CN102101910A - Polymer, manufacturing method of same, optical element having same and optoelectronic device having same - Google Patents
Polymer, manufacturing method of same, optical element having same and optoelectronic device having same Download PDFInfo
- Publication number
- CN102101910A CN102101910A CN2009102624371A CN200910262437A CN102101910A CN 102101910 A CN102101910 A CN 102101910A CN 2009102624371 A CN2009102624371 A CN 2009102624371A CN 200910262437 A CN200910262437 A CN 200910262437A CN 102101910 A CN102101910 A CN 102101910A
- Authority
- CN
- China
- Prior art keywords
- polymkeric substance
- refractive index
- transmittance
- monomer
- high refractive
- 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.)
- Granted
Links
- 0 *=N*1CCC1 Chemical compound *=N*1CCC1 0.000 description 3
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/52—PV systems with concentrators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention relates to a polymer, a manufacturing method of the same, an optical element having the same and an optoelectronic device having the same. The polymer has high refractive index and high transmittance. The polymer is formed by the polymerization of the following initiative materials: (a) bisphenol fluorine derivative monomers including compounds having a structure shown by a molecular formula (I), wherein Rs are independent and are hydrogen atoms, C1 to C8 alkyls, C1 to C8 alkoxys, carboxyls or halogen atoms, and i and j are independent and are 0 or integers from 1 and 5; and (b) diisocyanate monomers.
Description
Technical field
The present invention relates to a kind of polymkeric substance and comprise its optical element and optoelectronic equipment, particularly a kind of high refractive index and high-transmittance polymkeric substance and comprise its optical element and optoelectronic equipment.
Background technology
Photodiode (Light Emitting Diode, be called for short LED) is widely used in the various demonstration products because of it has advantages such as high brightness, volume are little, in light weight, cracky, low power consumption and life-span be not long.
The whole luminous efficacy of photodiode (LED) mainly is subjected to wafer, structure dress form and packaged material to be influenced.Progress along with crystal epitaxy technology (epitaxy growth technology), the wafer internal light emission efficiency has reached more than 90%, but for fear of structure dress form and packaged material influence, it is 30% only that optical efficiency is got in the final outside of photodiode, it serves to show structure dress form and the packaged material importance to light-emitting diode luminance.According to the Shi Naier law, light advances to the zone with low-refraction in a certain critical angle (with respect to the surface normal direction) from the zone with high refractive index, with the zone of passing through than low-refraction.To the surface can be not pass with the light that surpasses critical angle arrival surface, but inner full-reflection (TIR) can be experienced.In the situation of LED, TIR light is sustainable in the LED internal reflection, till being absorbed.Because this reflex, most light that produced by existing LED are not launched, and have reduced the efficient of itself.
With the white light emitting diode is example, the wafer specific refractory power is about 2～4, as the specific refractory power of GaN (n=2.5) and GaP (n=3.45) all far above the specific refractory power (n=1.40～1.53) of Resins, epoxy or silicone resin packaged material, refractive index difference is excessive to cause taking place total reflection, light reflected back wafer inside can't effectively be derived, and the specific refractory power that therefore improves packaged material can reduce the generation of total reflection.White light emitting diode assembly with blue light wafer/yellow YAG phosphor powder is an example, and the wafer specific refractory power of blue light-emitting diode is 2.5, and when the specific refractory power of packaged material was increased to 1.7 from 1.5 the time, light took out efficient and improved nearly 30%.Therefore, improving the specific refractory power reduction wafer of packaged material and the refractive index difference between packaged material and reach the raising light emitting efficiency, is the target of demanding urgently studying.
For addressing the above problem, U.S. Pat 5,633,331 have disclosed a kind of packaged material with high refractive index, it carries out the blending gained by fluorenes carbonic ether (Fluorene Carbonate) polymer and polysulfones (Polysulfone), have the polymer of high refractive index group by importing, improve the specific refractory power of packaged material.
In addition, U.S. Pat 7,446,159 have disclosed a kind of packaged material with high refractive index, and (its structure is with fluorenes monomer with esters of acrylic acid functional group for it
Wherein X is-(CH
2CH
2O)
n-,-(CH
2CH
2O)-CH
2CH (OH) CH
2O-, n are 1 to 5, and R is acrylic or methacrylic acid group) carry out polyreaction preparation and get.Right because monomer whose viscosity is too high, and film-forming properties is not good, so its application is restricted (all being difficult for implementing as modes such as film coated, silk screen printing, sputters).
The relevant Patent publish of Osaka gas and company of Nippon Steel by multi-thiol and the reaction of polynary lsothiocyanates and polymkeric substance have good optical index, be suitable as the packaged material of LED.But the shortcoming of this polymkeric substance is that it has in time and xanthochromia.
[summary of the invention]
One embodiment of the present of invention propose the polymkeric substance of a kind of high refractive index and high-transmittance, and it is following initiator polymerization products therefrom, and this initiator comprises:
(a) bisphenol fluorene derivative (bisphenol fluorene derivative) monomer comprises the compound with structure shown in molecular formula (I):
Wherein, R is independent separately and be hydrogen, C
1-8Alkyl, C
1-8Alkoxyl group, carboxyl or halogen; I and j be independence and be 0 or 1～5 integer separately; And
(b) vulcabond (diisocyanate) monomer.
Another embodiment of the present invention proposes a kind of optical element, and it comprises above-mentioned high refractive index and high-transmittance polymkeric substance, and this optical element comprises packaged material, transparency carrier, lens or functional film.
Another embodiment of the present invention also provides optoelectronic equipment, and it comprises above-mentioned optical element, and this optoelectronic equipment comprises photodiode, solar cell, semiconductor device or display unit.
Below by a plurality of embodiment, illustrate further the present invention in conjunction with the accompanying drawings, but be not to be used for limiting the scope of the invention, scope of the present invention should be as the criterion with appended claim.
Description of drawings
Fig. 1 is the transmitance of polymeric film of embodiment 13 gained and the graph of a relation of wavelength.
Embodiment
The present invention discloses a kind of polymkeric substance and its manufacture method with high refractive index and high-transmittance, and the optical element and the optoelectronic equipment that comprise it.Polymkeric substance with high refractive index and high-transmittance of the present invention, it is following initiator polymerization products therefrom, this initiator comprises:
(a) bisphenol fluorene derivatives monomer comprises the compound with structure shown in molecular formula (I):
Wherein, R is independent separately and be hydrogen, C
1-8Alkyl, C
1-8Alkoxyl group, carboxyl or halogen; I and j be independence and be 0 or 1～5 integer separately.Noticeable, when R is alkyl (for example methyl, propyl group, butyl), because this bisphenol fluorene derivatives monomer has alkyl substituent on phenyl ring, can increase the solubleness of compound in organic solvent, thereby can modulate the high refractive index colloidal material of high solids content; And
(b) diisocyanate monomer.
According to embodiment of the present invention, the ratio of mole number that wherein should (a) bisphenol fluorene derivatives monomer and mole number that should (b) diisocyanate monomer is more than or equal to 0.1, or preferably between 0.2-1.
According to embodiment of the present invention, should can have following structure by (a) bisphenol fluorene derivatives monomer
Or
Wherein R is independent separately and be hydrogen, C
1-8Alkyl, C
1-8Alkoxyl group, carboxyl or halogen.
According to embodiment of the present invention, this diisocyanate monomer comprises the compound with structure shown in molecular formula (II):
OCN-A-NCO molecular formula (II)
Wherein, A is aliphatics or aromatic group.In the present invention, the non-aromatic structure represented in " aliphatic group (aliphaticgroup) " speech, can be the arbitrary combination of carbon atom and hydrogen atom, and can connect halogen, oxygen, nitrogen, silicon, sulphur or other atoms to form various substituting groups.Aliphatics can be straight chain, side chain or annular form, and may comprise one or more unsaturated groups, for example two keys and/or triple bond; The hydrocarbon aromatic nucleus of monocycle or multi-loop system represented in " aromatic group (aromatic group) " speech, for example: phenyl, tolyl, naphthyl, tetrahydro naphthyl (tetrahydronaphthyl), xenyl (biphenyl), phenanthryl (phenanthryl), anthryl (anthracyl) etc.In addition, can have one or more heteroatomss (as nitrogen, oxygen, sulphur) in the aromatic nucleus and constitute assorted aromatic nucleus, for example pyridyl (pyridyl), furyl (furyl), thienyl (thienyl), imidazolyl (imidazolyl).
In addition, according to some embodiment of the present invention, should can comprise by (b) diisocyanate monomer: aliphatic diisocyanate monomer, alicyclic diisocyanate monomer, fragrant fat subsitutes family (araliphatic) diisocyanate monomer, aromatic diisocyanate monomer or its mixing.This aromatic diisocyanate monomer can comprise 2,4-and 2,6-tolylene diisocyanate (TDI), perhydro-2,4 '-and-4,4 '-diphenylmethanediisocyanate (HMDI), 4,4 '-, 2,4 '-and 2,2 '-diphenylmethanediisocyanate (MDI), naphthalene-1,5-vulcabond (NDI), phenylene vulcabond (PPDI), 2,3,5,6-tetramethyl--1,4-two isocyanato benzene, 3,3 '-dimethyl-4,4 '-two isocyanato biphenyl (TODI) or its mixing.This alicyclic diisocyanate monomer can comprise dicyclohexyl methane diisocyanate (H
12MDI), 1-isocyanato-3,3,5-trimethylammonium-5-isocyanato methyl-cyclohexyl alkane (IPDI), hexanaphthene-1,3-and-1,4-vulcabond (CHDI), 1,3-and 1,4-two-(isocyanato methyl)-hexanaphthene (H
6XDI), 1,3-and 1,4-two (isocyanato methyl) hexanaphthene (BIC) or its mixing.This aliphatic diisocyanate monomer comprises 1,6-hexamethylene diisocyanate (HDI), 1,12-ten dimethylene diisocyanates, 2,2,4-and 2,4,4-trimethylammonium-1,6-hexamethylene diisocyanate (TMDI), 2-methyl pentamethylene-1,5-vulcabond, 1,4-two isocyanatos-2,2,6-trimethyl-cyclohexane (TMCDI), Methionin-and Methionin ester vulcabond or its mixing.This virtue fat subsitutes (cyclo) aliphatic diisocyanates monomer comprises 1,3-and 1,4-tetramethylxylylene diisocyanate (TMXDI), and terephthalylidene vulcabond (XDI) or its mixing.
According to other embodiment of the present invention, this has the polymkeric substance of high refractive index and high-transmittance, can comprise by (a) bisphenol fluorene derivatives monomer, (b) diisocyanate monomer and (c) initiator such as dibasic alcohol monomer carry out the polyreaction products therefrom.Wherein should (a) bisphenol fluorene derivatives monomer with the ratio of the mole number of should the monomeric total mole number of (c) dibasic alcohol and should (b) diisocyanate monomer more than or equal to 1, or between 1-5.
According to embodiment of the present invention, this dibasic alcohol monomer can comprise the compound with structure shown in molecular formula (III):
Wherein, B is
X is independent separately and be halogen, and R is independence and be hydrogen, C separately
1-8Alkyl, C
1-8Alkoxyl group, carboxyl or halogen, n=1～2.In addition, this dibasic alcohol monomer also can comprise the compound with structure shown in molecular formula (IV) simultaneously:
(HO)
2Q (COOH)
mMolecular formula (IV)
Wherein, Q is C
2-12The hydro carbons group of straight chain or branching, m are 0 or 1～4 integer.
Meeting above-mentioned dibasic alcohol monomer can for example be: dihydroxyphenyl propane (Bisphenol A), tetrabromo-bisphenol (TBBPA), bisphenol b (Bisphenol B), bis-phenol E (Bisphenol E), Bisphenol F (Bisphenol F), bisphenol S (Bisphenol S), 3,3 '-dihydroxyl diphenyl disulfide, ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, cyclohexanediol, cyclohexyl dimethanol (cyclohexyldimethanol, CHDM), ethohexadiol, neopentyl glycol (neopentyl glycol, NPG), neopentyl glycol (trimethylpentanediol, TMPD), xylyl alcohol, dihydroxy-benzene, cresorcin, glycol ether, Triethylene glycol, dipropylene glycol or tripropylene glycol, dimethylol propionic acid (DMPA), dimethylol propionic acid (DMBA), tartrate or its mix, or the derivative of the halogen of above-claimed cpd replacement.In addition, be to increase the flexibility of polymkeric substance, can also be when the synthetic formulation of reaction back segment polyoxyethylene glycol (PEG, molecular weight preferably less than 1000, for example PEG-200, PEG-600) be imported, produce the phenomenon of be full of cracks with the polymeric film of avoiding gained.
According to other embodiment of the present invention, this initiator can further comprise stiffening agent, and wherein this stiffening agent system comprises the compound with structure shown in the molecule formula V
The molecule formula V
Wherein R is independent separately and be hydrogen, C
1-8Alkyl, C
1-8Alkoxyl group, carboxyl or halogen.In addition, this stiffening agent also can further comprise acid anhydrides (anhydride), for example: cis-1,2,3,6-Tetra Hydro Phthalic Anhydride (cis-1,2,3,6-Tetrahydrophthalic anhydride).Because employed stiffening agent also comprises the bisphenol fluorene structure, therefore can further improve specific refractory power.
One of major technique feature of the present invention be with volume less and for high refractive index, high heat-stablely have the bisphenol fluorene derivative of alcohol radical and the monomer of vulcabond (for example: TDI, MDI, IPDI, HDI or the like) carries out polymerization, and can further add have chlorine, the dibasic alcohol monomer of bromine or sulphur atom carries out polymerization, to increase specific refractory power and thermopolymerization efficient.In addition, the diatomic alcohol compounds (for example: tartrate, DMPA) that will have carboxylic acid functional imports polyreaction, and its major function is to provide the polymkeric substance of gained to carry out thermofixation (thermal curing) with stiffening agent in back-end process.
In addition, the present invention also provides the manufacture method of above-mentioned high refractive index and high-transmittance polymkeric substance, may further comprise the steps:
Compositions formulated, said composition comprise above-mentioned (a) bisphenol fluorene derivatives monomer, and (b) diisocyanate monomer, or can further comprise (C) dibasic alcohol monomer, and thermal initiator.Then, the heating said composition obtains the polymkeric substance of this high refractive index and high-transmittance to carry out polyreaction.In addition, before the heating said composition, stiffening agent can be added in the said composition.It should be noted that owing to be used as the bisphenol fluorene derivatives monomer and the dibasic alcohol monomer of reaction monomers in the above-mentioned reaction itself to have splendid dissolving power, therefore when the preparation feedback composition, can improve solid content, even can not need plus solvent.In other words, above-mentioned composition can not comprise the organic solvent that other do not participate in this polyreaction.Therefore, when above-mentioned composition carries out polyreaction (or curing), the polymkeric substance thickness acute variation that causes because of solvent evaporates in the time of can reducing the system film.
Below by the following example high refractive index of the present invention and high-transmittance polymkeric substance are described, in order to further to illustrate technical characterictic of the present invention.
Synthesizing of high refractive index and high-transmittance polymkeric substance
Table 1 lists and is used for synthesizing high refractive index and the employed bisphenol fluorene derivatives monomer of high-transmittance polymkeric substance, diisocyanate monomer and dibasic alcohol monomer in the various embodiments of the present invention, and its chemical structure separately is all detailed lists in the table.
Table 1
For further specifying the preparation method of organic compound of the present invention, below special embodiment 1,2,4,5,7,9, and the polymer manufacture mode of 11-13 of describing in detail.
Embodiment 1
Get 0.1 mole of F9PEO powder and place the 500ml reaction flask, add gamma-butyrolactone (γ-butyrolactone, GBL) solvent (solid content is about 30%), and fed nitrogen 30 minutes, stirring makes its dissolving, its solvent temperature be about 90 ℃.Then, utilize addition funnel that 0.1 mole of IPDI is added in the reaction flask, (NCO) disappear (detecting with IR in per 30 minutes), reaction can be stopped (about 16 hours of reaction times) up to isocyanato.At this, the mol ratio of this F9PEO and this IPDI is 1: 1.Then, utilize the polymkeric substance of gpc measurement gained, record its molecular weight Mw=7240, Mn=3485 and Mw/Mn=2.07.
The reaction formula of above-mentioned polyreaction is as follows:
Then, before curing, this polymer composition (5g) added stiffening agent (0.25g) and baking 1 hour in 100 ℃ of baking ovens, and become the 1mm film.After the measurement, the specific refractory power of this film is 1.56 as can be known.At this, this stiffening agent comprises 0.01 mole of F9PG (4.62 gram) and the acid anhydrides (cis-1,2,3,6-Tetra Hydro Phthalic Anhydride) (1.52 gram) that is dissolved in the 40 gram gamma-butyrolactone solvents.
F9PG cis-1,2,3, the 6-Tetra Hydro Phthalic Anhydride
Embodiment 2
Get 0.05 mole of F9PEO, and 0.05 mole of DMPA place the 500ml reaction flask, add gamma-butyrolactone solvent (solid content is about 30%), and fed nitrogen 30 minutes, stirring makes its dissolving, its solvent temperature be about 110 ℃.And add several thermo-stabilizer CHINOX TP-10H (Taiwan two key chemical industry) to prevent the xanthochromia phenomenon when synthetic.Then, utilize addition funnel that 0.1 mole of IPDI is added in the reaction flask, (NCO) disappear (detecting with IR in per 30 minutes), reaction can be stopped (about 5 hours of reaction times) up to isocyanato.At this, the mol ratio of this F9PEO, this DMPA and this IPDI is 1: 1: 2.Then, utilize the polymkeric substance of gpc measurement gained, record its molecular weight Mw=8008, Mn=3782 and Mw/Mn=2.11.
The reaction formula of above-mentioned polyreaction is as follows:
Then, before curing, this polymer composition (5g) added stiffening agent (0.25g) and baking 1 hour in 100 ℃ of baking ovens, and become the 1mm film.After the measurement, the specific refractory power of this film is 1.57 as can be known.At this, this stiffening agent comprises 0.01 mole of F9PG (4.62 gram) and the acid anhydrides (cis-1,2,3,6-Tetra Hydro Phthalic Anhydride) (1.52 gram) that is dissolved in the 40 gram gamma-butyrolactone solvents.
Embodiment 4
Get 0.05 mole of F9PEO, and 0.05 mole of bisphenol S place the 500ml reaction flask, add gamma-butyrolactone solvent (solid content is about 30%), and fed nitrogen 30 minutes, stirring makes its dissolving, its solvent temperature be about 90 ℃.And add several thermo-stabilizer CHINOX TP-10H to prevent the xanthochromia phenomenon when synthetic.Then, utilize addition funnel that 0.1 mole of IPDI is added in the reaction flask, (NCO) disappear (detecting with IR in per 30 minutes), reaction can be stopped at this, the mol ratio of this F9PEO, this bisphenol S and this IPDI is 1: 1: 2 up to isocyanato.Then, utilize the polymkeric substance of gpc measurement gained, record its molecular weight Mw=11774, Mn=6419 and Mw/Mn=1.82.
The reaction formula of above-mentioned polyreaction is as follows:
Then, before curing, this polymer composition (5g) added stiffening agent (0.25g) and baking 1 hour in 100 ℃ of baking ovens, and become the 1mm film.After the measurement, the specific refractory power of this film is 1.57 as can be known.At this, this stiffening agent comprises 0.01 mole of F9PG (4.62 gram) and the acid anhydrides (cis-1,2,3,6-Tetra Hydro Phthalic Anhydride) (1.52 gram) that is dissolved in the 40 gram gamma-butyrolactone solvents.
Get 0.03 mole of F9PEO, 0.03 mole of bisphenol S and 0.04 mole of DMPA and place the 500ml reaction flask, add gamma-butyrolactone solvent (solid content is about 30%), and fed nitrogen 30 minutes, stirring makes its dissolving, its solvent temperature be about 100 ℃.And add several thermo-stabilizer CHINOXTP-10H to prevent the xanthochromia phenomenon when synthetic.Then, utilize addition funnel that 0.1 mole of IPDI is added in the reaction flask, (NCO) disappear (detecting with IR in per 30 minutes), reaction can be stopped up to isocyanato.At this, the mol ratio of this F9PEO, this bisphenol S, this DMPA and this IPDI is 3: 3: 4: 10.Then, utilize the polymkeric substance of gpc measurement gained, record its molecular weight Mw=69334, Mn=2980 and Mw/Mn=2.32.
The reaction formula of above-mentioned polyreaction is as follows:
Then, before curing, this polymer composition (5g) added stiffening agent (0.25g) and baking 1 hour in 100 ℃ of baking ovens, and become the 1mm film.After the measurement, the specific refractory power of this film is 1.57 as can be known.At this, this stiffening agent comprises 0.01 mole of F9PG (4.62 gram) and the acid anhydrides (cis-1,2,3,6-Tetra Hydro Phthalic Anhydride) (1.52 gram) that is dissolved in the 40 gram gamma-butyrolactone solvents.
Embodiment 7
Get 0.06 mole of F9PEO, 0.01 mole of TBBPA and 0.04 mole of DMPA and place the 500ml reaction flask, add gamma-butyrolactone solvent (solid content is about 30%), and fed nitrogen 30 minutes, stirring makes its dissolving, its solvent temperature be about 100 ℃.And add several thermo-stabilizer CHINOXTP-10H to prevent the xanthochromia phenomenon when synthetic.Then, utilize addition funnel that 0.1 mole of IPDI is added in the reaction flask, (NCO) disappear (detecting with IR in per 30 minutes), reaction can be stopped up to isocyanato.At this, the mol ratio of this F9PEO, this TBBPA, this DMPA and this IPDI is 6: 1: 4: 10.
The reaction formula of above-mentioned polyreaction is as follows:
Then, before curing, this polymer composition (5g) added stiffening agent (0.25g) and baking 1 hour in 100 ℃ of baking ovens, and become the 1mm film.After the measurement, the specific refractory power of this film is 1.59 as can be known.At this, this stiffening agent comprises 0.01 mole of F9PG (4.62 gram) and the acid anhydrides (cis-1,2,3,6-Tetra Hydro Phthalic Anhydride) (1.52 gram) that is dissolved in the 40 gram gamma-butyrolactone solvents.
Embodiment 9
Get 0.1 mole of F9Ph and place the 500ml reaction flask, add gamma-butyrolactone solvent (solid content is about 35%), and fed nitrogen 30 minutes, stirring makes its dissolving, its solvent temperature be about 45 ℃.And add several thermo-stabilizer CHINOX TP-10H to prevent the xanthochromia phenomenon when synthetic.Then, utilize addition funnel that 0.1 mole of MDI is added in the reaction flask, (NCO) disappear (detecting with IR in per 30 minutes), reaction can be stopped up to isocyanato.At this, this F9Ph, with the mol ratio of this MDI be 1: 1.
The reaction formula of above-mentioned polyreaction is as follows:
Then, before curing, this polymer composition (5g) added stiffening agent (0.25g) and baking 1 hour in 100 ℃ of baking ovens, and become the 1mm film.After the measurement, the specific refractory power of this film is 1.59 as can be known.At this, this stiffening agent comprises 0.01 mole of F9PG (4.62 gram) and the acid anhydrides (cis-1,2,3,6-Tetra Hydro Phthalic Anhydride) (1.52 gram) that is dissolved in the 40 gram gamma-butyrolactone solvents.
Embodiment 11
Get 0.05 mole of F9Ph, and the TBBA of 0.04mol place the 500ml reaction flask, add gamma-butyrolactone solvent (solid content is about 35%), and fed nitrogen 30 minutes, stirring makes its dissolving, its solvent temperature be about 45 ℃.And add several thermo-stabilizer CHINOX TP-10H to prevent the xanthochromia phenomenon when synthetic.After fully stirring, add 0.01 mole of PEG600 in reaction flask and fed nitrogen 30 minutes.Then, utilize addition funnel that 0.1 mole of MDI is added in the reaction flask, (NCO) disappear (detecting with IR in per 30 minutes), reaction can be stopped up to isocyanato.The PEG600 that adds the soft chain of part is mainly used in the pliability of regulation and control macromolecular material, produces the phenomenon of be full of cracks to prevent material in the process of system film.
The reaction formula of above-mentioned polyreaction is as follows:
Then, before curing, this polymer composition (5g) added stiffening agent (0.25g) and baking 1 hour in 100 ℃ of baking ovens, and become the 1mm film.After the measurement, the specific refractory power of this film is 1.59 as can be known.At this, this stiffening agent comprises 0.01 mole of F9PG (4.62 gram) and the acid anhydrides (cis-1,2,3,6-Tetra Hydro Phthalic Anhydride) (1.52 gram) that is dissolved in the 40 gram gamma-butyrolactone solvents.
Embodiment 12
Get 0.05 mole of F9Ph, and 0.05 mole of bisphenol S place the 500ml reaction flask, add gamma-butyrolactone solvent (solid content is about 35%), and fed nitrogen 30 minutes, stirring makes its dissolving, its solvent temperature be about 45 ℃.And add several thermo-stabilizer CHINOX TP-10H to prevent the xanthochromia phenomenon when synthetic.After fully stirring, adds 0.01 mole of PEG600 and move in the reaction flask and fed nitrogen 30 minutes.Then, utilize addition funnel that 0.05 mole of MDI and 0.05 mole of IPDI are added in the reaction flask, (NCO) disappear (detecting with IR in per 30 minutes), reaction can be stopped up to isocyanato.The mol ratio of this F9Ph, this bisphenol S, this MDI, this IPDI is=1: 1: 1: 1.
Then, before curing, this polymer composition (5g) added stiffening agent (0.25g) and baking 1 hour in 100 ℃ of baking ovens, and become the 0.88mm film.After the measurement, the UV transmitance of this film and specific refractory power are respectively 86% and 1.573 as can be known.At this, this stiffening agent comprises 0.01 mole of F9PG (4.62 gram) and the acid anhydrides (cis-1,2,3,6-Tetra Hydro Phthalic Anhydride) (1.52 gram) that is dissolved in the 40 gram gamma-butyrolactone solvents.
Embodiment 13
Get 0.06 mole of F9Ph, and 0.04 mole of PEG200 place the 500ml reaction flask, add gamma-butyrolactone solvent (solid content is about 35%), and fed nitrogen 30 minutes, stirring makes its dissolving, its solvent temperature be about 45 ℃.And add several thermo-stabilizer CHINOX TP-10H to prevent the xanthochromia phenomenon when synthetic.After fully stirring, utilize addition funnel that 0.09 mole of MDI and 0.01 mole of IPDI are added in the reaction flask, (NCO) disappear (detecting with IR in per 30 minutes), reaction can be stopped up to isocyanato.The mol ratio of this F9Ph, this PEG200, this MDI, this IPDI is=6: 4: 9: 1.
The reaction formula of above-mentioned polyreaction is as follows:
Then, before curing, this polymer composition (5g) added stiffening agent (0.25g) and baking 1 hour in 100 ℃ of baking ovens, and become film.After the measurement, the UV transmitance of this film and specific refractory power are respectively 95% and 1.615 as can be known.The relation of its wavelength and transmitance as shown in Figure 1.At this, this stiffening agent comprises 0.01 mole of F9PG (4.62 gram) and the acid anhydrides (cis-1,2,3,6-Tetra Hydro Phthalic Anhydride) (1.52 gram) that is dissolved in the 40 gram gamma-butyrolactone solvents.
In addition, above-mentioned polymer formation film is attached on the money base material, and utilizes 100 ℃ storing temperature (toasting 1 hour).Then, test piece is positioned in the red ink aqueous solution of preparation.Soak after 30 minutes, do not observe red ink and infiltrate in the film.This represents that this polymkeric substance has splendid adhesive ability.
Comprehensively above-mentioned, the present invention utilizes the mode of Molecular Structure Design, importing contains the bisphenol fluorene derivatives monomer (for example F9Ph, F9PEO) of high refractive index and has the mode of the derivative of two isocyanate functional groups by addition polymerization, synthesizes the macromolecular material with high refractive index.In addition, also further contain the bis-phenol of heteroatom group of sulphur or bromine or the specific refractory power that dibasic alcohol is regulated and control its material by adding.Moreover, in certain embodiments of the invention, also use PEG oligopolymer as dibasic alcohol, with the flexibility of balance block polymer with soft chain; Or add stiffening agent with bisphenol fluorene structure, strengthen thermotolerance and hardness.
Polymkeric substance of the present invention, except having high refractive index, high light transmittance, also have character such as high heat resistance, high adhesive force, low-yellowing and high film build, Fresnel lens (fresnel lenes)) or optical element such as functional film (for example:, (for example: the application requiring of optical elements such as concentrating solar battery (concentratorphotovoltaic), semiconductor device or display unit more meet photodiode, solar cell can be used as packaged material, transparency carrier, lens.
Though the present invention discloses as above with a plurality of preferred embodiments, so it is not in order to qualification the present invention, any the technical staff in the technical field of the invention, and without departing from the spirit and scope of the present invention, Ying Kezuo is change and retouching arbitrarily.Therefore, protection scope of the present invention should be as the criterion with the appended claims restricted portion.
Claims (20)
1. the polymkeric substance of high refractive index and high-transmittance is following initiator polymerization products therefrom, and this initiator comprises:
(a) bisphenol fluorene derivatives monomer comprises the compound with structure shown in molecular formula (I):
Wherein, R is independent separately and be hydrogen, C
1-8Alkyl, C
1-8Alkoxyl group, carboxyl or halogen; I and j be independence and be 0 or 1～5 integer separately; And
(b) diisocyanate monomer.
2. the polymkeric substance of high refractive index as claimed in claim 1 and high-transmittance, wherein this diisocyanate monomer comprises the compound with structure shown in molecular formula (II):
OCN-A-NCO molecular formula (II)
Wherein, A is aliphatics or aromatic group.
3. the polymkeric substance of high refractive index as claimed in claim 1 and high-transmittance, wherein this diisocyanate monomer comprises aliphatic diisocyanate monomer, alicyclic diisocyanate monomer, fragrant fat subsitutes (cyclo) aliphatic diisocyanates monomer, aromatic diisocyanate monomer or its mixing.
4. the polymkeric substance of high refractive index as claimed in claim 1 and high-transmittance, wherein this diisocyanate monomer comprises dicyclohexyl methane diisocyanate, 1, the 6-hexamethylene diisocyanate, 2-methyl pentamethylene-1, the 5-vulcabond, 2,2,4-and 2,4,4-trimethylammonium-1,6-hexamethylene diisocyanate, 1,12-ten dimethylene diisocyanates, hexanaphthene-1,3-and-1, the 4-vulcabond, 1-isocyanato-3,3,5-trimethylammonium-5-isocyanato methyl-cyclohexyl alkane, perhydro-2,4 '-and-4,4 '-diphenylmethanediisocyanate, 1,4-two isocyanatos-2,2, the 6-trimethyl-cyclohexane, between and the terephthalylidene vulcabond, 1,3-and 1,4-tetramethylxylylene diisocyanate, 1,3-and 1,4-two-(isocyanato methyl)-hexanaphthene (H
6XDI), 2,4-and 2,6-tolylene diisocyanate, 4,4 '-, 2,4 '-and 2,2 '-diphenylmethanediisocyanate, phenylene vulcabond, 2,3,5,6-tetramethyl--1,4-two isocyanato benzene, naphthalene-1,5-vulcabond, 3,3 '-dimethyl-4,4 '-two isocyanato biphenyl, Methionin-and Methionin ester vulcabond, 1,3-and 1,4-two (isocyanato methyl) hexanaphthene or its mixing.
5. the polymkeric substance of high refractive index as claimed in claim 1 and high-transmittance, wherein the ratio of the mole number of the mole number of this (a) bisphenol fluorene derivatives monomer and this (b) diisocyanate monomer is more than or equal to 0.1.
6. the polymkeric substance of high refractive index as claimed in claim 1 and high-transmittance, wherein this initiator further comprises:
(c) dibasic alcohol monomer.
7. the polymkeric substance of high refractive index as claimed in claim 6 and high-transmittance, wherein (a) bisphenol fluorene derivatives monomer and the ratio of the mole number of should the monomeric total mole number of (c) dibasic alcohol and should (b) diisocyanate monomer be more than or equal to 1, or be 1-5.
8. the polymkeric substance of high refractive index as claimed in claim 6 and high-transmittance, wherein this dibasic alcohol monomer comprises the compound with structure shown in molecular formula (III):
Wherein, B is
X is independent separately and be halogen, and R is independence and be hydrogen, C separately
1-8Alkyl, C
1-8Alkoxyl group, carboxyl or halogen, n=1～2.
9. the polymkeric substance of high refractive index as claimed in claim 6 and high-transmittance, wherein this dibasic alcohol monomer comprises the compound with structure shown in molecular formula (IV):
(HO)
2Q (COOH)
mMolecular formula (IV)
Wherein, Q is C
2-12The hydro carbons group of straight chain or branching, m are 0 or 1～4 integer.
10. the polymkeric substance of high refractive index as claimed in claim 6 and high-transmittance, wherein this dibasic alcohol monomer is selected from dihydroxyphenyl propane, tetrabromo-bisphenol, bisphenol b, bis-phenol E, Bisphenol F, bisphenol S, 3,3 '-dihydroxyl diphenyl disulfide, ethylene glycol, polyoxyethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, cyclohexanediol, the cyclohexyl dimethanol, ethohexadiol, neopentyl glycol, neopentyl glycol, xylyl alcohol, dihydroxy-benzene, cresorcin, glycol ether, Triethylene glycol, dipropylene glycol or tripropylene glycol, dimethylol propionic acid, dimethylol propionic acid, tartrate, or has an above-claimed cpd of halogenic substituent.
11. the polymkeric substance of high refractive index as claimed in claim 6 and high-transmittance, wherein this initiator further comprises stiffening agent, and wherein this stiffening agent comprises the compound with structure shown in the molecule formula V:
Wherein R is independent separately and be hydrogen, C
1-8Alkyl, C
1-8Alkoxyl group, carboxyl or halogen.
12. an optical element, it comprises the described polymkeric substance of claim 1.
13. optical element as claimed in claim 12, wherein this optical element comprises packaged material, transparency carrier, lens or functional film.
14. an optoelectronic equipment comprises the described optical element of claim 12.
15. optoelectronic equipment as claimed in claim 14, wherein this optoelectronic equipment comprises photodiode, solar cell, semiconductor device or display unit.
16. the manufacture method of high refractive index and high-transmittance polymkeric substance comprises:
Compositions formulated, said composition comprises:
(a) bisphenol fluorene derivatives monomer comprises the compound with structure shown in molecular formula (I):
Wherein, R is independent separately and be hydrogen, C
1-8Alkyl, C
1-8Alkoxyl group, carboxyl or halogen; I and j be independence and be 0 or 1～10 integer separately; And
(b) diisocyanate monomer; And
Said composition is carried out polyreaction, obtain this high refractive index and high-transmittance polymkeric substance.
17. the manufacture method of high refractive index as claimed in claim 16 and high-transmittance polymkeric substance, wherein said composition comprises the organic solvent that does not participate in this polyreaction.
18. the manufacture method of high refractive index as claimed in claim 16 and high-transmittance polymkeric substance, wherein said composition further comprises initiator.
19. the manufacture method of high refractive index as claimed in claim 16 and high-transmittance polymkeric substance, wherein said composition further comprises:
(c) dibasic alcohol monomer.
20. the manufacture method of high refractive index as claimed in claim 16 and high-transmittance polymkeric substance, wherein said composition further comprises stiffening agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910262437.1A CN102101910B (en) | 2009-12-18 | 2009-12-18 | Polymer, manufacturing method of same, optical element having same and optoelectronic device having same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910262437.1A CN102101910B (en) | 2009-12-18 | 2009-12-18 | Polymer, manufacturing method of same, optical element having same and optoelectronic device having same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102101910A true CN102101910A (en) | 2011-06-22 |
| CN102101910B CN102101910B (en) | 2014-05-14 |
Family
ID=44154997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910262437.1A Active CN102101910B (en) | 2009-12-18 | 2009-12-18 | Polymer, manufacturing method of same, optical element having same and optoelectronic device having same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102101910B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432996A (en) * | 2011-10-11 | 2012-05-02 | 上海路久橡塑新材料有限公司 | Nylon nucleating agent and its preparation method and use |
| CN102660111A (en) * | 2012-05-10 | 2012-09-12 | 东南大学 | Polycarbonate optical waveguide material and preparation method thereof |
| CN108342179A (en) * | 2018-02-07 | 2018-07-31 | 袁林林 | A kind of Corrosion-Resistant Adhesive and preparation method thereof |
| CN109563222A (en) * | 2016-09-30 | 2019-04-02 | 太阳油墨制造株式会社 | Photocurable resin composition, dry film, solidfied material and printed circuit board |
| CN110218438A (en) * | 2019-06-27 | 2019-09-10 | 深圳市上古光电有限公司 | A kind of solar panel compound resin thin-film material and preparation method thereof |
| CN112162463A (en) * | 2020-08-28 | 2021-01-01 | 上海玟昕科技有限公司 | Negative high-elasticity photosensitive resin composition |
| WO2021005912A1 (en) * | 2019-07-08 | 2021-01-14 | 日本ポリテック株式会社 | Polyurethane and curable composition |
| KR20210071396A (en) * | 2019-12-06 | 2021-06-16 | 주식회사 엘지화학 | Positive-type photosensitive resin comopsition and display device comprising black bank formed by using same |
| CN114957598A (en) * | 2022-06-10 | 2022-08-30 | 万华化学集团股份有限公司 | Low-melting-point high-hardness TPU and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005068256A (en) * | 2003-08-22 | 2005-03-17 | Mitsubishi Gas Chem Co Inc | Anti-glare material |
| JP2009138073A (en) * | 2007-12-05 | 2009-06-25 | National Institute Of Advanced Industrial & Technology | Fluorene-containing polyurethane and efficient production method |
-
2009
- 2009-12-18 CN CN200910262437.1A patent/CN102101910B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005068256A (en) * | 2003-08-22 | 2005-03-17 | Mitsubishi Gas Chem Co Inc | Anti-glare material |
| JP2009138073A (en) * | 2007-12-05 | 2009-06-25 | National Institute Of Advanced Industrial & Technology | Fluorene-containing polyurethane and efficient production method |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432996A (en) * | 2011-10-11 | 2012-05-02 | 上海路久橡塑新材料有限公司 | Nylon nucleating agent and its preparation method and use |
| CN102660111A (en) * | 2012-05-10 | 2012-09-12 | 东南大学 | Polycarbonate optical waveguide material and preparation method thereof |
| CN102660111B (en) * | 2012-05-10 | 2013-09-04 | 东南大学 | Polycarbonate optical waveguide material and preparation method thereof |
| CN109563222A (en) * | 2016-09-30 | 2019-04-02 | 太阳油墨制造株式会社 | Photocurable resin composition, dry film, solidfied material and printed circuit board |
| CN109563222B (en) * | 2016-09-30 | 2021-10-15 | 太阳油墨制造株式会社 | Photocurable resin composition, dry film, cured product, and printed wiring board |
| CN108342179A (en) * | 2018-02-07 | 2018-07-31 | 袁林林 | A kind of Corrosion-Resistant Adhesive and preparation method thereof |
| CN110218438A (en) * | 2019-06-27 | 2019-09-10 | 深圳市上古光电有限公司 | A kind of solar panel compound resin thin-film material and preparation method thereof |
| CN114096579A (en) * | 2019-07-08 | 2022-02-25 | 日保丽公司 | Polyurethane and curable composition |
| WO2021005912A1 (en) * | 2019-07-08 | 2021-01-14 | 日本ポリテック株式会社 | Polyurethane and curable composition |
| KR20210071396A (en) * | 2019-12-06 | 2021-06-16 | 주식회사 엘지화학 | Positive-type photosensitive resin comopsition and display device comprising black bank formed by using same |
| KR102637326B1 (en) | 2019-12-06 | 2024-02-15 | 주식회사 엘지화학 | Positive-type photosensitive resin comopsition and display device comprising black bank formed by using same |
| CN112162463A (en) * | 2020-08-28 | 2021-01-01 | 上海玟昕科技有限公司 | Negative high-elasticity photosensitive resin composition |
| CN112162463B (en) * | 2020-08-28 | 2021-09-28 | 上海玟昕科技有限公司 | Negative high-elasticity photosensitive resin composition |
| CN114957598A (en) * | 2022-06-10 | 2022-08-30 | 万华化学集团股份有限公司 | Low-melting-point high-hardness TPU and preparation method thereof |
| CN114957598B (en) * | 2022-06-10 | 2023-07-14 | 万华化学集团股份有限公司 | Low-melting-point high-hardness TPU and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102101910B (en) | 2014-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102101910B (en) | Polymer, manufacturing method of same, optical element having same and optoelectronic device having same | |
| TWI596156B (en) | Resin composition, stretched film, circularly polarizing plate, and image display device | |
| CN101215370B (en) | Substituted fluorene polymers, their preparations and use in optical devices | |
| CN102234360B (en) | Resin-type lightguide plate composition, backlight unit, and liquid crystal display | |
| US8945815B2 (en) | Alkaline soluble resin and light sensible resin composition comprising same and use thereof | |
| Efremova et al. | Polymerisable octahedral rhenium cluster complexes as precursors for photo/electroluminescent polymers | |
| CN103019032B (en) | Photosensitive resin composition, the forming method of cured film, cured film, organic EL display and liquid crystal display device | |
| TW201134857A (en) | Process for preparing clustered functional polyorganosiloxanes, and methods for their use | |
| CN103172626A (en) | Dye compound | |
| CN107077024A (en) | Liquid crystal represents element | |
| TW201718685A (en) | Polyurethane compound and resin composition containing same | |
| CN107075069A (en) | Urethanes and the resin combination containing it | |
| CN109790186A (en) | Nitrogenous compound and color conversion coatings film comprising it | |
| KR20140137676A (en) | Polymer dots and Optical film containing that | |
| JP2013163767A (en) | Fluorescent substance and its use | |
| Han et al. | Iridium-catalyzed polymerization of benzoic acids and internal diynes: a new route for constructing high molecular weight polynaphthalenes without the constraint of monomer stoichiometry | |
| CN106833009B (en) | Coumarins green light dyestuff containing triphenylamine ethylene lateral chain | |
| CN106793354B (en) | A kind of luminous paint system | |
| CN105467640A (en) | Manufacturing method for display panel substrate, display panel substrate, and touch panel display device | |
| CN108389512A (en) | The manufacturing method of laminated body, flexible devices and laminated body | |
| JP5328705B2 (en) | Composition for silicone resin | |
| TWI438215B (en) | Polymers and method for forming the same, optical elements, and photoelectric devices employing the same | |
| CN109790187A (en) | Nitrogenous compound and color conversion coatings film comprising it | |
| CN110475780A (en) | Nitrogenous cyclic compound and color-changing membrane comprising it | |
| CN106188544A (en) | A kind of the macromolecule organic silicon carbon coated quantum dot and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |