CN101134818A - Material for forming organic inorganic compound, organic inorganic compound and optical element using the same - Google Patents
Material for forming organic inorganic compound, organic inorganic compound and optical element using the same Download PDFInfo
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- CN101134818A CN101134818A CNA2007101478222A CN200710147822A CN101134818A CN 101134818 A CN101134818 A CN 101134818A CN A2007101478222 A CNA2007101478222 A CN A2007101478222A CN 200710147822 A CN200710147822 A CN 200710147822A CN 101134818 A CN101134818 A CN 101134818A
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Abstract
The invention provides a material for forming organic-inorganic composite, which is characterized in that the material comprises a fluorene compound containing acryloyl or methacryloyl, acrylic acid (ester) monomers besides the fluorene compound, metal oxide particles, alkylamine and photopolymerization initiator containing phenyl and organic amine.
Description
Technical field
The organic mineral complex that the present invention relates to contain metal oxide microparticle, can form the organic mineral complex with high refractive index forms uses material, makes its polymerization obtain organic mineral complex, and optical element.
Background technology
Because non-spherical lens can reduce the aberration of lens, so can reduce employed lens, can realize miniaturization, lightweight, the cost degradation of product.Therefore, in having the portable phone of photographic camera, digital camera etc., the needs of non-spherical lens are increased to some extent.
The non-spherical lens of glass utilizes the manufacturing of grinding very difficult, uses the mold glass of low melting glass also to have problems such as metal pattern life-span weak point, is not suitable for low cost, mass production.
On the other hand, resinous non-spherical lens is with glassy phase specific volume easy-formation, have mass production.But organic compound is removed outside halogenide, the sulfide etc., even have the base that phenyl etc. improves specific refractory power, at most also only to 1.6, the refractive index ratio glass of resin is little for specific refractory power.Therefore, using resin to make under the situation of non-spherical lens, existing the degree of freedom of product design to descend, be difficult to realize miniaturization, light-weighted problem.
As the method that improves the resin specific refractory power, the known ZrO that in resin, sneaks into
2, Nb
2O
5, TiO
2The method of the nano particle of the metal oxide high etc. specific refractory power.ZrO is disclosed in TOHKEMY 2005-306641 communique and TOHKEMY 2003-192348 communique etc.
2, Nb
2O
5, TiO
2Dispersion liquid Deng metal oxide nanoparticles.
In the dispersion liquid of these metal oxide nanoparticles, contain organic carboxyl acid and organic amine, metal oxide nanoparticles disperses in organic solvents such as ethanol easily.In addition, be dispersed in the ethanol the niobium oxides dispersion liquid with the commodity " バ イ ラ-Le " by name produced of many wooden chemistries society etc. by commercially available.
In resin the mixed metal oxide nano particle, make when having the resin of high refractive index, have two following problems.
First problem is, owing to mixed metal oxide nano particle in resin, the problem of the intensity variation of resin.Under secular high temperature, high humidity environment or be in repeatedly in the high temperature one cryogenic thermal cycling test, there is the problem that cracks etc.Particularly the content of nano particle is many more, is easy to generate crackle more.
Second problem is that the water-soluble height of these metal oxides easily with water-soluble high mixed with resin, but is difficult to mix with non-water-soluble resin.If mixed metal oxide nano particle in non-water-soluble resin the nano particle aggegation will occur, produce the problem of gonorrhoea.The resin that contains more phenyl or naphthyl, because the specific refractory power height, so can make the high resin combination of specific refractory power.But, contain the resin of phenyl or naphthyl, become non-water-soluble resin easily, so be difficult to the dispersing metal oxides nano particle.Therefore, in order to make resin combination with high refractive index, even mixed metal oxide nano particle in the resin with more phenyl or naphthyl is because the dispersion state of metal oxide nanoparticles is poor, so problems such as resin combination deposits yields gonorrhoea occur.
On the other hand, if, just can access dispersion state preferably, but in order to obtain high refractive index to not or mixed metal oxide nano particle in the resin of less phenyl or naphthyl is arranged, need the heavy addition metal oxide nanoparticles, the problem of generation tree oil/fat composition strength degradation.
For above-mentioned reason, in the prior art, make metal oxide nanoparticles with good dispersion state be blended in contain more phenyl or naphthyl resin for example fluorenes be to be unusual difficulty in the high resin of specific refractory power such as resin.
Summary of the invention
The object of the present invention is to provide a kind of make metal oxide microparticle be dispersed in fluorenes be in the resin and gonorrhoea does not take place, the organic mineral complex that can form the organic mineral complex with high refractive index forms and to use material, the organic mineral complex that obtains with making its polymerization, and the optical element that uses this complex body.
Organic mineral complex of the present invention forms and is characterised in that with material, contains: have the fluorenes based compound of acryl or methacryloyl, vinylformic acid (ester) class monomer, metal oxide microparticle, alkylamine, the organic amine with phenyl and the Photoepolymerizationinitiater initiater beyond this fluorenes based compound.
In the present invention, because contain alkylamine and have the organic amine of phenyl, so can improve the dispersiveness of metal oxide microparticle, even metal oxide microparticle is dispersed in the fluorenes based compound, gonorrhoea can not take place, can mix with good dispersion state yet.
The inventor thinks, because alkylamine can improve the dispersiveness to organic system solvent and resin.And the inventor thinks, owing to have the organic amine of phenyl, can also improve the dispersiveness to non-water-soluble resin.Therefore, by adjusting alkylamine and having the organic amine blending ratio of phenyl, can control the dispersiveness of metal oxide microparticle.
As alkylamine, can use disclosed amine compound in patent documentation 1 and the patent documentation 2.Particularly, can primary amines such as ethamine, propylamine, allylamine, butylamine, amylamine, octylame, 3 methoxypropyl amine, aniline be shown example, secondary amine compounds such as diethylamine, dipropyl amine, diallylamine, dibutylamine, N-carbinol methine amine, triethylamine, tripropyl amine, triallylamine, trolamine, N, tertiary amine compound and quarternary ammonium salt compounds such as tetramethyl ammonium hydroxide, chlorination trimethyl ammonium such as N-dimethylethanolamine.Wherein, in these ammonium compounds, from solvability and reactive viewpoint, the most preferred primary, second month in a season and alkyl amine compound.As particularly preferred amine compound, can the butylamine of primary amine, the dibutylamine of secondary amine compound, the tripropyl amine of tertiary amine compound be shown example, but be not limited to this.
As mentioned above, owing to contain the organic amine with phenyl, the good dispersion in the fluorenes based compound that has more phenyl also is difficult to take place gonorrhoea even add metal oxide microparticle.As organic amine, can list aniline, pentanoic etc. with phenyl.
Organic mineral complex of the present invention forms the content with alkylamine in the material, amount with respect to niobium oxides contained in the organic mineral complex, be preferably the scope of mol ratio 0.2～2, form with respect to organic mineral complex and use material, be preferably below the 5 weight %.If alkylamine content is very few, may cause descending for the dispersiveness of organic system solvent and resin.In addition, if the content of alkylamine greater than 5 weight %, may cause the strength degradation of organic mineral complex.
In addition, the organic amine content with phenyl is preferably the scope of 2～5 weight %.If it is very few to have the organic amine content of phenyl, may cause descending to the dispersiveness of fluorenes based compound.If content is too much, the strength degradation of organic mineral complex may cause easily cracking owing to thermal shocking etc.
Organic mineral complex of the present invention forms with the fluorenes based compound that uses in the material, has acryl or methacryloyl, is the compound that the two aryl fluorenes with structure as follows are basic framework.
Particularly, for example, can list in general formula as follows, at R
1And R
2The position possess substituent compound with propenyl or methacryloyl etc.
As common commercially available fluorenes based compound, can list compound with structure as follows.N and m are usually in 1～5 scope.
In an embodiment, the trade(brand)name " ォ グ ソ-Le EA-0200 " (production of Osaka Gas Chemicals society) as the fluorenes based compound has structure as follows.
Wherein, the fluorenes based compound of said structure (9,9-two [4-(2-acryl oxygen oxyethyl group) phenyl]) fluorenes is with trade(brand)name: " NK ester A-BPEF " (production of Xin Zhong village chemical industry society) is by commercially available.
The content of fluorenes based compound is preferably the scope of 30～85 weight %.If the content of fluorenes based compound is very few, because the fluorenes based compound is the high refractive index composition, so can not obtain the organic mineral complex of high refractive index sometimes.And if the content of fluorenes based compound is too much, the content of metal oxide microparticle reduces relatively, can not form the organic mineral complex with high refractive index sometimes.
The vinylformic acid of Shi Yonging (ester) class monomer is vinylformic acid (ester) the class monomer beyond the above-mentioned fluorenes based compound in the present invention, can be polyfunctional vinylformic acid (ester) class monomer, also can be vinylformic acid (ester) the class monomer of simple function.Preferably, contain vinylformic acid (ester) the class monomer or the oligopolymer of multifunctional vinylformic acid (ester) class monomer or oligopolymer and simple function as vinylformic acid (ester) class monomer.Wherein, in present specification, vinylformic acid (ester) class monomer is the monomer with acryl or methacryloyl.
Owing to contain polyfunctional vinylformic acid (ester) class monomer or oligopolymer, can improve cross-linking density, can make owing to contain the crosslinked radix increase of the per unit volume that metal oxide microparticle descends.
In addition, owing to contain vinylformic acid (ester) the class monomer or the oligopolymer of simple function, the flexibility of organic mineral complex increases, and can improve the resiliency to physical impact.
As the monomeric preference of multifunctional vinylformic acid (ester) class, can list the pentaerythritol triacrylate of trifunctional.In addition, the preference as the acrylate monomer of simple function can list benzyl methacrylate (benzyl methacrylate).Preferably combination is used pentaerythritol triacrylate and benzyl methacrylate.Because pentaerythritol triacrylate has the OH base, so can improve the dispersiveness of metal oxide microparticle.
And situation with vinylformic acid (ester) the class monomer of multifunctional vinylformic acid (ester) class monomer or oligopolymer and simple function or oligopolymer under, preferred its ratio of mixture (multifunctional: simple function) with weight ratio be illustrated in 1: 3～3: 1 scope in, can in this scope, according to circumstances change weight ratio, adjust the flexibility of resin.
In addition, as polyfunctional acrylic ester, can use dual functional acrylate.Dual functional acrylate be can also only use, and polyfunctional acrylic ester and monofunctional acrylate do not made up.Bifunctional acrylate as this moment preferably uses acrylate such as dipropylene glycol diacrylate, 1,6 hexanediol diacrylate, tri (propylene glycol) diacrylate.And, not only can use acrylate, also can use methacrylic ester.
The vinylformic acid that uses among the present invention (ester) class monomer so long as have the monomer of acryl or methacryloyl, can use ad lib; usually; because the fluorenes based compound has high viscosity, so under situations such as use metal pattern formation lens, be difficult to sometimes handle.In order to reduce the viscosity of all material, the preferred use monomer lower than the viscosity of oligopolymer also can use as thinner by the monomer that viscosity is low.
Organic mineral complex of the present invention forms the scope that is preferably 10～35 weight % with the monomeric content of the vinylformic acid in the material (ester) class.For the intensity that improves the organic mineral complex that polymerization obtains, prevent to crack and add vinylformic acid (ester) class monomer, so, cause mechanical strength of resin to descend, be easy to generate crackle sometimes if the monomeric content of vinylformic acid (ester) class is very few.And if the monomeric content of vinylformic acid (ester) class is too much, because the monomeric specific refractory power of vinylformic acid (ester) class is low usually, so be difficult to form organic mineral complex sometimes with high refractive index.
As the metal oxide microparticle among the present invention, can list ZrO
2, Nb
2O
5, TiO
2Deng metal oxide nanoparticles.Especially preferably use Nb
2O
5Nano particle.Nb
2O
5The nano particle of (niobium oxides) with ethanol dispersive niobium oxides nanoparticulate dispersion by commercially available.For example, as mentioned above, the trade(brand)name " バ イ ラ-Le " of producing with many wooden chemistries society is by commercially available.In these commercially available products, also comprise and contain the commercially available product of alkylamine as dispersion agent.
The content of metal oxide microparticle is preferably in the scope of 1～30 weight %.If the content of metal oxide microparticle is very few, can't form the organic mineral complex of high refractive index sometimes.And if the content of metal oxide microparticle is too much, cause the intensity of organic mineral complex just to descend sometimes, be easy to generate crackle.
Form with in the material at organic mineral complex of the present invention, in the scope of not damaging effect of the present invention, also can contain other composition.
Be antioxidant particularly by containing hindered phenol, the organic mineral complex that can suppress to make organic mineral complex to form to obtain with the material polymerization through the time variation flavescence that causes.As hindered phenol is the content of antioxidant, preferably in the scope of 0.1～0.3 weight %.Because contain metal oxide microparticles such as niobium oxides, flavescence takes place in organic mineral complex easily.
Organic mineral complex of the present invention is characterised in that, the organic mineral complex formation of the invention described above is obtained with the material polymerization.
Organic mineral complex of the present invention for example, can make the organic mineral complex of the invention described above form with material and carry out photopolymerization and obtain.Usually irradiation ultraviolet radiation makes its polymerization and obtains.Particularly as described later, preferred illumination wavelength is that the above ultraviolet ray of 365nm makes its polymerization.
Optical element of the present invention is characterised in that, uses the organic mineral complex of the invention described above.As optical element, can list optical lens, diffraction grating, hologram component, prism element, antireflection multilayer film, guided wave element etc.
In addition, as optical element, can list the compound non-spherical lens that on base material, is formed with the optical resin layer that the organic mineral complex by the invention described above constitutes.
Optical devices of the present invention are characterised in that, use the optical element of the invention described above.As Optical devices of the present invention, for example, can list optical communication equipments such as photoswitch, light transceiver breath module, opticcoupler, display unit such as liquid-crystal display, plasma display, OLED display, projector, projector, opticses such as microlens array, totalizing instrument, light guiding plate, photographic cameras such as digital camera, camera heads such as pick up camera, photographing modules such as CCD camera module, CMOS camera module, opticinstruments such as visual telescope, microscope, magnifying glass etc.
The manufacture method of organic mineral complex of the present invention is characterised in that, use the organic mineral complex formation material of the invention described above, make organic mineral complex, comprising: the operation of modulating the dispersion liquid of the above-mentioned metal oxide microparticle that contains abovementioned alkyl amine and above-mentioned organic amine; Mix aforesaid propylene acid (ester) class monomer, above-mentioned Photoepolymerizationinitiater initiater and above-mentioned fluorenes based compound in this dispersion liquid, the modulation organic mineral complex forms the operation with material; With above-mentioned organic mineral complex is formed use the material polymerization, the operation of formation organic mineral complex.
Adopt manufacture method of the present invention, can make metal oxide microparticle be dispersed in fluorenes is in the resin and gonorrhoea does not take place, and can make the organic mineral complex with high refractive index.
When material is used in the above-mentioned organic mineral complex formation of modulation, can use solvent.As solvent, so long as can dissolve the solvent of each organic composition, there is no particular limitation, for example, can list acetone, methylethylketone, mibk etc.
In manufacture method of the present invention, preferred irradiation ultraviolet radiation forms organic mineral complex and uses the material polymerization, forms organic mineral complex.In this case, more preferably illumination wavelength is that the above ultraviolet ray of 365nm makes its polymerization.As illumination wavelength is ultraviolet method more than the 365nm, for example, can list the spectral filter that uses wavelength to see through as the ultraviolet ray more than the 365nm, the method for irradiation ultraviolet radiation etc.As spectral filter, can enumerate the absorption-type spectral filter that the above ultraviolet ray of the specific wavelength of sening as an envoy to sees through or only make linear interference light filter that specific wavelength sees through etc.
The invention effect
According to the present invention, can make metal oxide microparticle be dispersed in fluorenes is in the resin and gonorrhoea does not take place, and can form the organic mineral complex with high refractive index.
Description of drawings
Fig. 1 is the sectional view that schematically shows the optical element of the embodiment of the invention.
Fig. 2 is the sectional view that schematically shows the Optical devices camera module of the embodiment of the invention.
Fig. 3 is the sectional view that two fold-type portable phones of existing camera module are disposed in expression.
Fig. 4 is the sectional view of the portable phone of the expression embodiment of the invention.
Fig. 5 is the sectional view that schematically shows the diffraction grating of optical element embodiment of the present invention.
Embodiment
Below, utilize specific embodiment explanation the present invention, but the invention is not restricted to following embodiment.
The Nb that in following embodiment and comparative example, uses
2O
5Nanoparticulate dispersion and TiO
2Nanoparticulate dispersion such as modulated.
＜Nb
2O
5The modulation of nanoparticulate dispersion 〉
(many wooden chemistries society produces, Nb to commercially available oxalic acid stable form niobium oxides colloidal sol
2O
5=10.2 weight %, oxalic acid/Nb
2O
5(mol ratio)=0.62) adds the citric acid monohydrate compound in, make citric acid/Nb
2O
5(mol ratio)=0.20 is used ammonia soln (15 weight %) then, and pH is adjusted into 8.5.Use ultra-filtration equipment (society of Asahi Chemical Industry produces for microza UF (マ イ Network ロ one ザ UF), model SLP-1053), this colloidal sol is carried out ultrafiltration, Nb
2O
5Concentration be adjusted into 20 weight %.Then, add the citric acid monohydrate compound, make citric acid/Nb
2O
5(mol ratio)=0.15.The oxalic acid one citric acid stabilization niobium oxides colloidal sol that obtains, pH is 3.8, citric acid/oxalic acid (mol ratio)=1.94, oxalic acid/Nb
2O
5(mol ratio)=0.18.The niobium oxides concentration of the colloidal sol that obtains is 10 weight %.
The 200g oxalic acid one citric acid stable form niobium oxides colloidal sol that operation like this is obtained stirs on one side, Yi Bian add n-Butyl Amine 99, makes n-Butyl Amine 99/Nb
2O
5(mol ratio)=0.6.To wherein adding 600g ethanol, carry out concentration operation repeatedly 4 times with Rotary Evaporators, making total amount is about 200g, improves organic solvent replacement rate gradually.Then, being concentrated to total amount is 130g, obtains Nb
2O
5Concentration is that 30.5 weight %, water ratio are that 1.9 weight %, median size are that 10.2nm, mist rate are 6.7%, viscosity is the ethanol decentralized niobium oxides dispersion liquid of 13.5cp.Use ethanol that it is adjusted, make Nb
2O
5Concentration is 20 weight %, obtains Nb
2O
5Nanoparticulate dispersion.
＜TiO
2The modulation of nanoparticulate dispersion 〉
To the 2000g titanium oxychloride aqueous solution (TiO
2=2 weight %) in, under stirring at normal temperature, slowly add 2212g ammoniacal liquor (NH
3=2 weight %) (NH
3/ Cl equivalence ratio=1.3), generate titanic hydroxide gel.It is filtered washing, and chlorion is with respect to titanium gel (TiO in filtrate
2) be below the 100ppm, to obtain TiO
2=10 weight %, NH
3The gel of=0.3 weight %.
In this titanium oxide gel of 400g, add 3.66g n-Butyl Amine 99 (n-Butyl Amine 99/TiO
2Mol ratio=0.1) and the 70 weight % oxyacetic acids of 27.2g (society produces with the pure pharmaceutical worker of light industry), makes oxyacetic acid/TiO
2(mol ratio)=0.5 adds it in autoclave, carries out 6 hours hydrothermal treatment consists under 120 ℃, obtains crystalline titanium oxide colloidal sol (TiO
2=9.3 weight %).Then, in this colloidal sol of 100g, add ethanol, carry out component distillation repeatedly, obtain ethanol decentralized TiO
2Nanoparticulate dispersion.This dispersion liquid is analyzed result, TiO
2=20 weight %, n-Butyl Amine 99=1.5 weight %, oxyacetic acid=5.7 weight %, n-Butyl Amine 99/TiO
2(mol ratio)=0.08, oxyacetic acid/TiO
2(mol ratio)=0.3, the amount of moisture in the dispersion medium are 4 weight %.
(embodiment 1)
(1) to the above-mentioned Nb of 0.5ml
2O
5In the nanoparticulate dispersion, add 0.028ml aniline, 0.049ml pentaerythritol triacrylate, 0.096ml benzyl methacrylate, 0.016g Photoepolymerizationinitiater initiater (trade(brand)name: " Irgacure (イ Le ガ キ ュ ア) 184 ") successively while stirring, under 90 ℃, heat, make ethanol evaporation.Add the 1ml acetone solution in the liquid after removing ethanol, obtain liquid (A) with viscosity.
(2) the difunctionality fluorenes with 0.582g is that acrylate (Osaka Gas Chemicals society produces, trade(brand)name: " just グ ソ one Le EA-0200 ") is dissolved in the 1ml acetone, obtains liquid (B).
(3) in liquid (A), add liquid (B), under 90 ℃, make acetone evaporated, placed 30 minutes down at 110 ℃ then, remove residual acetone fully, obtain organic mineral complex formation material.
The above-mentioned organic mineral complex of expression forms the content with each composition of material in the table 1.
Table 1
| Composition | Content (weight %) |
| Nb 2O 5 | 11.2 |
| Aniline | 3.0 |
| Pentaerythritol triacrylate | 5.5 |
| Benzyl methacrylate | 10.5 |
| Irgacure 184 | 1.8 |
| EA0200 | 63.1 |
| Contained n-Butyl Amine 99 in the dispersion liquid | 2.1 |
| Contained other dispersion agent in the dispersion liquid | 2.7 |
Use the material irradiation ultraviolet radiation to above-mentioned organic mineral complex formation, make its polymerizing curable, obtain organic mineral complex.Measure the specific refractory power and the Abbe number of this organic mineral complex, specific refractory power is 1.63, and Abbe number is 26.
With in the material, aniline content is 3 weight %, changes the aniline amount of adding in above-mentioned organic mineral complex formation, modulates the organic mineral complex formation material that aniline content is 2 weight %, 5 weight % and 10 weight % with above-mentioned same operation.
On glass at the BK7 that is coated with organic silane coupling agent, coating aniline content is each organic mineral complex formation material of 2 weight %, 3 weight %, 5 weight % and 10 weight %, irradiation ultraviolet radiation solidifies it, and forming thickness is the tabular organic mineral complex of 120 μ m.
The transmitance of each organic mineral complex that mensuration obtains, result, the transmitance under the wavelength 430nm, aniline content is that the complex body of 2 weight % is 74%, the complex body of 3 weight % is that the complex body of 82%, 5 weight % is that the complex body of 80%, 10 weight % is 79%.When aniline content was 2 weight %, transmitance descended slightly, but can confirm to form as a whole transparent resin.
Give fierce temperature variation to above-mentioned tabular organic mineral complex again, research has or not and cracks.Fierce temperature variation is undertaken by promptly move each circulation in the freezing tank of 120 ℃ high temperature groove and-50 ℃.Maintenance is after 20 minutes down at 120 ℃, and maintenance is 20 minutes under-50 ℃, keeps 20 minutes down at 120 ℃ again, is taken out to room temperature then, the surface of observation organic mineral complex.As a result, when aniline content is 2 weight %, 3 weight % and 5 weight %, in organic mineral complex surface variation unconfirmed.With respect to this, aniline content is the complex body of 10 weight %, cracks on the surface of organic mineral complex.
(comparative example 1)
Except not adding aniline, to operate equally with the foregoing description 1, the modulation organic mineral complex forms uses material.
The organic mineral complex that obtains forms and uses material, and the aggegation of niobium oxides nano particle is the gonorrhoea state.Therefore, specific refractory power and Abbe number average can not be measured.
(embodiment 2)
Except being the Nb of 0.5ml
2O
5(the first industrial pharmacy society produces for nanoparticulate dispersion, 0.028ml aniline, 0.01ml pentaerythritol triacrylate, 0.148g hydroxyethyl tribromophenol acrylate, trade(brand)name: " ニ ュ one Off ロ Application テ ィ ア BR-31 "), beyond the 0.015g Photoepolymerizationinitiater initiater, operate equally with the foregoing description 1, the modulation organic mineral complex forms uses material.
Use the material irradiation ultraviolet radiation to the organic mineral complex formation that obtains, make its curing, obtain organic mineral complex.Measure specific refractory power and Abbe number, specific refractory power is 1.63, and Abbe number is 26.
In addition, operate equally with the foregoing description 1, making thickness is the tabular organic mineral complex of 120 μ m, gives fierce temperature variation, studies to have or not to crack the generation of result's crackle unconfirmed.
(embodiment 3)
In the present embodiment, be the combination example in addition of polyfunctional acrylic ester and monofunctional acrylate as vinylformic acid (ester) class monomer, bifunctional acrylate's example is used in expression.
Except using the Nb of 0.5ml
2O
5Beyond nanoparticulate dispersion, 0.028ml aniline, 0.12ml dipropylene glycol diacrylate, the 0.015g Photoepolymerizationinitiater initiater, operate equally with the foregoing description 1, the modulation organic mineral complex forms uses material.
With above-mentioned same operation, measure the specific refractory power and the Abbe number of organic mineral complex, result, specific refractory power are 1.62, Abbe number is 26.
In addition, with above-mentioned same operation, give fierce temperature variation, research has or not and cracks the generation of result's crackle unconfirmed.
(embodiment 4)
(1) to the above-mentioned TiO of 0.6ml
2In the nanoparticulate dispersion, add 0.1ml benzyl methacrylate, 0.016g Photoepolymerizationinitiater initiater (trade(brand)name: " Irgacure184 ") successively while stir, and be heated to 90 ℃, make ethanol evaporation.Add the 1ml acetone solution in the liquid after removing ethanol, obtain liquid (A) with viscosity.
(2) be that acrylate is dissolved in the 1ml acetone with 0.582g and above-mentioned same difunctionality fluorenes, obtain liquid (B).
(3) in liquid (A), add liquid (B) and 0.045ml aniline, under 90 ℃, make acetone evaporated, kept 30 minutes down, remove residual acetone fully, obtain organic mineral complex formation material at 110 ℃.
Use the material irradiation ultraviolet radiation to this organic mineral complex formation, make its curing, form organic mineral complex.Measure the specific refractory power and the Abbe number of this organic mineral complex, result, specific refractory power are 1.65, and Abbe number is 25.
(embodiment 5)
(1) to the above-mentioned Nb of 0.5ml
2O
5In the nanoparticulate dispersion, to add 0.028ml aniline, 0.049ml pentaerythritol triacrylate, 0.096ml benzyl methacrylate, 0.014g Photoepolymerizationinitiater initiater (trade(brand)name: " Irgacure 184 "), 0.003g hindered phenol successively be antioxidant (trade(brand)name: " Sumilizer (ス ミ ラ イ ザ one) GA-80 " while stirring, Sumitomo Chemical society produces), be heated to 90 ℃, make the ethanol volatilization.Add the 1ml acetone solution in the liquid after removing ethanol, obtain liquid (A) with viscosity.
(2) will be added with 0.003g sulphur in advance is secondary antioxidant (trade(brand)name: " SumilizerTP-D ", the production of Sumitomo Chemical society) difunctionality fluorenes is that (Osaka Gas Chemicals society produces acrylate, trade(brand)name: " just グ ソ one Le EA-0200 ") 0.582g is dissolved in the 1ml acetone, obtains liquid (B).
(3) in liquid (A), add liquid (B), under 90 ℃, make acetone evaporated, placed 30 minutes down at 110 ℃ then, remove residual acetone fully, obtain organic mineral complex formation material.The above-mentioned organic mineral complex of expression forms the content with each composition of material in the table 2.
Table 2
| Composition | Content (weight %) |
| Nb 2O 5 | 11.2 |
| Aniline | 3.1 |
| Pentaerythritol triacrylate | 10.8 |
| Benzyl methacrylate | 5.4 |
| Irgacure 184 | 1.5 |
| EA0200 | 62.8 |
| Contained n-Butyl Amine 99 in the dispersion liquid | 2.1 |
| Contained other dispersion agent in the dispersion liquid | 2.7 |
| Sumilizer GA-80 | 0.3 |
| Sumilizer TP-D | 0.3 |
Use the material irradiation ultraviolet radiation to above-mentioned organic mineral complex formation, make its polymerizing curable, obtain organic mineral complex.Measure the specific refractory power and the Abbe number of this organic mineral complex, specific refractory power is 1.63 as a result, and Abbe number is 26.
[to the evaluation of organic mineral complex flavescence]
On the substrate that constitutes by pyrex, be coated with above-mentioned organic mineral complex formation and use material, irradiation ultraviolet radiation that it is solidified, forming thickness is the film of the organic mineral complex of 140 μ m.As ultraviolet light source, the SP-7 that uses USHIO society to produce, use the absorption-type spectral filter, block wavelength that ultrahigh pressure mercury lamp that the SP-7 that produces from USHIO society uses sends wavelength components less than 365nm, for example 254nm, 313nm etc., the ultraviolet ray that illumination wavelength 365nm (I ray) is above is solidified.After the curing, under 120 ℃, cured 6 hours, remove residual volatile components such as acetone.
To the organic mineral complex sample that obtains, measure the transmitance under the wavelength 430nm, be 80.2%.By high temperature and humidity test (85 ℃-85%), this sample is carried out 500 hours accelerated tests, measure the transmitance under the 430nm once more, be 79.1%.Therefore, before the test of high temperature and humidity test and after the test is-1.1% through rate variance, does not almost change, and can confirm that flavescence is very low.
(embodiment 6～17)
Except the additive shown in the table 3 that uses addition shown in the table 3, replace operating equally with the foregoing description 5 beyond SumilizerGA-80 and the Sumilizer TP-D additive, form organic mineral complex formation material.
The organic mineral complex that use obtains forms and uses material, operates equally with the foregoing description 5, makes the sample of organic mineral complex.But,, when irradiation ultraviolet radiation, do not use spectral filter to shine to embodiment 7～16.Therefore, also illumination wavelength less than the ultraviolet ray of 365nm.
To the sample of the organic mineral complex that obtains, operate equally with the foregoing description 5, before the test of high temperature and humidity test and after the test, measure the transmitance of wavelength 430nm.Table 3 expression measurement result.
Wherein, the additive of expression is as described below in the table 3.
Irganox (イ Le ガ ノ ッ Network ス) 1076: hindered phenol is an antioxidant, and CibaSpecialty Chemicals society produces
Sumilizer DS: being with the butadiene-based polymkeric substance stablizer of phenol system compound as effective constituent, is to utilize intramolecular pair of key to catch the stablizer that adds the polymkeric substance alkyl diradical of man-hour under anaerobic, and Sumitomo Chemical society produces
Irganox 1010: hindered phenol is an antioxidant, and Ciba Specialty Chemicals society produces
Wherein, embodiment 16 and 17 does not add additive, forms organic mineral complex formation material.
Sumilizer GA-80 adds use in the aforesaid liquid (A), Sumilizer TP-D, Sumilizer GS, Irganox 1076 and Irganox 1010, and being blended in the difunctionality fluorenes shown in above-mentioned embodiment 5 is to use in the acrylate (EA-0200).
(comparative example 2)
The organic mineral complex formation material as the oxide compound niobium particulate of metal oxide microparticle is not added in modulation.Particularly, the difunctionality fluorenes that uses 70 weight % is phenoxyethyl alcohol acrylate (Phenoxy EthylAcrylate) (the Xin Zhong village chemistry society production of acrylate (EA-0202), 28.5 weight %, trade(brand)name: " NK ESTER AMP-10G "), the Irgacure 184 (1-hydroxyl-cyclohexyl-phenyl ketone) of 1.5 weight %, with acetone is solvent, makes organic mineral complex and forms the solution of using material.
Except using this organic mineral complex to form with material, do not use the spectral filter irradiation ultraviolet radiation, operate the film of formation organic mineral complex equally with the foregoing description 5.
To the film of this comparative example, operate equally with the foregoing description 5, before the test of high temperature and humidity test and after the test, measure the transmitance under the 430nm, represent measurement result in the table 3.
Table 3
| Additive | Niobium oxides | Spectral filter during irradiation ultraviolet radiation | Transmitance under the 430nm (%) | ||||
| Kind | Addition (weight %) | Before the test | After the | Difference | |||
| Embodiment | |||||||
| 5 | Sumilizer GA-80/ Sumilizer TP-D | 0.3/0.3 | Have | Have | 80.2 | 79.1 | -1.1 |
| Embodiment 6 | lrganox 1076 | 0.3 | Have | Have | 75.6 | 74.7 | -0.9 |
| Embodiment 7 | Sumilizer GS | 0.1 | Have | Do not have | 72.7 | 50.2 | -22.5 |
| Embodiment 8 | Sumilizer GA-80 | 0.1 | Have | Do not have | 73.1 | 71.8 | -1.3 |
| Embodiment 9 | Sumilizer GA-80 | 0.3 | Have | Do not have | 72.2 | 63.6 | -8.6 |
| |
Sumilizer GA-80/ Sumilizer TP-D | 0.1/0.1 | Have | Do not have | 74.4 | 67.4 | -7.0 |
| Embodiment 11 | Sumilizer GA-80/ Sumilizer TP-D | 0.3/0.3 | Have | Do not have | 76.3 | 66.2 | -10.1 |
| |
Irganox 1010 | 0.1 | Have | Do not have | 73.4 | 69.6 | -3.8 |
| |
Irganox 1010 | 0.3 | Have | Do not have | 73.5 | 66.1 | -7.4 |
| |
Irganox 1076 | 0.1 | Have | Do not have | 70.0 | 60.1 | -9.9 |
| Embodiment 15 | lrganox 1076 | 0.3 | Have | Do not have | 77.4 | 73.8 | -3.6 |
| Embodiment 16 | Do not have | - | Have | Do not have | 70.0 | 53.0 | -17.0 |
| Embodiment 17 | Do not have | - | Have | Have | 79.1 | 59.3 | -19.8 |
| Comparative example 2 | Do not have | - | Do not have | Do not have | 85.8 | 84.4 | -1.4 |
As shown in Table 3, using hindered phenol is embodiment 6 and the embodiment 8～15 of antioxidant as additive, with not adding hindered phenol is that the embodiment 7 of antioxidant compares with embodiment 16～17, and the rate variance that sees through before the test of high temperature and humidity test and after the test reduces flavescence decline.Particularly use the ultraviolet embodiment 5 and 6 of spectral filter, the above wavelength of irradiation 365nm when irradiation ultraviolet radiation, flavescence significantly reduces.
The embodiment 17 that uses spectral filter when not adding additive, irradiation ultraviolet radiation do not use when not adding additive, irradiation ultraviolet radiation spectral filter embodiment 16 more as can be known, use spectral filter during by irradiation ultraviolet radiation, only shine the above ultraviolet ray of 365nm, before the test of high temperature and humidity test and after the test, can access high permeability.Therefore as can be known, use spectral filter during by irradiation ultraviolet radiation, the ultraviolet ray of the above wavelength of irradiation 365nm can access the high organic mineral complex of transmitance.
In addition, in the comparative example 2 of oxygen-free niobium, before the test of high temperature and humidity test and after the test, the difference of transmitance reduces.Therefore as can be known, the flavescence of organic mineral complex is owing to the amine compound that contains metal oxide microparticle or interpolation produces.In the present invention, contain metal oxide microparticle,, produce the problem that flavescence is increased owing to contain metal oxide microparticle for the specific refractory power that improves organic mineral complex.As mentioned above, this flavescence can be that antioxidant reduces by containing hindered phenol.In addition, when carrying out polymerization under irradiation ultraviolet radiation, use spectral filter etc., block the wavelength components less than 365nm, the ultraviolet ray of the above wavelength of irradiation 365nm can further reduce flavescence.
(embodiment 18)
Fig. 1 is the sectional view of expression optical element embodiment of the present invention.The non-spherical lens 1 that Fig. 1 (a) expression is formed by organic mineral complex of the present invention.This non-spherical lens 1 can use organic mineral complex of the present invention to form and use material, by making such as metal pattern (mold) moulding.
The compound non-spherical lens 2 of organic mineral complex of the present invention is used in Fig. 1 (b) expression.On optical element 3, across organosilane coupler layer 4, use metallic membrane etc. makes optical resin layer 5 moulding that are made of organic mineral complex of the present invention and forms.
As optical element 3, can use glass, plastics, pottery etc., use glass of high refractive index (ohara of Co., Ltd. produces, trade(brand)name: " S-LAH79 ", specific refractory power is about 2.0) in the present embodiment.
Fig. 1 (c) expression possesses the non-spherical lens 6 of the optical resin layer that is made of organic mineral complex of the present invention.On optical element 7, use metallic membrane etc. forms the optical resin layer 8 that organic mineral complex of the present invention constitutes.In the present embodiment, as optical element 7, use plastics (Japanese zeon society produce cyclic olefin polymer, trade(brand)name: " ZEONEX ").Use plastics as optical element, thus good with the binding property of organic mineral complex, on optical element 7, directly form optical resin layer 8.
Fig. 1 (b) and (c) shown in spherical lens, use optical element as spherical lens, form the optical resin layer of aspherical shape thereon, become compound non-spherical lens thus.
(embodiment 19)
Fig. 2 is the sectional view that schematically shows the camera module 10 that uses compound non-spherical lens shown in Figure 1.As shown in Figure 2, imaging apparatus 14 is provided with 3 non-spherical lenses 11,12 and 13, and these non-spherical lenses are kept by automatic focusing mechanism 15.Camera module 10 has above-mentioned 3 non-spherical lenses 11～13, the camera module of 2～5 megapixels that can use as portable phone.
In the present embodiment, non-spherical lens 11～13 uses the compound non-spherical lens of Fig. 1 (c).Compound non-spherical lens shown in Fig. 1 (c), optical resin layer 8 uses the organic mineral complex with high refractive index of the present invention, so the lens number can be kept to 3 from common 4.Therefore, can make the height of the camera module of present embodiment is about 7.5mm.
In addition, in the present embodiment, all lens 11～13 are non-spherical lens, but according to the design of camera module, needn't make whole lens be non-spherical lens, and making at least 1 lens is that non-spherical lens gets final product.Camera module shown in Figure 2 is characterised in that to have compound lens, imaging apparatus of being made up of a plurality of lens and the support that is used to keep them, and in a plurality of lens at least 1 is the non-spherical lens as optical element of the present invention.
With in the camera module, the specific refractory power of optical resin layer that is arranged at the lens in the camera module is only below 1.61 at existing portable phone, and must make the lens number is 4, so in existing camera module, it is highly for about about 10mm.
Fig. 3 is that expression highly is the sectional view of the portable phone that disposes two fold-types that have camera module now of 10mm.
Fig. 3 (a) and (b) shown in two folding states under, height H is 25mm.In the portable phone shown in Fig. 3 (a), upper height h
1With lower height h
2Be respectively 12.5mm, be same height.Possess camera module 10 on top, be built-in with TV frequency modulator 21, hard disk drive 22 and indicating meter 23 etc.In Fig. 3 (a), because upper height h
1Be low to moderate 12.5mm,, possess little indicating meter 23 so the existence of camera module 10 becomes obstacle.Be built-in with keyboard 24 and battery 25 etc. in the bottom.
In the portable phone shown in Fig. 3 (b), upper height h
1Be 14.5mm, lower height h
2Be 10.5mm.To increase upper height h
1Mode design, so can dispose big indicating meter 23.On the other hand, because lower height h
2Be 10.5mm, so the volume of battery 25 reduces the problem that exists cell container to reduce.
Fig. 4 is the sectional view of the portable phone of expression one embodiment of the invention.
At Fig. 4 (a) with in the portable phone (b), be built-in with Optical devices camera module 10 of the present invention.The height of camera module 10 of the present invention is low to moderate for example about 8mm, so shown in Fig. 4 (a), even dispose big indicating meter 23, also needn't increase upper height h
1, can make lower height h
2With upper height h
1Be similarly 12.5mm.Therefore, can built-in jumbo battery 25.
In addition, shown in Fig. 4 (b), can dispose camera module 10 respectively in the upper and lower.Therefore, can carry out the photography of stereo-picture, can also photograph with high-quality face to oneself.In addition, the application that can use the output signal of the full shot of many photographic cameras or a plurality of photographic cameras of electrosynthesis substantially to improve light sensitivity etc.
(embodiment 20)
In addition, camera module shown in Figure 2 can be as the camera module of vehicle mounted Monitor for reverse device.In the vehicle mounted camera module, require weather resistance to temperature variation, for example, can use the non-spherical lens of Fig. 1 (c).In addition, the non-spherical lens of Fig. 1 (c) has high refractive index, so can enlarge the visual angle.
(embodiment 21)
Fig. 5 is the sectional view that schematically shows as the diffraction grating of optical element embodiment of the present invention.On glass substrate 31, be formed with organosilane coupler layer 32, on organosilane coupler layer 32, be formed with the diffraction grating layer 33 that forms by organic mineral complex of the present invention.Organosilane coupler layer 32 forms by the organic silane coupling agent of coating on substrate 31.In addition, diffraction grating layer 33 can use organic mineral complex of the present invention to form and use material, and employing is made the method moulding firm by ramming and formed.As mentioned above, organic mineral complex of the present invention has high refractive index, can increase diffraction grating.Therefore, suitable to the material that forms diffraction grating.
Diffraction grating 30 can be used for optical sensor for example, optical splitter, the optical communication wide spectrum with optical elements such as facility, Fresnel lens etc.
Claims (19)
1. an organic mineral complex forms and uses material, it is characterized in that, contains:
Have the fluorenes based compound of acryl or methacryloyl, described fluorenes based compound vinylformic acid (ester) class monomer, metal oxide microparticle, alkylamine, organic amine and Photoepolymerizationinitiater initiater in addition with phenyl.
2. an organic mineral complex forms and uses material, it is characterized in that described organic amine is aniline or pentanoic.
3. organic mineral complex as claimed in claim 1 forms and uses material, it is characterized in that the content of described organic amine is 2～5 weight %.
4. organic mineral complex as claimed in claim 1 forms and uses material, it is characterized in that described metal oxide microparticle is a niobium oxides.
5. organic mineral complex as claimed in claim 1 forms and uses material, it is characterized in that, as described vinylformic acid (ester) class monomer, comprises vinylformic acid (ester) the class monomer or the oligopolymer of polyfunctional vinylformic acid (ester) class monomer or oligopolymer and simple function.
6. organic mineral complex as claimed in claim 1 forms and uses material, it is characterized in that also containing hindered phenol is antioxidant.
7. an organic mineral complex is characterized in that, the described organic mineral complex of claim 1 is formed obtain with the material polymerization.
8. an organic mineral complex is characterized in that, the described organic mineral complex of claim 2 is formed obtain with the material polymerization.
9. an organic mineral complex is characterized in that, the described organic mineral complex of claim 3 is formed obtain with the material polymerization.
10. an organic mineral complex is characterized in that, the described organic mineral complex of claim 4 is formed obtain with the material polymerization.
11. an organic mineral complex is characterized in that, the described organic mineral complex of claim 5 is formed obtain with the material polymerization.
12. an organic mineral complex is characterized in that, the described organic mineral complex of claim 6 is formed obtain with the material polymerization.
13. an optical element is characterized in that, uses the described organic mineral complex of claim 7.
14. optical element as claimed in claim 13 is characterized in that, it is for being formed with the compound non-spherical lens of the optical resin layer that is made of the described organic mineral complex of claim 7 on base material.
15. Optical devices is characterized in that, use the described optical element of claim 13.
16. Optical devices is characterized in that, use the described optical element of claim 14.
17. the manufacture method of an organic mineral complex is characterized in that, uses the described organic mineral complex of claim 1 to form and uses material, makes organic mineral complex,
Comprise: the operation of modulating the dispersion liquid of the described metal oxide microparticle that contains described alkylamine and described organic amine;
Mix described vinylformic acid (ester) class monomer, described Photoepolymerizationinitiater initiater and described fluorenes based compound in described dispersion liquid, the modulation organic mineral complex forms the operation with material; With
Described organic mineral complex is formed use the material polymerization, form the operation of organic mineral complex.
18. the manufacture method of organic mineral complex as claimed in claim 17 is characterized in that, forms to described organic mineral complex and uses the material irradiation ultraviolet radiation, makes its polymerization.
19. the manufacture method of organic mineral complex as claimed in claim 18 is characterized in that, illumination wavelength is the above ultraviolet ray of 365nm.
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|---|---|---|---|
| JP2006233973 | 2006-08-30 | ||
| JP2006233973 | 2006-08-30 | ||
| JP2007142854 | 2007-05-30 |
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|---|---|---|---|
| CNA2007101478222A Pending CN101134818A (en) | 2006-08-30 | 2007-08-30 | Material for forming organic inorganic compound, organic inorganic compound and optical element using the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104603215A (en) * | 2012-09-03 | 2015-05-06 | 乐金华奥斯有限公司 | Composition for coating highly refractive layer, and transparent conductive film comprising same |
| CN105409327A (en) * | 2013-05-22 | 2016-03-16 | 三菱丽阳株式会社 | Light extraction film, method for producing same, and surface light emitting body |
| CN109716172A (en) * | 2016-09-16 | 2019-05-03 | 康宁股份有限公司 | High refractive index nano compound |
| CN115755525A (en) * | 2022-12-12 | 2023-03-07 | 之江实验室 | Preparation method of high-refractive-index laser direct-writing photoresist and high-curvature photon lead |
-
2007
- 2007-08-30 CN CNA2007101478222A patent/CN101134818A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104603215A (en) * | 2012-09-03 | 2015-05-06 | 乐金华奥斯有限公司 | Composition for coating highly refractive layer, and transparent conductive film comprising same |
| CN105409327A (en) * | 2013-05-22 | 2016-03-16 | 三菱丽阳株式会社 | Light extraction film, method for producing same, and surface light emitting body |
| CN109716172A (en) * | 2016-09-16 | 2019-05-03 | 康宁股份有限公司 | High refractive index nano compound |
| CN115755525A (en) * | 2022-12-12 | 2023-03-07 | 之江实验室 | Preparation method of high-refractive-index laser direct-writing photoresist and high-curvature photon lead |
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Application publication date: 20080305 |