherical lens 5 of the present invention.
Claims (11)
1. curable organometallic composition is characterized in that:
Comprise: have-organometallic polymer of M-O-M-key and aryl and have acryl or the fluorenes based compound of methacryloyl, wherein, M is an atoms metal.
2. curable organometallic composition as claimed in claim 1 is characterized in that:
Also comprise (methyl) acrylate with 2 above functional groups.
3. curable organometallic composition as claimed in claim 1 is characterized in that:
Also comprise (methyl) acrylate with 1 above aryl.
4. curable organometallic composition as claimed in claim 2 is characterized in that:
Also comprise the aromatic urethane origoester acrylate.
5. curable organometallic composition as claimed in claim 1 is characterized in that:
Also comprise only have one can hydrolysis metal alkoxide and/or its hydrolyzate of base.
6. curable organometallic composition as claimed in claim 1 is characterized in that:
Also comprise anhydrous organic acid and/or organic acid.
7. curable organometallic composition as claimed in claim 1 is characterized in that:
The atoms metal M of described organometallic polymer is at least one that is selected among Si, Nb, Ti and the Zr.
8. an Organometallic polymer material is characterized in that, obtains by the described curable organometallic composition of claim 1 is carried out polymerization.
9. an optics is characterized in that,
Use the described Organometallic polymer material of claim 8 to form light transmissive region.
10. optics as claimed in claim 9 is characterized in that:
It is the compound non-spherical lens that forms described light transmissive region on the parts of light transmission.
11. Optical devices is characterized in that:
Possesses the described optics of claim 9.
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| JP2006086025 | 2006-03-27 | ||
| JP2006086025 | 2006-03-27 | ||
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538346B (en) * | 2008-03-17 | 2011-03-23 | 迎辉科技股份有限公司 | Monomer composition for preparing light-condensing sheet and application thereof |
| CN102902162A (en) * | 2007-12-14 | 2013-01-30 | 旭化成电子材料株式会社 | Photosensitive resin composition |
| CN107922548A (en) * | 2015-09-02 | 2018-04-17 | 日产化学工业株式会社 | Polymerizable composition, polymerizable composition containing the silesquioxane compound with acryloyl group |
| TWI712650B (en) * | 2014-02-28 | 2020-12-11 | 日商日產化學工業股份有限公司 | Polymerizable composition containing reactive silsesquioxane compound |
| CN113178529A (en) * | 2021-04-07 | 2021-07-27 | 武汉华星光电半导体显示技术有限公司 | Display panel |
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- 2007-03-27 CN CN 200710091530 patent/CN101045788A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102902162A (en) * | 2007-12-14 | 2013-01-30 | 旭化成电子材料株式会社 | Photosensitive resin composition |
| CN101802033B (en) * | 2007-12-14 | 2013-03-13 | 旭化成电子材料株式会社 | Photosensitive resin composition |
| CN101538346B (en) * | 2008-03-17 | 2011-03-23 | 迎辉科技股份有限公司 | Monomer composition for preparing light-condensing sheet and application thereof |
| TWI712650B (en) * | 2014-02-28 | 2020-12-11 | 日商日產化學工業股份有限公司 | Polymerizable composition containing reactive silsesquioxane compound |
| CN107922548A (en) * | 2015-09-02 | 2018-04-17 | 日产化学工业株式会社 | Polymerizable composition, polymerizable composition containing the silesquioxane compound with acryloyl group |
| CN107922548B (en) * | 2015-09-02 | 2021-06-18 | 日产化学工业株式会社 | Polymerizable composition containing silsesquioxane compound having acryloyl group |
| CN113178529A (en) * | 2021-04-07 | 2021-07-27 | 武汉华星光电半导体显示技术有限公司 | Display panel |
| CN113178529B (en) * | 2021-04-07 | 2022-04-01 | 武汉华星光电半导体显示技术有限公司 | Display panel |
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