CN1940598A - Optical material and optical element - Google Patents
Optical material and optical element Download PDFInfo
- Publication number
- CN1940598A CN1940598A CN 200610159970 CN200610159970A CN1940598A CN 1940598 A CN1940598 A CN 1940598A CN 200610159970 CN200610159970 CN 200610159970 CN 200610159970 A CN200610159970 A CN 200610159970A CN 1940598 A CN1940598 A CN 1940598A
- Authority
- CN
- China
- Prior art keywords
- optical
- resin material
- optical resin
- metal alkoxide
- lens
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
An optical resin material containing a hydrolysis/polycondensation product, having at least a hydroxyl group in a molecule, of metal alkoxide, a volatile low-molecular component and an organic polymer, wherein the volatile low-molecular component has a polar group (for example, a carboxylic acid group, a carbonyl group, and a hydroxyl group) which can bind to the hydroxyl group of the hydrolysis/polycondensation product of metal alkoxide.
Description
Technical field
The optical element that the present invention relates to can be used for the optical resin material of optical component etc. and use this material.
Background technology
Resin material is lower than glass material because of its cost, the property produced in batches height, so be widely used as the optical component material.But mobile phone with parts, optical communication with in the parts etc., demand can stand the hot and humid preservation test of 85 ℃ of temperature, humidity 85%, optical component not only naturally need not destroy and distortion with material, but also needs change of optical property such as refractive index little.Acrylic resin, epikote, great majority in the ordinary optical resins such as epoxy acrylic esters resin, polyurethanes resin can be aging gradually under the hot and humid environment of 85 ℃ of temperature, humidity 85%, and refractive index reduces gradually.The reduction of this refractive index will cause obstacle with parts, optical communication with the application in the parts at mobile phone to optical resin material.
For suppressing the reduction of this refractive index, in the prior art, proposing has by material itself being strengthened the method for guaranteed performance.For example, in Japanese kokai publication hei 11-322864 communique, disclosed in containing the polymkeric substance of thio group, by making optimizations such as sulfur content, viscosity, to improve the technology of dependability scheme.But, in these class methods,, therefore can't seek to make optical characteristics stabilizations such as refractive index, Abbe number from optical design because aspects such as material and manufacturing conditions are subjected to severely restricts.
Summary of the invention
The objective of the invention is to, a kind of optical element that can be reduced in the optical resin material of variations in refractive index under the hot and humid environment and use this material is provided.
The present invention relates to a kind of optical resin material, it contains the hydrolytie polycondensation product and the volatility low molecular composition of the metal alkoxide that has a hydroxyl in the molecule at least.It is characterized in that: the volatility low molecular composition have can with the group of the hydroxyl Cheng Jian of the hydrolytie polycondensation product of metal alkoxide.In addition, metal alkoxide of the present invention is meant and has an organometallics that can form the group of OH base by hydrolysis at least.
The inventor etc. notice: the resinoid refractive index of acrylic resin, epikote and polyurethane as optical resin material will reduce under hot and humid environment all the time.The inventor thinks that under hot and humid environment, the reduction of refractive index is owing to following reason.
The refractive index of macromolecular material is used formula (1) expression usually.According to formula (1) as can be known, if the value on equation right side increases, show that then refractive index increases.
In the formula, n
DBe the refractive index of macromolecular material, [R] is the atomic refraction sum, V=M/ ρ, wherein, M is the monomer molecule amount, and ρ is a density polymer, and formula 1 is drawn the volume quarterly from Japanese Chemical Society---interim " the refractive index control of light transmission polymkeric substance " of No.39 in 1998 of " chemistry is always said ".
According to following formula (1) as can be known, by the little key of increase atomic refraction, or reduce density, refractive index reduces.Under the hot and humid environment of 85 ℃ of temperature, humidity 85%, following variation will take place.
(1),,, reduces producing high-molecular because of causing the big OH base of atomic refraction along with the carrying out of hydrolytie polycondensation owing to the humidity height.
(2) the crosslinked disconnection between strand, the carbon single bond that atomic refraction is big change into the little two keys of atomic refraction.
(3) because of the volatilization of the constitute that constitutes resin, cause density to reduce.
In addition, the inventor also considers the following reason that causes refractive index to reduce except that the variation of above-mentioned macromolecule state.
(4), and introduce the little water of refractive index owing to moisture absorption.
As mentioned above, existing resin as optical resin material causes the reduction of refractive index because of a variety of causes under hot and humid environment.
Contain the hydrolytie polycondensation product of above-mentioned metal alkoxide and the optical resin material of the present invention of above-mentioned volatility low molecular composition, have the characteristic that refractive index raises under hot and humid environment.Therefore, by optical resin material of the present invention is mixed use with existing optical resins such as esters of acrylic acids, just can have the reduction of the refractive index of optical resin now, thereby can be controlled at change of refractive under the hot and humid environment with the rising counteracting of the refractive index of optical resin material of the present invention.
Therefore, the optical resin material according to others of the present invention is characterised in that: contain the hydrolytie polycondensation product and the above-mentioned volatility low molecular composition of above-mentioned metal alkoxide, also contain organic polymer.
In optical resin material of the present invention, because of the volatilization of volatility low molecular composition, refractive index raises.Volatility low molecular composition of the present invention have can with the group of the hydroxyl Cheng Jian of metal alkoxide hydrolytie polycondensation product.Form hydrogen bond between the hydroxyl of the hydrolytie polycondensation product of metal alkoxide and the group of low molecular composition, or, make the volatility of low molecular composition controlled, can seek the stabilization of long-term refractive index by one-tenth keys such as polycondensations.
The group of low molecular composition can be enumerated carboxylic acid group, carbonyl and the hydroxyl etc. with polarity.
Low molecular composition of the present invention can be enumerated the monomer that generated by metal alkoxide or oligomer, organic acid, alcohols, ketone etc.The preferred monomer that generates by metal alkoxide or oligomer, the organic acid of adopting.In addition, low molecular composition preferably adopts the compound that contains the low fluorine atom of molecular refraction.Therefore, preferred low molecular composition can be enumerated metal alkoxide, organic acid, alcohol and the ketone etc. of contain fluorine atoms.
Metal alkoxide of the present invention especially preferably adopts alkoxy silane.Metal alkoxide preferably adopts the metal alkoxide that contains methacryloxy and/or acryloxy or have styryl.By using this class to have the metal alkoxide of two keys, just can utilize the energy line irradiation to make this double-bond polymerization, and then realize solidifying.
Among the present invention used organic polymer can enumerate acrylic resin, epikote, the potpourri of polyurethanes resin, polyester acrylic esters resin, epoxy acrylic esters resin and above-mentioned resin.Also can enumerate the Organometallic polymer material that above-mentioned metal alkoxide hydrolysis is generated.In addition, can also be to make SiO
2, TiO
2, ZrO
2, Nb
2O
5Be dispersed in material in these resins Deng the metal oxide molecule.In addition, the organic polymer among the present invention can also be the organic polymer that methacryloxy and acryloxy etc. have two keys.Because organic polymer has the two keys of this class, therefore just can pass through the irradiation energy line, makes double-bond polymerization, and then realizes solidifying.In addition, have under the situation of two keys, make these pairs key Cheng Jian, just can realize crosslinked at metal alkoxide hydrolytie polycondensation product.
The optical resin material of the present invention that contains organic polymer preferably the change of refractive under the hot and humid environment of 85 ℃ of temperature, humidity 85% be per 500 hours below ± 0.001.
In optical resin material of the present invention, cooperation ratio to the hydrolytie polycondensation product of metal alkoxide, low molecular composition, organic polymer is carried out appropriate regulation, stably to control refractive index, although be not particularly limited, but the hydrolytie polycondensation product of preferably metal alkoxide is 4～95 weight %, organic polymer is 4～95 weight %, and low molecular composition is 1～30 weight %.
Optical element of the present invention is characterised in that: the optical resin material that uses the invention described above.
Composite optical element of the present invention is characterised in that: the mother metal surface is formed with the optical resin layer that the optical resin material by the invention described above constitutes.
Preferred implementation according to composite optical element of the present invention is characterised in that: mother metal is lens, and optical resin layer is formed on the optical surface of lens.
Mother metal can be enumerated the material that is made of glass, plastics, light transparent ceramic or optical crystal.
Glass can be enumerated ordinary optical glass and glass of high refractive index etc.
In addition, plastic material can enumerate acrylic resins such as polymethylmethacrylate, epikote, organic siliconresin, fluororesin, polyolefin resin, polycarbonate, polyethylene terephthalate, PEN, polymethylpentene, polystyrene, polyacrylate, polysulfones, polyethersulfone, polyetherimide, polyimide, tygon, polypropylene etc.
Light transparent ceramic can be enumerated aluminium oxide, MgF
2, CaF
2, (ZrTi) O of spinel sintered body, (PbLa)
3(PLZT), yttrium aluminum garnet sintered body, Murata Manufacturing Co. Ltd.'s system trade name " LUMICERA " etc.
Optical crystal can be enumerated crystal, rutile, spinel, sapphire, lithium niobate, lithium tantalate, potassium niobate, lead zirconate titanate, lanthanumdoped lead zirconate-lead titanate, metatitanic acid potassium phosphate, barium titanate, yttrium aluminum garnet, yttrium iron garnet, beta-barium borate, three lithium borates; Semiconductor such as silicon, germanium; II-VI such as selenium sulfide, zinc selenide compound semiconductor and mix-crystal thereof; III-V compound semiconductors such as gallium arsenide, gallium phosphide, indium phosphide, aluminium arsenide, gallium nitride, aluminium nitride and mix-crystal thereof etc.
Optical devices of the present invention are characterised in that: the composite optical element that comprises the invention described above.
Optical devices of the present invention can be enumerated for example optical communication equipments such as photoswitch, light transmitting-receiving module, photo-coupler; Display devices such as liquid crystal display, plasma display equipment, organic EL display apparatus, projector, projector; Optical components such as microlens array, integraph, light guide plate; Cameras such as digital camera; Camera heads such as video camera; Shooting such as CCD photograph module, CMOS photograph module module; Optical devices such as telescope, microscope, magnifier etc.
Use contains the optical resin material of the present invention of organic polymer, can form the change of refractive that reduces under the hot and humid environment, and shows the optical resin material of stable refractive index.
Because optical resin of the present invention uses the optical material of the invention described above, even therefore can make the optical element that under hot and humid environment, also can show stable refractive index.
Description of drawings
Fig. 1 is the synoptic diagram of expression according to the state in the optical resin material among a certain embodiment of the present invention.
Fig. 2 is the sectional view of expression according to the compound non-spherical lens of making in the embodiments of the invention.
Fig. 3 is illustrated under the situation of using spherical lens optically focused the light intensity distributions figure of focal point.
Fig. 4 is illustrated under the situation of using compound non-spherical lens optically focused the light intensity distributions figure of focal point.
Fig. 5 is the sectional view of the compound type lens of expression embodiment 7 manufacturings.
Fig. 6 is take a picture the according to an embodiment of the invention diagrammatic cross-section of module of expression.
Fig. 7 is for representing before compound type lens (a) high temperature and humidity test according to an embodiment of the invention and (b) curve (simulation) of the focal point after the test.
Fig. 8 for compound type lens (a) high temperature and humidity test of expression comparative example before and (b) curve (simulation) of focal point after the test.
Fig. 9 is the structural drawing of expression use according to the digital camera of the photograph module of the embodiment of the invention.
Figure 10 is the projector architecture synoptic diagram of expression use according to compound type lens of the present invention.
Figure 11 uses the diagrammatic cross-section of receiving and dispatching module according to the light of compound type lens of the present invention for expression.
Embodiment
Below, by embodiment the present invention is described, but the present invention is not limited to following embodiment.
Comparative example 1
The urethane acrylate resinoid uses the viscous fluid before the curing that the 1-hydroxy cyclohexyl phenylketone as Photoepolymerizationinitiater initiater by the benzyl methacrylate of the polyurethane end group methacrylate oligomers that contains toluene support diisocyanate of about 55 weight %, the trimethylolpropane triacrylate of about 25 weight %, about 18 weight % and about 2 weight % constitutes, and uses illumination 500mW/cm
2Mercury light viscous fluid before this solidifies shone 4 minutes, make its curing.Under the hot and humid environment of 85 ℃ of temperature, humidity 85%, this solidfied material carried out 500 hours burin-in process.Initial index of refraction is 1.5350, and refractive index is 1.5338 after the burin-in process.Therefore, the change of refractive amount is-0.0012.In addition, Noland Co., Ltd. system propenyl resinoid " NOA60 " owing to the burin-in process under the equal conditions, causes refractive index to reduce too.
Comparative example 2
6.0ml is added in the 15.0ml ethanol as the 3-methacryloxypropyl triethoxysilane (MPTES) of metal alkoxide, and one side stirs, and one side drips the hydrochloric acid of the 2N of 1.2ml.It was placed two days, and being hydrolyzed makes its polycondensation.Then, add 1.5mg polymerization initiator 1-hydroxy cyclohexyl phenylketone, then under 100 ℃ to its heating, remove ethanol, obtain the hydrolytie polycondensation product of metal alkoxide.
Use illumination 500mW/cm
2Mercury light to its irradiation 4 minutes, make its curing.
The same with comparative example 1, under the hot and humid environment of 85 ℃ of temperature, humidity 85%, this solidfied material carried out 100 hours burin-in process.Initial index of refraction is 1.4845, and the refractive index of burin-in process after 100 hours is 1.4868, confirms that the change of refractive amount is+0.0023.
Said sample is carried out infrared absorption spectrum analysis, results verification, after the burin-in process, the OH base increases to some extent.The inventor thinks that this is that the result has caused the refractive index rising because originally stable Si-O-Si key hydrolysis under humid tropical condition has generated the big Si-OH of molecular refraction.
By organic polymers such as the hydrolytie polycondensation product of this metal alkoxide and esters of acrylic acid, epoxies, polyurethanes is mixing cured, can control change of refractive under the hot and humid environment.But in the method, according to the blending ratio of the hydrolytie polycondensation product of metal alkoxide, the stability of refractive index changes to some extent.Because blending ratio also influences other characteristics such as hardness, thermotolerance, therefore, only adopt this method can not make refractive index stable fully.
In the present invention, by adding the volatility low molecular composition again, great changes will take place not make the blending ratio of metal alkoxide hydrolytie polycondensation product and organic polymer, can guarantee that refractive index is stable.
Comparative example 3
In this example, the volatility low molecular composition is mixed in the organic polymer, estimates the effect that reaches by this interpolation.Use trifluoroacetic acid as the volatility low molecular composition, use urethane acrylate resinoid with comparative example 1 as organic polymer.Add the trifluoroacetic acid of 20mg in 10g urethane acrylate resinoid, same as above after the interpolation, irradiation ultraviolet radiation is cured.The gained solidfied material is same as above, places under the hot and humid environment, measures change of refractive.After 100 hours, can make variations in refractive index very little, reach-0.0001; And after 500 hours, reach-0.0010, be and the refractive index of not adding the sample equal extent of low molecular composition.
From The above results as can be known, only by add the volatility low molecular composition in organic polymer, low molecular composition can not make the refractive index long-term stability volatilizing than stage morning.In the present invention, use have can with the low molecular composition of the group of the hydroxyl Cheng Jian of the hydrolytie polycondensation product of metal alkoxide, by Cheng Jian between the group of the hydroxyl of the hydrolytie polycondensation product of metal alkoxide and low molecular composition, control the evaporation rate of volatility low molecular composition, guarantee the stability of long-term refractive index.
In addition, between the hydrolytie polycondensation product and organic polymer of metal alkoxide, also be preferably formed because any keys such as key that key, hydrogen bond, the pi-electron that the polymerization of propenyl forms overlaps to form.
In the present embodiment, use MPTES, use trifluoroacetic acid, use urethane acrylate class optical resin with comparative example 1 as organic polymer as the volatility low molecular composition as metal alkoxide.The method for making of sample is as described below.
(1) MPTES of adding 6.0ml in 15.0ml ethanol, one side stirs the hydrochloric acid that one side drips the 2N of 1.2ml.It was placed 2 days, make it that hydrolysis condensation reaction take place.
(2) under 100 ℃, said hydrolyzed polycondensation reaction thing is heated, remove ethanol.Can access the hydrolytie polycondensation product of metal alkoxide thus.
(3) before 10g is with the curing of comparative example 1, add the hydrolytie polycondensation product of the above-mentioned metal alkoxide of 1g, the trifluoroacetic acid of 20mg in the viscous fluid, stir.
(4) use illumination 500mW/cm
2Mercury light to gained potpourri irradiation 4 minutes, make its curing.
Shown in the MPTES following (Chemical formula 1), silicon and three ethoxys and a methacryloxy Cheng Jian.
(Chemical formula 1)
In the operation of above-mentioned (Chemical formula 1), by adding hydrochloric acid, make the water reaction in ethoxy and the hydrochloric acid and separate, shown in (Chemical formula 2), other MPTES molecule Cheng Jian that separates with same ethoxy.
(Chemical formula 2)
This reaction is carried out continuously, forms strand, and shown in (Chemical formula 2), part ethoxy and water reaction form the OH base.
Shown in (chemical formula 3), form hydrogen bond between trifluoroacetic acid and this OH base.
(chemical formula 3)
If irradiation ultraviolet radiation more just as (chemical formula 4) shown in, disconnects with two keys of the methacryloxy of MPTES strand Cheng Jian, with the methacryloxy Cheng Jian of other strand of same pair of keys disconnection.
(chemical formula 4)
Like this, by the binding reaction between the strand, cause the curing of resin.In addition, because the urethane acrylate resinoid also has methacryloxy or acryloxy, so same binding reaction also takes place between these pairs key.
As mentioned above, the sample that irradiation ultraviolet radiation is solidified carries out 500 hours burin-in process under the hot and humid environment of 85 ℃ of temperature, humidity 85%, the refractive index after the mensuration burin-in process.The result is as shown in table 1.In addition, table 1 has also shown the result of comparative example 1 simultaneously.
As shown in table 1, initial index of refraction is 1.5304, and the refractive index of burin-in process after 500 hours is 1.5303, and change of refractive is-0.0001.Change of refractive when independent with the urethane acrylate resinoid is compared for-0.0012, has suppressed change of refractive significantly.
In addition, when using 3-methyl allyl acyloxypropyl trimethoxysilane (MPTMS) to replace MPTES, also can reach same effect as metal alkoxide.In addition, except that MPTES and MPTMS, other metal alkoxide with methacryloxy, for example, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, or have styryl to the styrene trimethoxy silane, also can reach same effect.In addition, also can use and have the 3-acryloyl-oxy propyl trimethoxy silicane etc. that acryloxy replaces methacryloxy.In addition, can also there be the metal alkoxide of methacryloxy to replace a part in the metal alkoxide with these methacryloxies or acryloxy with phenyltrimethoxysila,e (PhTMS), dimethoxydiphenylsilane (DPhDMS) etc.
In addition, the volatility low molecular composition mixes trifluoroethanol or trifluoroacetone without trifluoroacetic acid but replace, and also can reach same effect.In addition, can also be the organofluorine compound that trifluoro-benzoic acid, trifluoroacetophenone, difluoroacetic acid, difluoro-benzoic acid etc. have polarity.
In addition, organic polymer can also be with SiO
2, TiO
2, ZrO
2, Nb
2O
5Deng metal oxide microparticle be dispersed in Organometallic polymer material that the metal alkoxide hydrolysis generates, acrylic resin, epikote, alloy in polyurethanes resin, polyester acrylic esters resin, epoxy acrylic esters resin and their potpourri thereof.
In the present embodiment, metal alkoxide uses MPTES, and the volatility low molecular composition uses the trifluoro propyl trimethoxy silane (TFPTMS) as metal alkoxide, and organic polymer uses the urethane acrylate resinoid with comparative example 1.The method for making of sample is as described below.
(1) MPTES of adding 6.0ml in 15.0ml ethanol, one side stirs the hydrochloric acid that one side drips the 2N of 1.2ml.It was placed 2 days, make it that hydrolysis condensation reaction take place.
(2) add the TFPTMS of 2.0ml again, stir.
(3) under 100 ℃, said mixture is heated, remove ethanol, obtain the hydrolytie polycondensation product of metal alkoxide.
(4) will mix stirring with the hydrolytie polycondensation product of above-mentioned metal alkoxide according to 20: 1 ratio with viscous fluid before the curing of comparative example 1.
(5) use illumination 500mW/cm
2Mercury light to gained potpourri irradiation 4 minutes, make its curing.
In the present embodiment, shown in (chemical formula 5), the strand of MPTES further with the strand Cheng Jian of TFPTMS.Because TFPTMS does not contain methacryloxy and acryloxy, so, compare the easier disconnection of key with MPTES, urethane acrylate resinoid.
(chemical formula 5)
Under the hot and humid environment of 85 ℃ of temperature, humidity 85%, said sample carried out 500 hours burin-in process, measure the refractive index after the burin-in process.The result is as shown in table 1.As shown in table 1, initial index of refraction is 1.5314, is 1.5315 after the burin-in process, and change of refractive is+0.0001.Compare with the situation that the urethane acrylate resinoid is independent, can suppress change of refractive significantly.In addition, in the present embodiment, metal alkoxide also can adopt and the same material shown in the foregoing description 1 with organic polymer.
Polymerization initiator only is contained in the organic polymer, solidifies promptly enough fully, but as required, polymerization initiators such as 1-hydroxy cyclohexyl phenylketone is added in the hydrolytie polycondensation product of metal alkoxide, also may shorten set time.
In the present embodiment, use MPTES and DPhDMS, use trifluoroacetic acid, use urethane acrylate resinoid with comparative example 1 as organic polymer as the volatility low molecular composition as metal alkoxide.Be with the difference of embodiment 1, heat, promote the Cheng Jian of the strand of trifluoroacetic acid and metal alkoxide by adding trifluoroacetic anhydride.The method for making of sample is as described below.
(1) MPTES, the DPhDMS of 3.3ml of adding 4.0ml in 15.0ml ethanol, one side stirs the hydrochloric acid that one side drips the 2N of 1.2ml.It was placed 2 days, make it that hydrolysis condensation reaction take place, 100 ℃ of heating down, remove ethanol then.
(2) then, add the trifluoroacetic anhydride of 1ml and the trimethylethoxysilane of 3.75ml, being stirred to does not have segregation phenomenon.
(3) after placing 24 hours, 100 ℃ of heating down, drying is removed trifluoroacetic anhydride and trimethylethoxysilane.
(4) be dissolved in trimethylethoxysilane once more, stir to wherein adding water.
(5) fully place separate after, take out supernatant, heat and remove trimethylethoxysilane.
(6) will mix according to 3: 7 ratio with above-mentioned product with viscous fluid before the curing of comparative example 1, stir.
(7) use illumination 500mW/cm
2Mercury light to gained potpourri irradiation 4 minutes, be cured.
Shown in (chemical formula 6), the separation of the ethoxy of MPTES not only forms strand, and a part wherein also replaces with the water reaction and by the OH base.In the present embodiment, shown in (chemical formula 6), in operation (2)～(3), utilize the potent dehydration of trifluoroacetic anhydride to handle, this OH base is further replaced by trifluoroacetic acid.Be combined in trifluoroacetic acid on this strand and become low-refraction composition in the present embodiment.
(chemical formula 6)
Under the hot and humid environment of 85 ℃ of temperature, humidity 85%, said sample carried out 500 hours burin-in process, measure the refractive index after the burin-in process.Measurement result is as shown in table 1.As shown in table 1, initial index of refraction is 1.5295, and the refractive index of burin-in process after 500 hours is 1.5293, and change of refractive is-0.0002.Compare with the resinoid variations in refractive index of urethane acrylate, can suppress change of refractive significantly.
The inventor thinks: because in the operation (6) and (7) of present embodiment, the reaction residue in the uncured resin dissolves in water separates out, therefore, and hardly can be as the trifluoroacetic acid of the strand formation hydrogen bond of also residual and metal alkoxide as described in the embodiment 1.So, since with the trifluoroacetic acid of strand Cheng Jian under hot and humid environment, separate volatilization according to the process hydrolysis opposite with process shown in (chemical formula 6), refractive index raises.In addition, in the present embodiment, metal alkoxide and organic polymer equally also can adopt the foregoing description 1 described material.
Polymerization initiator only is contained in the organic polymer, solidifies promptly enough fully, but as required, by polymerization initiators such as 1-hydroxy cyclohexyl phenylketone are added in the hydrolytie polycondensation product of metal alkoxide, also may shorten set time.
Research changes the organic polymer mixing ratio below, to the influence of the refractive index of gained solidfied material.In above-mentioned operation (6), make with the blending ratio of viscous fluid (organic polymer) and above-mentioned product before the curing of comparative example 1 as shown in table 2, according to the mixing ratio that makes organic polymer is that 10 weight %, 20 weight % and 40 weight % mix, and uses illumination 30mW/cm
2Mercury light to this potpourri irradiation 4 minutes, make its curing, obtain solidfied material.Same as above, under the hot and humid environment of 85 ℃ of temperature, humidity 85%, the gained solidfied material carried out 500 hours burin-in process, measure before the burin-in process and the refractive index after the burin-in process, try to achieve variations in refractive index.Measurement result is as shown in table 2.
In addition, only to the viscous fluid before the curing of comparative example 1 (organic polymer) as described above the product behind overcuring similarly estimate, evaluation result shows that the organic polymer mixing ratio is 100%.
By the result shown in the table 2 as can be known, the mixing ratio by making organic polymer can reduce change of refractive in 20～40 weight % scopes, make its stabilization.
In above-mentioned operation (6), make with viscous fluid before the curing of comparative example 1 and above-mentioned product and mix according to 3: 7 ratio, the mixing ratio of organic polymer is controlled at 30 weight % in the above-mentioned scope.
In the present embodiment, in the resin that synthesizes by MPTES and DPhDMS, add trifluoroacetic anhydride, sneak into urethane acrylate resinoid, and be cured with comparative example 1.Its structure is as (chemical formula 7) and shown in Figure 1.
The method for making of sample is as described below.
(1) add the MPTES of 15.3ml and the DPhDMS of 6.34ml in the ethanol of 40ml, one side stirs the hydrochloric acid that one side drips the 2N of 3.8ml.
(2) then, add the trifluoroacetic anhydride of 1ml and the trimethylethoxysilane of 3.75ml, being stirred to does not have segregation phenomenon.
(3) after placing 24 hours, 100 ℃ of heating down, drying is removed trifluoroacetic anhydride and trimethylethoxysilane.
(4) will mix according to 4: 6 ratio with said mixture with viscous fluid before the curing of comparative example 1.
(5) use illumination 500mW/cm
2Mercury light to the composition that obtains as mentioned above irradiation 4 minutes, be cured.
In the present embodiment, owing to omitted the operation of removing the reaction residue that causes because of water, so the strand of major part in the trifluoroacetic acid that the trifluoroacetic anhydride hydrolysis generates and metal alkoxide forms hydrogen bond, remainder is present in the resin with the form of covalent bond.
Under the hot and humid environment of 85 ℃ of temperature, humidity 85%, said sample is carried out 500 hours burin-in process, measure the refractive index after the burin-in process.Measurement result is as shown in table 1.As shown in table 1, initial index of refraction is 1.5308, and the refractive index after the burin-in process is 1.5312, and change of refractive is+0.0004.Therefore, compare, can suppress change of refractive significantly with the situation that the urethane acrylate class is independent.In addition, in the present embodiment, metal alkoxide also can adopt with above-mentioned embodiment 1 described the same material with organic polymer.
Polymerization initiator only is contained in the organic polymer, solidifies promptly enough fully, but as required, by polymerization initiators such as 1-hydroxy cyclohexyl phenylketone are added in the hydrolytie polycondensation product of metal alkoxide, also may shorten set time.
Table 1
| Refractive index | |||
| Initially | After the burin-in process | Change | |
| Comparative example 1 | 1.5350 | 1.5338 | -0.0012 |
| | 1.5304 | 1.5303 | -0.0001 |
| | 1.5314 | 1.5315 | +0.0001 |
| | 1.5295 | 1.5293 | -0.0002 |
| | 1.5308 | 1.5312 | +0.0004 |
Table 2
| The organic polymer mixing ratio | Refractive index | ||
| Initially | After the burin-in | Change | |
| 10％ | 1.534 | 1.5348 | 0.0008 |
| 20％ | 1.5345 | 1.5348 | 0.0003 |
| 40％ | 1.5345 | 1.5343 | -0.0002 |
| 100％ | 1.5313 | 1.5302 | -0.0011 |
Fig. 2 is the sectional view of expression present embodiment lens.As shown in Figure 2, in the present embodiment, on the sphere 1a of mother metal spherical lens 1, setting has aspheric optical resin layer 2.Mother metal spherical lens 1 is the BK7 glass, has the sphere 1a of radius-of-curvature 5mm, diameter 5mm, focal length 9mm.Have aspheric optical resin layer 2 by on this sphere 1a, being provided with, form compound non-spherical lens.
Aspheric shape can be represented by the formula usually:
R: radius-of-curvature K: the constant of the cone
In following formula, A is called as the constant of the cone, is the major parameter of decision aspherical shape.In addition, R represents radius-of-curvature.In the present embodiment, be purpose to revise spherical aberration, the design aspheric surface, radius of curvature R is the same with the mother metal spherical lens, is 5mm, and constant of the cone K is-0.55.In addition, omitted high-order term.In the lens center, the thickness of optical resin layer 2 is 0.1mm.And the material of optical resin layer 2 uses the resin of the foregoing description 3.
Fig. 3 represents to use formation aspherics resin bed mother metal spherical lens 1 before, gathers the HeNe laser beam of wavelength 633nm, utilizes the beam analysis instrument to measure the result of the light intensity distributions of focal point.As shown in Figure 3, under the situation of using spherical lens 1, because spherical aberration can not be collected at light a bit.
Fig. 4 represents to use the compound non-spherical lens that is formed with aspherics resin bed 2 on spherical lens 1 shown in Figure 2, and is same as above, utilizes the beam analysis instrument to measure the result of the light intensity distributions of focal point.As shown in Figure 4, owing to use the compound non-spherical lens of present embodiment, therefore light can be collected on the small point.
Optical element of the present invention is not limited only to the described element of the foregoing description, can also be the diffraction optical element that for example is applied to be formed with at sheet glass or lens surface diffraction grating, the only lens that formed by optical resin, prism, diffraction optical element etc.In addition, it is that glass, SF are ordinary optical glass such as glass that the material of sheet glass or lens also can adopt BK glass, F outside the BK7 glass of present embodiment, for example OHARA Co., Ltd. makes optical glass such as S-TIH system, S-LAH system, S-LAL system, S-YGH system, perhaps plastics, high index of refraction light transparent ceramic etc.
In addition, optical material of the present invention can be used for: the various application resin materials that are coated with such as antireflection film; Optical component module resin materials such as LED, optical sensor, photo-coupler, optical chopper, reflective optical system; Photoswitch, light are received and dispatched optical component resin materials such as lens used in the optical communication equipments such as module, photo-coupler, optical fiber, optical waveguide, light filter; Optical component resin material such as used lens, microlens array, integraph, light guide plate in the display device such as LCD, plasma scope, OLED display, projector, projector; Comprise optical component resin materials such as plastic lens used in the shooting modules such as picture pick-up device, CCD shooting module, CMOS shooting module such as camera installation, video camera of digital camera etc. and compound non-spherical lens; And optical component resin material such as used plastic lens and compound non-spherical lens in the optical instrument such as telescope, microscope, contact lens, glasses, magnifier.
In the present embodiment, the mother metal lens material among the embodiment 5 is changed to optical plastic by BK7 glass.Plastic material uses cyclic olefin resins (Japanese ZEON Co., Ltd. system, commodity are called " ZEONEX ").The aspherical shape of mother metal lens shape and optical resin layer, identical with embodiment 5, the material of optical resin layer is also the same with embodiment 5, uses the resin of embodiment 3.Because the refractive index difference of mother metal, so focal length is 8.7mm.
In the present embodiment, also the same with embodiment 5, can obtain Fig. 3 and flux curve shown in Figure 4, light beam can be collected on the small point.
The use cyclic olefin resins (JSR Corp.'s system, commodity are called " ARTON "; Mitsui Chemicals, Inc's system, commodity are called " APEL "; And Poly Plastics Co., Ltd. system, commodity are called " TOPAS ") and fluorenes (fluorene) kind polyester resin (Osaka Gas Chemical Co., Ltd. system, commodity are called " OKP4 ") replace above-mentioned resin, form under the situation of optical resin layer, also can obtain aforesaid result.
In the present embodiment, the same with embodiment 5, on the mother metal spherical glass lens, form the optical resin layer of aspheric surface shape, not only carried out the correction of spherical aberration, and, form achromatic lens system by a compound type lens, also can reduce chromatic aberation.
Fig. 5 is the sectional view of the compound type lens 5 of the achromatic lens system of expression present embodiment.The two sides of glass lens mother metal 3 is the convex sphere, and lens diameter is 3mm, and the radius-of-curvature of first 3a is 3mm, and the radius-of-curvature of second 3b is 1.6mm.Use the resin material of embodiment 3, on second 3b, form optical resin layer 4.The radius-of-curvature of the aspheric surface 4a of optical resin layer 4 is 5.6mm, and the constant of the cone is 5.95.At the lens central portion, the thickness of optical resin layer 4 is 0.05mm.
In addition, make the compound type lens that the resin material that uses comparative example 1 forms optical resin layer 4, as a comparative example.Shape and size are substantially the same with the compound type lens of above-mentioned present embodiment, but because the refractive index difference of optical resin layer 4, so the constant of the cone is 5.45.
For the optically focused performance of the compound type lens of estimating present embodiment that use makes as mentioned above and comparative example, make photograph module as shown in Figure 6.In the bottom of metal framework 6 imaging apparatus (CCD) 8 is installed, is utilized fixture 7 that compound type lens 5 is installed in the opening 6a of imaging apparatus top, make the photograph module.
Use the present embodiment make as mentioned above and the photograph module of comparative example, shoot with video-corder the light of the white point light source that is arranged at far-end, one side is observed the output image of CCD, and one side is regulated and the position of fixed lens, makes the invocation point minimum.
Then, this shooting module is introduced in 85 ℃, 85% exerciser, is placed after 500 hours, shoot with video-corder the light of the white point light source that is arranged at far-end once more, the output image of observation CCD.
In the shooting module of the compound type lens that uses present embodiment, with the same before test is introduced, optically focused well.And in the shooting module of the compound type lens that uses comparative example, optically focused is insufficient, and focus departs from.
For the difference of compound type lens in above-mentioned high temperature and humidity test of the compound type lens and the comparative example of clear and definite present embodiment, utilize simulation (simulation) to ask for the figure of the focal point before and after the test.Particularly, utilize Image Synthesis by Ray Tracing, simulate by the mother metal lens of compound type lens and the surface configuration and the refractive index thereof of optical resin layer.
Fig. 7 represents the curve of the focal point of present embodiment, (a) is the curve before the high temperature and humidity test, (b) is the curve behind the high temperature and humidity test.And Fig. 8 represents the curve of comparative example, (a) is the curve before the high temperature and humidity test, (b) is the curve behind the high temperature and humidity test.
By the result of Fig. 7 and Fig. 8 as can be known, the compound type lens of present embodiment is compared with the compound type lens of comparative example, can be suppressed at weakening of optically focused performance under the hot and humid environment.
Fig. 9 is the structural drawing of the digital camera of the photograph module of expression use the foregoing description 7.By the simulating signal that the photographic element 8 of photograph module 9 sends, utilize AD converter 10 to be converted to digital signal, be sent to digital signal processor 11.Give display 12 from the digital signal transfers that digital signal processor 11 sends, carry out image and show.And deliver in the internal storage 14 and to store.In addition, digital signal processor 11 is connecting and is being used for and the outside external interface 13 that is connected.
Embodiment 9
Figure 10 uses the synoptic diagram of the projector architecture of composite optical element of the present invention for expression.In projector 20, be provided with illuminating lamp 21, the light that is positioned at illuminating lamp 21 penetrates the illuminating lens 22 of direction, LCD (LCD) 23.In the place ahead of LCD 23, be equipped with compound type lens 5.
Used compound type lens 5 adopts the system S-FPL51 of OHARA Co., Ltd. as the glass lens mother metal in the present embodiment, and lens diameter is 50mm, and first radius-of-curvature is 60mm, and second radius-of-curvature is 32mm.Use the resin of embodiment 3, form the optical resin layer of compound type lens 5 on second, radius-of-curvature is 112mm, and the constant of the cone is-2.5.In addition, at the lens central portion, the optical resin layer thickness is 2mm.
Because the projector of present embodiment uses compound type lens of the present invention, therefore, can be suppressed at weakening of lens performance under the hot and humid environment.
Figure 11 uses the diagrammatic cross-section of the light transmitting-receiving module of composite optical element of the present invention for expression.
One end 31a of optical fiber 31 inserts in the light transmitting-receiving module 30, with the relative position of optical fiber 31 1 end 31a, be provided with light-emitting component 33.In the place ahead of light-emitting component 33, be provided with and be equipped with according to compound type lens 5 of the present invention, between the end 31a of compound type lens 5 and optical fiber 31, the wavelength that is provided with 45 ° is selected light filter 32.Below wavelength selection light filter 32,, be provided with photo detector 35 across lens 34.
The light that penetrates from light-emitting component 33 is by compound type lens 5, and selects light filter 32 by wavelength, enters in the optical fiber 31 and is transmitted from end 31a.
In addition, the light of importing from optical fiber 31 passes through end 31a, selects light filter 32 reflections by wavelength, and scioptics 34 are received by photo detector 35.
In the present embodiment, using oscillation wavelength is that the semiconductor laser of 1.3 μ m is as light-emitting component 33.The light that is sent by light-emitting component 33 uses according to compound type lens 5 of the present invention, makes efficiently to be transmitted into optical fiber 31.Use the glass lens mother metal of BK7 glass as compound type lens 5.The lens diameter of glass lens mother metal is 2mm, and the aspheric curvature radius of first, second and optical resin layer is 1.2mm.The aspheric constant of the cone of optical resin layer is-3.5.At the lens central portion, the optical resin layer thickness is 0.1mm.
In addition, for relatively,, make the light transmitting-receiving module same with present embodiment except that adopting the resin that uses comparative example 1 to form the comparison compound type lens of optical resin layer.
At once, no matter be present embodiment or the light of comparative example transmitting-receiving module after making module, the output light of semiconductor laser and the joint efficiency of optical fiber all are about 60%.These light transmitting-receiving modules are inserted in 85 ℃, 85% exerciser, place after 500 hours, measure the joint efficiency of the output light of semiconductor laser more as described above.Be about 60% in the present embodiment, almost do not change, and in the light transmitting-receiving module of comparative example, joint efficiency is reduced to about 45%.Hence one can see that, by using according to compound type lens of the present invention, even can obtain also demonstrating the light transmitting-receiving module of stable light Transceiver Features under hot and humid condition.
Claims (16)
1. optical resin material, hydrolytie polycondensation product and volatility low molecular composition that it contains the metal alkoxide that has a hydroxyl in the molecule at least is characterized in that:
Described volatility low molecular composition have can with the group of the hydroxyl Cheng Jian of the hydrolytie polycondensation product of described metal alkoxide.
2. optical resin material as claimed in claim 1 is characterized in that: also contain organic polymer.
3. optical resin material as claimed in claim 1 is characterized in that: the group of described low molecular composition is carboxylic acid group, carbonyl or hydroxyl.
4. optical resin material as claimed in claim 1 is characterized in that:
Key between the hydroxyl of the hydrolytie polycondensation product of described metal alkoxide and the group of described low molecular composition forms by hydrogen bond or polycondensation.
5. optical resin material as claimed in claim 1 is characterized in that: described low molecular composition is metal alkoxide, organic acid, alcohol or the ketone of contain fluorine atoms.
6. optical resin material as claimed in claim 2 is characterized in that:
Described organic polymer be selected from acrylic resin, epikote, at least a resin in epoxy acrylic esters resin and the polyurethanes resin.
7. optical resin material as claimed in claim 1 is characterized in that:
The hydrolytie polycondensation product of described metal alkoxide contains two keys, and by the irradiation energy line, this pair key generation polymerization is also solidified.
8. optical resin material as claimed in claim 2 is characterized in that:
Described organic polymer contains two keys, and by the irradiation energy line, this pair key generation polymerization is also solidified.
9. optical resin material as claimed in claim 1 is characterized in that:
The hydrolytie polycondensation product of described metal alkoxide contains two keys, before the irradiation energy line, is its uncured state.
10. optical resin material as claimed in claim 2 is characterized in that: described organic polymer contains two keys, before the irradiation energy line, is its uncured state.
11. optical resin material as claimed in claim 1 is characterized in that:
Variations in refractive index under the hot and humid environment of 85 ℃ of temperature, humidity 85% be per 500 hours below ± 0.001.
12. an optical element is characterized in that: use the described optical resin material of claim 1.
13. a composite optical element is characterized in that: be formed with the optical resin layer that constitutes by the described optical resin material of claim 1 on the mother metal surface.
14. composite optical element as claimed in claim 13 is characterized in that: described mother metal is lens, and described optical resin layer is formed on the optical surface of described lens.
15. composite optical element as claimed in claim 13 is characterized in that: described mother metal is made of glass, plastics, light transparent ceramic or optical crystal.
16. optical devices is characterized in that: comprise the described composite optical element of claim 13.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005287560 | 2005-09-30 | ||
| JP2005287560 | 2005-09-30 | ||
| JP2006208326 | 2006-07-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1940598A true CN1940598A (en) | 2007-04-04 |
Family
ID=37958951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610159970 Pending CN1940598A (en) | 2005-09-30 | 2006-09-28 | Optical material and optical element |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1940598A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107206271A (en) * | 2014-11-21 | 2017-09-26 | 洪国际有限公司 | dart board and dart board control device with light source |
| CN113462947A (en) * | 2021-06-18 | 2021-10-01 | 厦门钨业股份有限公司 | WC-based hard alloy and application thereof |
-
2006
- 2006-09-28 CN CN 200610159970 patent/CN1940598A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107206271A (en) * | 2014-11-21 | 2017-09-26 | 洪国际有限公司 | dart board and dart board control device with light source |
| CN113462947A (en) * | 2021-06-18 | 2021-10-01 | 厦门钨业股份有限公司 | WC-based hard alloy and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100346189C (en) | Image pickup lens | |
| CN1670548A (en) | Optical waveguide and the method of fabricating the same | |
| JP2007122016A (en) | Optical material and optical element | |
| JPWO2012008357A1 (en) | Imaging lens | |
| CN1668049A (en) | Portable device | |
| CN1930508A (en) | Zoom lens and imaging device using zoom lens | |
| CN101038413A (en) | Imaging lens | |
| CN101051111A (en) | Projection lens and projection type display device using the same | |
| TW201403119A (en) | Imaging Optical System, Imaging Device, and Digital Apparatus | |
| CN1782773A (en) | Optical system for high resolution using plastic lenses | |
| CN1841115A (en) | Zoom lens system | |
| CN1975503A (en) | Zoom lens system, imaging device and shooting apparatus | |
| CN1975502A (en) | Objective lens for endoscope | |
| CN1367879A (en) | Resin-bond type optical element, production method therefor and optical article | |
| CN1591075A (en) | Zoom lens system | |
| CN1388823A (en) | Adhesive composition and optical device using the same | |
| CN1766690A (en) | Minisize camera lens system | |
| CN1573378A (en) | Gradient-index lens and composite optical element utilizing the same | |
| CN1067770C (en) | Wide-angle zoom lens | |
| CN1093642C (en) | Mini-focal optical lens | |
| CN1392430A (en) | Objective lens, optical pick-up device and recording and/or reproducing device | |
| CN1788220A (en) | Optical system and imaging device | |
| CN1616523A (en) | Organometallic polymer material and process for preparing the same | |
| CN1940598A (en) | Optical material and optical element | |
| CN1305115A (en) | Variable focus lens system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20070404 |