CN100405088C - Microstructure-bearing articles of high refractive index - Google Patents
Microstructure-bearing articles of high refractive index Download PDFInfo
- Publication number
- CN100405088C CN100405088C CNB2004800410227A CN200480041022A CN100405088C CN 100405088 C CN100405088 C CN 100405088C CN B2004800410227 A CNB2004800410227 A CN B2004800410227A CN 200480041022 A CN200480041022 A CN 200480041022A CN 100405088 C CN100405088 C CN 100405088C
- Authority
- CN
- China
- Prior art keywords
- goods
- methyl
- monomer
- micromechanism
- component
- 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.)
- Expired - Fee Related
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/057—Metal alcoholates
Abstract
Blends of oligomeric urethane multi(meth)acrylate; optionally at least one other monomer selected from the group consisting of acrylic monomers, styrenic monomers and ethylenically unsaturated nitrogen heterocycles, preferably a polyol multi(meth)acrylate; and nanoparticles of an ethylenically unsaturated, preferably (meth)acrylic-functionalized, titanium or zirconium compound can be cured by ultraviolet radiation in contact with a photoinitiator to produce optical resinous articles having high refractive indices, haze ratings of at most 5% and other properties which may be tailored according to the desired use.
Description
Technical field
The present invention relates to have duplicate (replication) on micromechanism surface, relate more specifically to the resin-based composition class that so to duplicate.
Background technology
The micromechanism of resin surface is replicated in the different technologies field extremely important, for example manufacturing of traffic sign, and wherein reflectivity is provided by solid angle (cube-corner) embossed sheet; The production of Fresnel lens element and flexible video disc; Manufacturing with " the brightness enhancing " that be used for LCD or " photocontrol (lightmanagement) " film (, below being sometimes referred to as " LMF ") for for simplicity.In order to duplicate purposes, wish that resin has optimum physical property, comprise transparency basically, the viscoelastic property that is enough in storage and use, to keep the high glass transition temperature (Tg) of shape and promotes (typically passing through molding) moulding, and long-term shape retention, this comprises the micromechanism aspect of moulded products.The viscoelastic property that is fit to comprises glassy state and the modulus of rubbery state and the transition temperature that is fit between these attitudes in the certain limit.Adhere to LMF on substrate such as the polycarbonate and have excellent abrasive resistance and scratch-proofness also is desirable.
Manyly suitable be used for the resin combination that micromechanism duplicates and be disclosed in patent documentation.US patent 4,576,850 discloses large quantities of these based composition kinds.Wherein the composition of Miao Shuing is characterised in that " firmly " and " soft " segment or part is combined with the radiation polymerizable moiety.Modal is that all these three kinds of chain segment types are present in the same molecular.The key feature of " firmly " segment is wherein to have ring-type (being carbocyclic ring or heterocycle) group.The disclosed patent in back usually mentions 4,576,850, because it discloses the polymeric compositions and the precursor that are fit to.
Best, LMF has high index, preferably at least about 1.70.Reach so high refractive index, the resinous material that only uses should cost is impossible largely.The refractive index of the polymkeric substance of height monomer of bromination such as methacrylic acid penta-bromophenyl ester is about 1.71, but this base polymer has disadvantageous physical property sometimes.
US patent 6,291,070 openly has the highly transparent nanostructured mechanograph of various refractive indexes, by inorganic material (for example titania) but combine with the surface group of polymerizable or polycondensation (as derived from those of (methyl) acrylic compounds and epoxy compound) and prepare.Also can there be other monomeric substance, as (methyl) acrylate.
US patent 6,432,526 discloses the composition of high index, it metallic particles (as those of titania) that comprises highly crystalline in conjunction with organic solvent and dispersing aid to form colloidal solid.This type of particle can combine with organic polymer (for example those of derived from propylene acid esters and methacrylate), forms described composition.
Yet disclosed high index resin LMF material is significant in above-mentioned identical patent or other publication to develop other not having.Especially, it is significant providing the method that is easy to this type of material adjustment (tailor) one-tenth various characteristics.
Summary of the invention
The present invention relates to the organic and inorganic composition through mixing, they become to have the optical goods of high index by radiation-curable.Described composition can be applied to form the goods with the micromechanism of duplicating.Wherein each components in proportions can change so that wide characteristic variations to be provided.
One of them aspect of the present invention comprises goods, it becomes to have the optical resin goods on the micromechanism surface of duplicating through radiation-curable, this micromechanism of duplicating comprises a plurality of practical discontinuous (utilitarian discontinuities) with optical applications
Described goods are cured articles of the corresponding haze value of curable one-tenth maximum 5%, on the thick flat film of 3.2mm the bisphenol-a polycarbonate substrate is measured haze value according to ASTM method D1003, and described goods comprise:
(A) at least a oligomeric polyurethane (urethane) many (methyl) acrylate, randomly other monomer with at least a effective minimizing viscosity, improvement thermomechanical property or raising refractive index combines;
(B) at least a nano particle that is selected from the olefinic unsatuated metal compound of titanic and tetravalence zirconium compounds; With
(C) at least a light trigger.
Another aspect of the present invention is the optical resin goods that prepared through radiation curing by the foregoing curable goods.
Description of drawings
Fig. 1 is the LMF synoptic diagram in backlight liquid crystal displays.
Embodiment
Optical resin goods of the present invention, be characterised in that surface with the micromechanism of duplicating, it is discontinuous that this micromechanism of duplicating comprises a plurality of practicalities, as projection and depression, when using, under various conditions, its surface breaks away from from mould easily behind radiation curing and the details (detail) of not losing mould, and keeps duplicating of this type of details.These goods have various desired properties, as toughness, flexibility, optical clarity and homogeneity, and to the tolerance of common solvent.The micromechanism of this based article has high thermal dimensional stability, wearing quality and impact resistance, even and still have integrality during greatly to 180 ° when the goods angle of bend.
Term used herein " micromechanism " is as 4,576,850 definition of US patent and explain that its disclosure is hereby incorporated by.Therefore, this means and describe or characterize the predetermined required practical purposes of goods or the surface configuration of function has micromechanism.Discontinuous on described product surface, for example protrude and cave in, in section (profile), will depart from the average centerline of drawing by micromechanism, so that be included in the area summation that area summation in the above surface section of center line (surface profile) equals the following surface section of center line, described line is the nominal surface (nominalsurface) (having micromechanism) that is arranged essentially parallel to goods.About ± 0.005 to ± 750 microns usually of the height of described deviation are by representational surface characteristics length (for example 1-30 centimetre), according to the height of optics or the described deviation of determination of electron microscopy.Described average centerline can be plane (plano), concave surface, convex surface, aspheric surface or its combination.Wherein said deviation be low level (low order) (for example from ± 0.005 to ± 0.1 or, preferably, to ± 0.05 micron) and the goods of the rare or minimal generation of described deviation (i.e. surface without any significantly discontinuous) be that those surfaces that have micromechanism are " flat " or " smoothly " surperficial goods basically, this based article is useful, for example, as precison optical component or have the element at precision optics interface, as eyeglass (ophthalmic lenses).Described deviation is to comprise those goods with antireflection micromechanism in low level and the frequent goods that take place.Wherein said deviation is that the goods that high-order (high order) (for example from ± 0.1 to ± 750 micron) and being attributable to comprises the discontinuous micromechanism of a plurality of practicalities are goods of for example retroeflection solid angle thin slice (retroreflective cube-corner sheeting), linear Fresnel lens, video disc (video disc) and LMF ' s, and wherein these practicalities are discontinuous identical or different and with random or orderly mode spaced apart (spaced apart) or continuous (contiguous).Described low level and high-order both practical discontinuous can be contained in the surface that has a micromechanism.The discontinuous of outside (extraneous) or non--practicality can be contained in the surface that has micromechanism, as long as its amount or type hinder or influence unfriendly the predetermined required purposes of described goods significantly.Perhaps need or wish to select special oligomeric composition, (interfering) of this interference of this oligomer contraction when solidifying not causing is outside discontinuous, for example only shrinks the composition of 2-6%.
For example, provide detailed LMF structure and configuration in US patent 5,900,287, its disclosure is hereby incorporated by.Referring to accompanying drawing, backlight liquid crystal displays is generally shown at 10 places, comprises the LMF 11 that is usually located between diffusing globe (diffuser) 12 and LCD panel 14.Backlight liquid crystal displays also comprises light source 16 as fluorescent light, is used to transmit the photoconductive tube 18 of the light that reflects to LCD panel 14 and also be used for to the catoptrical white reflector 20 of LCD panel.The light that LMF 11 calibrations are penetrated from photoconductive tube 18, thus the brightness that improves LCD panel 14 can produce sharp image by LCD panel, and allow that the power of light source 16 reduces to produce selected brightness.LMF 11 in backlight liquid crystal displays is useful in the display of equipment such as computing machine, personal television, video recorder, mobile communications device and automobile and avionic device.
The component A of goods of the present invention is at least a oligomeric polyurethane many (methyl) acrylate.Term " (methyl) acrylate " is used to refer to the ester class of acrylic acid and methacrylic acid, " many (methyl) acrylate " refers to contain the molecule more than (methyl) acrylic groups, and be relative with " poly-(methyl) acrylate " of being commonly referred to (methyl) acrylate polymer.Modal many (methyl) acrylate is two (methyl) acrylate, but also can attempt using three (methyl) acrylate, four (methyl) acrylate or the like.
Oligomeric polyurethane many (methyl) acrylate can commercially obtain; For example from SartomerCo. they also can be by formula OCN-R
3The alkylidene diisocyanate of-NCO and the preparation of the initial reaction of polyvalent alcohol.Modal polyvalent alcohol is formula HO-R
4The glycol of-OH, wherein R
3Be C
2-100Alkylidene or arlydene, R
4Be C
2-100Alkylidene group.Intermediate product is the polyurethane diol diisocyanate then, and it can pass through the reaction with (methyl) acrylic acid hydroxy alkyl ester subsequently.The diisocyanate that is fit to comprises 2,2,4-trimethyl hexylidene diisocyanate and toluene diisocyanate; Usually preferred alkylidene diisocyanate.Particularly preferred compound can be by 2,2 in these types, and 4-trimethyl hexylidene diisocyanate, poly-(caprolactone) two are enjoyed with methacrylic acid 2-hydroxyethyl ester and being prepared.
The radiation curable composition that forms goods of the present invention also can comprise at least a effective minimizing viscosity, improve other monomer of thermomechanical property or raising refractive index.Monomer with these performances comprises acrylic monomer (being acrylate and methacrylate, acrylamide and Methacrylamide), styrene monomer and olefinic unsaturated nitrogen heterocycle.
The acrylic monomer that is fit to comprises (methyl) esters of acrylic acid of monomer.They comprise (methyl) alkyl acrylate such as methyl acrylate, ethyl acrylate, acrylic acid 1-propyl ester, methyl methacrylate and acrylic acid tertiary butyl ester.
Also comprise (methyl) esters of acrylic acid with other functional group.The example of the compound of these types has (methyl) acrylic acid 2-(N-butyl carbamyl) ethyl ester, acrylic acid 2; 4-dichlorophenyl ester, acrylic acid 2; 4,6-tribromo phenylester, acrylic acid tert-butyl-phenyl ester, phenyl acrylate, sulfo-phenyl acrylate, acrylic acid phenyl thio-ethyl ester, alkoxylate phenyl acrylate, isobornyl acrylate and acrylic acid phenoxy group ethyl ester.
These other monomers also can be that the N-of monomer replaces or N N-dibasic (methyl) acrylamide, particularly acrylamide.They comprise N-alkyl acrylamide and N, and N-dialkyl group acrylamide particularly contains C
1-4Those of alkyl.Example is N-N-isopropylacrylamide, N tert butyl acrylamide, N,N-DMAA and N, N-diethyl acrylamide.
These other monomers can further be many (methyl) acrylic acid multielement alcohol esters.This compounds is usually by the aliphatic diol that contains 2-10 carbon atom, triol and/or tetrol preparation.The example of poly-(methyl) acrylate that is fit to is ethylene glycol diacrylate, diacrylate 1,6-hexanediol ester, three acrylic acid 2-ethyl-2-methylols-1, corresponding methacrylate and (methyl) acrylate of oxyalkylated (being generally ethoxylation) derivant of ammediol ester (trimethyol propane triacrylate), tetrapropylene acid two (trimethylolpropane) ester, pentaerythritol tetracrylate, described polyvalent alcohol.
Be applicable to that the styrene compound as these other monomers comprises styrene, dichlorostyrene, 2,4,6-trichloro-benzenes ethene, 2,4,6-tribromo-benzene ethene, 4-methyl styrene and 4-phenoxy group styrene.Olefinic unsaturated nitrogen heterocycle comprises N-vinyl pyrrolidone and vinylpyridine.
B component is at least a olefinic unsatuated metal compound that is selected from titanic and tetravalence zirconium compounds, and titanium compound generally is preferred, because their rational costs and special adaptability.Because wherein unsaturated functionalized, it can enter in the polymkeric substance that forms when the radiation curing in conjunction with metallic compound.
In making goods of the present invention, importantly minimize light scattering.Therefore, B component is a form of nanoparticles." nano particle " meaning is that particle has the mean diameter of 200nm at the most.Preferably, particle diameter is 100mn at the most, more preferably 70nm and most preferably in about 5-50nm scope at the most.The particle of this size can comprise condensation in flame pyrolysis, plasma process, the gas phase (condensation) technology, colloid technology, depositing technology, sol-gel technology, controlled nucleation and growth technique, MOCVD technology and (little) emulsion technology by technology preparation well known in the art.Particularly suitable in many cases is the sol-gel technology that begins from corresponding alkoxide (being titanium or zirconium tetrol salt).
By contacting with alefinically unsaturated compounds (being generally unsaturated trialkoxy silane), can carry out or after nano particle forms, carry out the functionalized of metallic nano particle simultaneously with alkoxide or by the particle that wherein generates.Modal to be described compound be (methyl) acrylic compounds, and its Chang Youxuan (methyl) acryloxyalkyl trialkoxy silane is as 3-methacryloxypropyl trimethoxy silane (below be sometimes referred to as " MPTMS ").MPTMS is functionalized usually preferably to carry out existing under the free radical scavenger, and this free radical scavenger is for example by 4-hydroxyl-2,2,6, and 6-tetramethyl piperidine oxygen base (below be sometimes referred to as " 4-OH TEMPO ") is as the stabilized radical of example.It is believed that this functionalized main nano grain surface that influences, although the present invention does not rely on any principle of work.
Functionalized for this, normally used titanium and/or zirconium relatively the molar ratio of (methyl) acrylic compounds at about 5-10: in 1 scope.The ratio of free radical compounds is that the ratio (catalyticproportion) of catalytic action is reacted with effective promotion.Temperature of reaction is usually in about 30-80 ℃ scope.Also can there be solvent such as alkanol, heat up in a steamer (stripping) and wait except that desolvating as long as before forming curable product, carry by vacuum.As at suspending agent that is fit to such as the colloidal sol in the methyl proxitol acetate, nano particle usually is convenient to preparation.
The component C of radiation-curable goods of the present invention is at least a light triggers, effectively promotes the polymerization of described goods when being exposed to ultraviolet radiation.Suitable material as light trigger is determined in above-mentioned US patent 4,576,850 and reference works such as Encyclopedia of Polymer Technology.Example is benzoin ether, hydroxyl-and alkoxyalkyl phenyl ketone, alkylthio phenylmorpholine base alkyl ketone and acylphosphine oxide (acylphosphine oxide).Useful especially in many situations is the material of commercially available being called " Darocur 4265 ", and it comprises the potpourri of 2-hydroxyl-2-butyrophenone and (2,4, the 6-trimethylbenzoyl) diphenyl phosphine oxide.
Component ratio can change in wide scope in the radiation-curable goods of the present invention.In general, component A can comprise oligomeric polyurethane many (methyl) acrylate of about 30-100%, and surplus is another kind of (methyl) acrylate monomer.B component is the most common for comprising about 5-90% of component A and B total amount; All percentages are percent by weight.Component C (light trigger) can effectively promote existing in a small amount of polymerization when being exposed to ultraviolet radiation, and based on the polymerizable components total amount, this component is generally in about 0.005-3.0% scope and preferably about 0.005-1.0%.
The important performance of cured article of the present invention is that corresponding haze value is not more than 5%, the bisphenol-a polycarbonate substrate is measured on the thick flat film of 3.2mm according to ASTM method D1003.Other preferred performance is that the abrasion rate is not more than 20, preferably be not more than 10, measure according to falling sand abrasion test (ASTM method D968), with the bonding rate (adhesion rating) for bisphenol-a polycarbonate be 5B, measure according to grid test (crosshatch adhesion test) (ASTM method D3359).
Radiation-curable goods of the present invention can effectively mix to generate uniform potpourri by its component of blend simply, remove then anyly to be used to prepare the solvent of described component and to prepare.Chang Youxuan removes bubble by using vacuum or the like, if potpourri be viscosity adopt gentle heating, and curtain coating or the film that produces the gained blend on the contrary are to required surface.Then, film packed into has the mould of micromechanism to be duplicated, and by being exposed to polymerization under the ultraviolet radiation, generates the optical resin goods through solidifying with above-mentioned performance of the present invention.If polymerization occurs on the surface that is different from its surface that will use, the optical resin goods can be transferred on another surface.
This type of polymerization process is applicable to fast, large-scale production of articles, does not have the hostile environment influence, because do not have or only have than solvent or other volatile matter in a small amount to separate out, and polymerization can be carried out under environment temperature and pressure.This technology also is applicable to and has micromechanism the duplicating of goods of (this micromechanism comprises practical discontinuous for example projection and depression), when using, under various conditions, these goods are easy to deviate from from mould and the details of not losing mould, and keep duplicating of this type of details.Goods can be formed with various desired properties, as toughness, flexibility, optical clarity and homogeneity and to the tolerance of common solvent, even the micromechanism of this based article has high thermal dimensional stability, wearing quality and impact resistance and being kept perfectly property still when these goods are bent.
The present invention illustrates by the following examples.All parts and percentage number average by weight, except as otherwise noted.The percentage of monomer component (comprising B component) and light trigger is based on whole monomer component meters.
Embodiment 1
2,2 of the 31.2ml that in the 3 neck flasks that addition funnel (addition funnel), temperature probe and mechanical stirrer are housed, packs into, 4-trimethyl cyclohexane 1, the dibutyl tin laurate ester of 6-diisocyanate and 50mg.This addition funnel is equipped with the warm polycaprolactone glycol of 39.75g (Mn.530), in 55-60 ℃ of content that it is joined flask.Potpourri stirred 14 hours at 65 ℃ then.Subsequently, cooling flask to 55 ℃, and the potpourri of 18.7ml methacrylic acid 2-hydroxyethyl ester and 100mg hydroquinone monomethyl ether added, holding temperature is in 54-58 ℃ of scope simultaneously.Potpourri stirred 10-12 hour at 55 ℃, finished up to being confirmed to react by Infrared spectroscopy.This product is required oligomeric polyurethane dimethylacrylate, below is sometimes referred to as " oligomer dimethylacrylate ".
Embodiment 2
105g titanium tetraisonpropoxide (titanium tetraisopropoxide) stirs in the potpourri that adds 1000g 2-propyl alcohol, 49.05g concentrated hydrochloric acid and 5.25g distilled water down.Add after the 3-methacryloxypropyl trimethoxy silane of the 0.23g 33%4-OH TEMPO solution be dissolved in 1-methoxyl-2-propyl alcohol and 13.75g, the potpourri of gained stirred under room temperature 72 hours.The solution of 447g transferred to round-bottomed flask and use rotary evaporator to carry heat up in a steamer after most of volatile matter, solution was 50 ℃ of heating 6.5 hours.Add the 140g methyl proxitol acetate, continue under 55 ℃ and perfect vacuum, to carry and heat up in a steamer.Heat up in a steamer when solution weight stops to carry during for 171g, and add the 137g methyl proxitol acetate in addition in flask.Proceeding to carry and heat up in a steamer, is 236g up to solution weight.Heat up in a steamer whole volatile matters and carry out gravimetric analysis by carrying, with the solids content of the titaniferous nanoparticle dispersion of measuring gained, measurement result is 17.4 weight %.
Embodiment 3
49.5 the oligomeric polyester-polyurethane diacrylate ester admixture of part is can obtain from SartomerCo. on the market, trade mark is " CN-985B88 ", and vacuum is put forward the amount of heating up in a steamer in order to the product of embodiment 2 that 50 parts of titaniums are provided, adds " Darocur 4265 " (to be dissolved in 10% solution form in 1-methoxyl-2-propyl alcohol) of 0.5 part.The composition of gained is spun on the bisphenol-a polycarbonate plaque (plaque) from 1-methoxyl-2-propyl alcohol, and solidifies under the ultraviolet radiation of single by being exposed to " H " lamps emission.The coating of gained has 0.43% haze value, 25.7 abrasion rate and the bonding rate of 0B.Can expect that cohesive can be improved by multifunctional (methyl) acrylate monomer that adds than small scale, this cohesive is according to simple measuring.
Embodiment 4-10
Seven kinds of compositions, curable product and the goods through solidifying are prepared as light trigger and hexanediyl ester (" HDDA ") (in embodiment 5,6,8 and 10) by oligomer dimethylacrylate, the nanoparticle dispersion of embodiment 2, " Darocur4265 " (0.5%) of embodiment 1 in methyl proxitol acetate.
The have related parameter and the performance of the composition of gained provide in following table.For three kinds of samples, refractive index is measured at 589.878nm by ellipsometry (ellipsometry), and these results also are provided simultaneously.
| Embodiment | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| HDDA，％ | 0 | 67.5 | 45 | 0 | 12.5 | 0 | 6.25 |
| Embodiment 1, % | 90 | 22.5 | 45 | 50 | 37.5 | 25 | 18.75 |
| Embodiment 2, % | 10 | 10 | 10 | 50 | 50 | 75 | 75 |
| Mist degree, % | 0.29 | 0.50 | 0.42 | 1.22 | 0.50 | 2.77 | 4.07 |
| Wearability | 16.3 | 15.8 | 13.4 | 12.1 | 8.79 | 17.4 | 12.1 |
| Cohesive | 5B | 5B | 5B | 4B | 0B | 5B | 5B |
| Refractive index | -- | 1.5297 | -- | -- | 1.6289 | 1.6929 | -- |
Apparent from table, the goods through solidifying of the present invention have the refractive index (especially embodiment 9) near preferable range, haze value be not more than 5 and the abrasion rate within the required range.Except that the goods of embodiment 8, they also all have suitable bonding rate.As the goods of embodiment 3, can expect that the cohesive of embodiment 8 goods can be improved by multiple functionalized (methyl) acrylate monomer that adds than small scale, this cohesive is determined according to simple experiment.
For illustration purpose has been set forth typical embodiment, yet above-mentioned instructions and embodiment should not be considered as and limit the scope of the present invention.Therefore, can expect for those skilled in the art carrying out various improvement, modification and replacement and do not deviate from the spirit and scope of the present invention.
Claims (12)
1. goods, it becomes to have the optical resin goods on the micromechanism surface of duplicating through radiation-curable, and this micromechanism of duplicating comprises a plurality of the practical discontinuous of optical applications that have,
Described goods are cured articles of the corresponding haze value of curable one-tenth maximum 5%, on the thick flat film of 3.2mm the bisphenol-a polycarbonate substrate is measured haze value according to ASTM method D1003, and described goods comprise:
A. at least a oligomeric polyurethane many (methyl) acrylate, optional other monomer with at least a effective minimizing viscosity, improvement thermomechanical property or raising refractive index combines;
B. at least a nano particle that is selected from the olefinic unsatuated metal compound of titanic and tetravalence zirconium compounds; With
C. at least a light trigger.
2. according to the goods of claim 1, wherein B component is a titanium compound.
3. according to the goods of claim 2, wherein B component is the functionalized titanium compound of (methyl) acryloxyalkyl trialkoxy silane.
4. according to the goods of claim 3, wherein B component is the functionalized titanium compound of 3-methacryloxypropyl trimethoxy silane.
5. according to the goods of claim 2, wherein component A is 2,2,4-trimethyl cyclohexane 1, the reaction product of 6-diisocyanate, polycaprolactone glycol and methacrylic acid 2-hydroxyethyl ester.
6. according to the goods of claim 2, wherein said other monomer also exists.
7. according to the goods of claim 6, wherein this other monomer is acrylic monomer, styrene monomer or olefinic unsaturated nitrogen heterocycle.
8. according to the goods of claim 6, wherein this other monomer is many (methyl) acrylic acid multielement alcohol ester.
9. goods according to Claim 8, wherein said many (methyl) acrylic acid multielement alcohol ester is a hexanediol diacrylate.
10. according to the goods of claim 1, wherein B component is the functionalized zirconium compoundss of (methyl) acryloxyalkyl three alkane nitrogen base silanes.
11. according to the goods of claim 10, wherein B component is the functionalized zirconium compounds of 3-methacryloxypropyl trimethoxy silane.
12. goods, it becomes to have the optical resin goods on the micromechanism surface of duplicating through radiation-curable, and this micromechanism of duplicating comprises a plurality of the practical discontinuous of optical applications that have,
Described goods are that corresponding haze value of curable one-tenth maximum 5% and abrasion rate are not more than 20 cured article, wherein, on the thick flat film of 3.2mm, the bisphenol-a polycarbonate substrate are measured haze value according to ASTM method D1003, and measure the abrasion rate, and described goods comprise according to ASTM method D968:
A.2,2,4-trimethyl cyclohexane 1, the reaction product of 6-diisocyanate, polycaprolactone glycol and methacrylic acid 2-hydroxyethyl ester;
The nano particle of the titanium compound that B. at least a 3-methacryloxypropyl trimethoxy silane is functionalized; With
C. at least a light trigger.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2004/002049 WO2005083476A1 (en) | 2004-01-26 | 2004-01-26 | Microstructure-bearing articles of high refractive index |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101087596A Division CN101334494A (en) | 2004-01-26 | 2004-01-26 | High refractive index product possessing microscopic structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1906506A CN1906506A (en) | 2007-01-31 |
| CN100405088C true CN100405088C (en) | 2008-07-23 |
Family
ID=34912863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800410227A Expired - Fee Related CN100405088C (en) | 2004-01-26 | 2004-01-26 | Microstructure-bearing articles of high refractive index |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1711848A1 (en) |
| JP (1) | JP2007522499A (en) |
| CN (1) | CN100405088C (en) |
| AU (1) | AU2004316424A1 (en) |
| BR (1) | BRPI0418066A (en) |
| CA (1) | CA2554156A1 (en) |
| WO (1) | WO2005083476A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170076732A (en) * | 2014-10-22 | 2017-07-04 | 미츠비시 가스 가가쿠 가부시키가이샤 | Triacrylate compound, production method therefor, and composition |
| CN106350703B (en) * | 2015-07-16 | 2018-07-10 | 东北大学 | A kind of method for preparing kalzium metal with electrolysis raw aluminum liquid fused salt thermal reduction |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03145602A (en) * | 1989-11-01 | 1991-06-20 | Seiko Epson Corp | Laminate and production thereof |
| EP0832917A1 (en) * | 1995-06-09 | 1998-04-01 | Mitsubishi Rayon Co., Ltd. | Molded resin articles having marproof organic hard coat layer and nonfogging organic hard coat layer, process for the production of the same, and coating materials therefor |
| CN1192766A (en) * | 1995-08-30 | 1998-09-09 | 美国3M公司 | Back light reflection sheet for liquid cyrstal |
| US6291070B1 (en) * | 1997-05-13 | 2001-09-18 | Institut für Neue Materialien Gemeinnützige GmbH | Nanostructured moulded bodies and layers and method for producing same |
| CN1347432A (en) * | 1999-02-15 | 2002-05-01 | Dsm有限公司 | Resin composition and cured product |
| US6432526B1 (en) * | 1999-05-27 | 2002-08-13 | 3M Innovative Properties Company | Nanosize metal oxide particles for producing transparent metal oxide colloids and ceramers |
-
2004
- 2004-01-26 WO PCT/US2004/002049 patent/WO2005083476A1/en active Application Filing
- 2004-01-26 AU AU2004316424A patent/AU2004316424A1/en not_active Abandoned
- 2004-01-26 CN CNB2004800410227A patent/CN100405088C/en not_active Expired - Fee Related
- 2004-01-26 BR BRPI0418066-6A patent/BRPI0418066A/en not_active IP Right Cessation
- 2004-01-26 CA CA002554156A patent/CA2554156A1/en not_active Abandoned
- 2004-01-26 EP EP04705267A patent/EP1711848A1/en not_active Withdrawn
- 2004-01-26 JP JP2006551021A patent/JP2007522499A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03145602A (en) * | 1989-11-01 | 1991-06-20 | Seiko Epson Corp | Laminate and production thereof |
| EP0832917A1 (en) * | 1995-06-09 | 1998-04-01 | Mitsubishi Rayon Co., Ltd. | Molded resin articles having marproof organic hard coat layer and nonfogging organic hard coat layer, process for the production of the same, and coating materials therefor |
| CN1192766A (en) * | 1995-08-30 | 1998-09-09 | 美国3M公司 | Back light reflection sheet for liquid cyrstal |
| US6291070B1 (en) * | 1997-05-13 | 2001-09-18 | Institut für Neue Materialien Gemeinnützige GmbH | Nanostructured moulded bodies and layers and method for producing same |
| CN1347432A (en) * | 1999-02-15 | 2002-05-01 | Dsm有限公司 | Resin composition and cured product |
| US6432526B1 (en) * | 1999-05-27 | 2002-08-13 | 3M Innovative Properties Company | Nanosize metal oxide particles for producing transparent metal oxide colloids and ceramers |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007522499A (en) | 2007-08-09 |
| AU2004316424A1 (en) | 2005-09-09 |
| CA2554156A1 (en) | 2005-09-09 |
| CN1906506A (en) | 2007-01-31 |
| BRPI0418066A (en) | 2007-04-17 |
| WO2005083476A8 (en) | 2006-01-19 |
| WO2005083476A1 (en) | 2005-09-09 |
| EP1711848A1 (en) | 2006-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6844950B2 (en) | Microstructure-bearing articles of high refractive index | |
| TWI523922B (en) | A method for producing an organic-inorganic composite, a hardened composition, a hardened product of a hardened composition, a hard coat material, a hard coat film and a silane coupling agent | |
| US6815034B2 (en) | Light-curable resin composition having antistatic property | |
| TW200422336A (en) | Radiation curable resin composition and cured product thereof | |
| JP2008535949A (en) | Polymerizable oligomeric urethane composition containing nanoparticles | |
| CN1756968A (en) | Radiation curable microstructure-bearing articles | |
| CN104371068A (en) | Microstructured optical films | |
| US20110092653A1 (en) | Metal-Containing Compositions | |
| JP2015152691A (en) | Anti-glare anti-reflection film for insert molding and resin molded product produced using the same | |
| KR101347176B1 (en) | Ultraviolet Cured Organic-Inorganic Hybrid Resin and The Resin Composition For Optical Film | |
| CN109983092A (en) | The flexible hard coating of oligourethane comprising hydrogen bonding to acrylic polymer | |
| US20080103241A1 (en) | Resin composition and production method thereof | |
| JP2006188659A (en) | Radiation-curable resin composition and cured product thereof | |
| TW202330670A (en) | Active energy ray-curable resin, active energy ray-curable anti-fog resin composition, and cured product and article thereof using a copolymer (A) having a hydroxyl group and an isocyanate compound (B) having a (meth)acryloyl group as necessary reaction raw materials | |
| KR101025721B1 (en) | Non-Solvent Type, UV-Curable White Ink Composition | |
| JP2006152273A (en) | Radiation-curable composition and cured product thereof, and laminated form of the cured product | |
| CN104418958A (en) | Preparation method of organic mineral complex, curable composition, cured product of curable composition, hard coating material, hard coating film and silane coupling agent | |
| CN100405088C (en) | Microstructure-bearing articles of high refractive index | |
| JP6269125B2 (en) | Anti-glare film for insert molding | |
| JP2017171726A (en) | Curable composition, cured product thereof, and laminate | |
| CN101334494A (en) | High refractive index product possessing microscopic structure | |
| JP2005003772A (en) | Composition for optical material and optical element | |
| KR101251457B1 (en) | Acryl acrylate and resin composition including the same | |
| JP2005240014A (en) | Radiation-curable resin composition, method for producing the radiation-curable resin composition, cured product, laminated product, and optical recording medium | |
| JP2006152268A (en) | Radiation-curable composition and the resultant cured product, and laminated form of the cured product |
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 | ||
| ASS | Succession or assignment of patent right |
Owner name: SHABO BASE CREATION PLASTICS INTELLECTUAL PROPERT Free format text: FORMER OWNER: GENERAL ELECTRIC CO. Effective date: 20081107 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20081107 Address after: Bergen Op Zoom Holland Patentee after: Sabic Innovative Plastics Ip Address before: American New York Patentee before: General Electric Company |
|
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |