CN1965041A - Low refractive index coating composition - Google Patents
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- CN1965041A CN1965041A CN 200580012466 CN200580012466A CN1965041A CN 1965041 A CN1965041 A CN 1965041A CN 200580012466 CN200580012466 CN 200580012466 CN 200580012466 A CN200580012466 A CN 200580012466A CN 1965041 A CN1965041 A CN 1965041A
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Abstract
The present invention provides coating compositions that, when cured, provide a coating with low refractive index, surface hardness, scratch resistance, abrasion, resistance and good curability at low film thickness. In one embodiment, a composition is provided that comprises reactive nanoparticles free of fluorinated group, reactive nanoparticles having at least one fluorinated group, and an ethylenically unsaturated urethane fluorinated component.
Description
Technical field
The present invention relates to radiation curable coating composition, the coating by these compositions are solidify to form, prepare the method for these coatings and comprise the object of these coatings.One aspect of the present invention relates to the application of these coatings on hard coat film layer or indicating system.
Background technology
There were the various trials of development coating composition this area, but be to develop the coating composition that is used to prepare low refractive index coating more than the interest, described low refractive index coating has surface of good hardness, resistance to marring, wear resistance and good curing performance at thin film thickness.Purpose of the present invention comprises these coating compositions of preparation.
U.S. Pat 6,391,459 have discussed and have comprised the radiation-hardenable composition of fluoridizing oligourethane.United States Patent (USP) 6,160,067 has mentioned the active silicon dioxide granule that contains polymerisable unsaturated group.
Summary of the invention
Purpose of the present invention comprises the composition that provides following, and described composition is provided at the coating that thin film thickness has low-refraction, surface hardness, resistance to marring, wear resistance and good curing performance when solidifying.
An embodiment of composition of the present invention is a radiation-hardenable composition, and it comprises:
A) the active nano particle that does not have (or not existing) fluorinated groups;
B) contain the active nano particle of at least one fluorinated groups; With
C) ethylene linkage unsaturated urethane fluorinated component.
Another embodiment of the invention is a kind of object, and described object comprises:
A) substrate;
B) hard coat film layer;
C) high refractive index coating on described hard coat film layer; With
D) low refractive index coating, described low refractive index coating obtains by following composition is solidified, and described composition comprises:
I) there is not the active nano particle of fluorinated groups;
The active nano particle that ii) contains at least one fluorinated groups; With
Iii) ethylene linkage unsaturated urethane fluorinated component.
In other embodiments of the present invention, provide from the method for described preparation of compositions coating.Use composition of the present invention to be provided for various application examples as coating at optical fiber, photonic crystal fiber, printing ink and matrix, optical medium and/or indicating meter.
Another aspect of the present invention relates to uses composition of the present invention to form coating on substrate, described substrate comprises that for example watch-dog is (such as plansifter computer and/or TV monitor, for example use for example United States Patent (USP) 6 that is combined in this by reference, 091,184 and 6, those of 087,730 described technology), CD, touch-screen, smart card, flexible glass etc.There are a large amount of interest in the development of the plastic of LCD (liquid-crystal display) and OLED (Organic Light Emitting Diode) display application for example being used for.
Composition of the present invention can be used as coating composition and uses.For example, can use composition coated substrate of the present invention.The applied substrate that is fit to comprises organic substrate.Organic substrate preferred polymers (" plastics ") substrate, the substrate that for example comprises following polymkeric substance: polynorbornene, polyethylene terephthalate, polymethylmethacrylate, polycarbonate, polyethersulfone, polyimide, fluorenes polyester (for example main origin comes from 9, polymkeric substance or its mixture that the equal copolymerization repeating unit of two (4-hydroxyphenyl) fluorenes of 9-and m-phthalic acid, terephthalic acid is formed), Mierocrystalline cellulose (for example cellulosetri-acetate) and/or polyethers naphthalene.Particularly preferred substrate comprises polynorbornene substrate, fluorenes polyester substrate, cellulosetri-acetate substrate, polyimide substrate.
Another object of the present invention, advantage and feature have been described in this manual, and by check the following stated, wherein part will become obviously to those skilled in the art, perhaps can understand by practice of the present invention.Invention disclosed is not subject to any concrete one group of purpose, advantage and feature or its combination in this application.Intention is that the various combinations of purpose of description, advantage and feature form disclosed the present invention among the application.
The specific embodiment mode
Definition:
" nano particle " refers to that most of particle in the mixture wherein has the granular mixture less than 1 micron-scale.
" size of nano particle " (or " size of nano particle ") refers to particle diameter for spheroidal particle.For aspherical particle, it refers to the longest collinear distance of drawing to a relative side from a side of nano particle.
" (methyl) acrylate " refers to " acrylate and/or methacrylic ester ".
" active nano particle " refers to contain the nano particle of at least one active group (for example polymerizable groups).
Especially, the present invention relates to a kind of following radiation-hardenable composition, described radiation-hardenable composition comprises:
A) there is not the active nano particle of fluorinated groups;
B) contain the active nano particle of at least one fluorinated groups; With
C) ethylene linkage unsaturated urethane fluorinated component.
The active nano particle
Preparation active nano particulate method can change.In one embodiment, the active nano particle can comprise metal oxide nanoparticles (A) and chemically in conjunction with thereon component (B), wherein component (B) comprises at least one active group, for example polymerizable groups.
In one embodiment, metal oxide nanoparticles (A) comprises the nano particle that is selected from the group of being made up of the oxide compound of silicon, aluminium, zirconium, titanium, zinc, gallium, indium, tin, antimony and cerium.In one embodiment, nano particle (A) is single metal oxide of planting.In another embodiment, nano particle (A) is the mixture of different metal oxide.It should be appreciated by those skilled in the art that with regard to the object of the invention although can think that in common usage silicon is not " metal ", metal oxide nanoparticles of the present invention also comprises the oxide compound of silicon.
Can use metal oxide nanoparticles (A) with for example form of powder or with the form of water or solvent dispersion (colloidal sol).When metal oxide nanoparticles is the dispersion form, from the mutual solubility of other component and the viewpoint of dispersibility, organic solvent is preferably as dispersion medium.Requiring solidifying product to have in the application of excellent transparency, the solvent dispersion that uses metal oxide is suitable especially.The example of organic solvent comprises: alcohol is methyl alcohol, ethanol, Virahol, butanols and octanol for example; Ketone is acetone, methylethylketone, methyl iso-butyl ketone (MIBK) and pimelinketone for example; Ester is ethyl acetate, butylacetate, ethyl lactate and gamma-butyrolactone, propylene glycol methyl ether acetate and propylene glycol monoethyl ether acetate for example; Ether is ethylene glycol monomethyl ether and diethylene glycol monobutyl ether for example; Aromatic hydrocarbon is benzene, toluene and dimethylbenzene for example; With acid amides for example dimethyl formamide, N,N-DIMETHYLACETAMIDE and N-Methyl pyrrolidone.
In one embodiment, nano particle (A) comprises the colloidal silica nano particle.These nano SiO 2 particles are commercially available, its trade(brand)name for example: the Methanol Silica Sol that Nissan Chemical Industries, Ltd. produce, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL etc.The example of Powdered silicon-dioxide comprises the product that can obtain with following trade(brand)name: AEROSIL 130, AEROSIL 300, AEROSIL 380, AEROSIL TT600 and AEROSILOX50 (Japan Aerosil Co., Ltd. produces), Sildex H31, H32, H51, H52, H121, H122 (Asahi Glass Co., Ltd. produce), E220A, E220 (Nippon Silica Industrial Co., Ltd. produce), SYLYSIA470 (Fuji Silycia Chemical Co., Ltd. produces) and SG Flake (Nippon Sheet Glass Co., Ltd. produces).
The example of commercially available aluminium oxid-dispersion comprises water dispersion Alumina Sol-100 ,-200 ,-520 (Ltd. produces for trade(brand)name, Nissan Chemical Industries); The Virahol dispersion of aluminum oxide, AS-1501 (Ltd. produces for trade(brand)name, Sumitomo Osaka Cement Co.); With the toluene dispersion of aluminum oxide, AS-150T (Ltd. produces for trade(brand)name, Sumitomo Osaka Cement Co.).An example of zirconium white toluene dispersion is HXU-110JC (Ltd. produces for trade(brand)name, Sumitomo OsakaCement Co.).An example of the water dispersion product of zinc antimonates powder is Celnax (Ltd. produces for trade(brand)name, Nissan Chemical Industries).The example of the powder of aluminum oxide, titanium oxide, stannic oxide, Indium sesquioxide, zinc oxide and solvent dispersion product is to be purchased with for example trade(brand)name Nano Tek (Ltd. produces for trade(brand)name, CI Kasei Co.).An example of the water-dispersion colloidal sol of antimony-doped tin oxide is SN-100D (Ltd. produces for trade(brand)name, Ishihara Sangyo Kaisha).An example of ito powder is Misubishi Material Co., the product that Ltd. produces; With an example of the water dispersion of cerium oxide be Needral (Ltd. produces for trade(brand)name, Taki Chemical Co.).
The shape of metal oxide nanoparticles (A) can be the shape that is applicable to required application, comprises sphere, non-sphere, hollow, porous, bar-shaped, tabular, fibrous, amorphous and/or these combination.For example, nano particle can be a bar-shaped and hollow or tabular and porous etc.
In one embodiment, the great majority of nano particle (A) (for example at least 60%, at least 75%, at least 90%, at least 94%, at least 96% or at least 98%) for example have less than the size of 900nm less than 750nm, less than 600nm, less than 500nm, less than 300nm or less than 150nm, less than 100nm or even less than 75nm.In one embodiment, size for example at least 1nm, at least 5nm, at least 10nm or at least 20nm of the great majority of nano particle (A) (for example at least 60%, at least 75%, at least 90%, at least 94%, at least 96% or at least 98%) with 0.1nm at least.Be used for determining that the method for particle size comprises for example BET absorption, optics or scanning electronic microscope or atomic force microscope (AFM) imaging.
In one embodiment, the mean sizes of nano particle (A) is less than 900nm, for example less than 750nm, less than 600nm, less than 500nm, less than 300nm, less than 150nm, less than 100nm or even less than 75nm.In one embodiment, the mean sizes of nano particle (A) is 0.1nm at least, for example 1nm, 5nm, 10nm or 20nm at least at least at least at least.
Component (B) can be for example to comprise the organic constituent and/or the inorganic-organic constituent of active group.The example that is included in the active group in the component (B) comprises that for example the ethylene linkage unsaturated group is as (methyl) acrylate or vinyl ether.
In one embodiment, component (B) also comprises the one or more groups by following formula (1) expression:
-X-C(＝Y)-NH- (1)
Wherein X represents NH, O (Sauerstoffatom) or S (sulphur atom), and Y represents O or S.Group by formula (1) expression is, for example amino-formate bond [O-C (=O)-NH-] ,-O-C (=S)-NH-or thiocarbamate key [S-C (=O)-NH-].
Component (B) comprises silanol group or forms the group of silanol group by hydrolysis equally, in one embodiment.
The example of component (B) comprises, for example following organoalkoxysilane component, described organoalkoxysilane component in molecule, comprise amino-formate bond [O-C (=O)-NH-] and/or thiocarbamate key [S-C (=O) NH-] and at least two polymerisable unsaturated groups.
Be suitable for representing by following structural formula I with a specific examples of the component (B) of nano particle (A) reaction:
Formula I
Another example is the component of for example being represented by following formula (2):
R wherein
1The expression methyl, R
2Expression contains alkyl, the R of 1-6 carbon atom
3Expression hydrogen atom or methyl, m represent 1 or 2, n represents the integer of 1-5, X represents to contain the divalent alkyl of 1-6 carbon atom, and Y represents to contain straight chain, ring-type or the side chain bivalent hydrocarbon radical of 3-14 carbon atom, and Z represents to contain straight chain, ring-type or the side chain bivalent hydrocarbon radical of 2-14 carbon atom.Z can comprise ehter bond.
For example, can be by making multi-functional (methyl) acrylate reactions of sulfydryl organoalkoxysilane, vulcabond and hydroxyl, preparation is by the component of formula (2) expression.
Preparation method's a example is, for example make sulfydryl organoalkoxysilane and di-isocyanate reaction to obtain following intermediate, described intermediate comprises the thiocarbamate key, and multi-functional (methyl) acrylate reactions that makes remaining isocyanic ester and hydroxyl is to obtain comprising the product of amino-formate bond.
Multi-functional (methyl) acrylate reactions by making vulcabond and hydroxyl to be obtaining comprising the intermediate of amino-formate bond, and makes remaining isocyanic ester and the reaction of sulfydryl organoalkoxysilane, can obtain same products.Yet, because this method causes the generation of the acrylate-based addition reaction of sulfydryl organoalkoxysilane and (methyl), so degree of purity of production may be impaired.In addition, may form gel.
As being used for the example of preparation, can provide γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane, γ-sulfydryl propyl group three butoxy silanes, γ-sulfydryl propyl-dimethyl methoxy silane, γ-sulfydryl propyl group methyl dimethoxysilane etc. by the sulfydryl organoalkoxysilane of the component of formula (2) expression.Wherein, preferred γ-Qiu Jibingjisanjiayangjiguiwan and γ-sulfydryl propyl group methyl dimethoxysilane.
As the example of the commercially available product of sulfydryl organoalkoxysilane, can provide SH6062 (Toray-Dow Corning Silicone Co., Ltd. produces).
Example as vulcabond, tetramethylene vulcabond, hexamethylene vulcabond, isophorone diisocyanate, hydrogenated xylene diisocyanate, Hydrogenated Bisphenol A vulcabond, 2 can be provided, 4-tolylene diisocyanate, 2,6-tolylene diisocyanate etc.Wherein, preferred 2,4 toluene diisocyanate, isophorone diisocyanate and hydrogenated xylene diisocyanate.
Example as the commercially available product of polyisocyanate compounds, TDI-80/20, TDI-100, MDI-CR100, MDI-CR300, MDI-PH, NDI (Mitsui Nisso UrethaneCo. can be provided, Ltd. produce), Coronate T, Millionate MT, Millionate MR, HDI (NipponPolyurethane Industry Co., Ltd. produce), Takenate 600 (Takeda ChemicalIndustries, Ltd. produces) etc.
Example as multi-functional (methyl) acrylate of hydroxyl can provide TriMethylolPropane(TMP) two (methyl) acrylate, three (2-hydroxyethyl) isocyanuric acid ester two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate etc.Wherein, preferred three (2-hydroxyethyl) isocyanuric acid ester two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate and Dipentaerythritol five (methyl) acrylate.These compounds form at least two polymerisable unsaturated groups in the compound by formula (2) expression.
Multi-functional (methyl) acrylate of sulfydryl organoalkoxysilane, vulcabond and hydroxyl can be used in combination separately or with two or more.
In the preparation of the component of representing by formula (2), use multi-functional (methyl) acrylate of sulfydryl organoalkoxysilane, vulcabond and hydroxyl, make the mol ratio of vulcabond and sulfydryl organoalkoxysilane be preferably 0.8-1.5, and 1.0-1.2 more preferably.If mol ratio less than 0.8, may reduce the stability in storage of composition.If mol ratio surpasses 1.5, may reduce dispersibility.
Preferably in dry air preparation by the component of formula (2) expression to prevent the hydrolysis of acrylate-based anaerobic polymerization and organoalkoxysilane.Temperature of reaction is preferably 0-100 ℃, and more preferably 20-80 ℃.
In the preparation of the component of representing by formula (2), can in the carbamate formation reaction, use conventional catalyst to reduce preparation time.As described catalyzer, can provide dibutyl tin laurate, two lauric acid dioctyl tins, two (2 ethyl hexanoic acid) dibutyl tins and nitrilotriacetic tin octylate.In one embodiment, with total amount be the amount interpolation catalyzer of 0.01-1 weight % with respect to catalyzer and vulcabond.
In preparation, can add thermal polymerization inhibitor to stop thermopolymerization by the compound of formula (2) expression.As the example of thermal polymerization inhibitor, can provide p methoxy phenol, Resorcinol etc.Be that the amount of 0.01-1 weight % is added thermal polymerization inhibitor preferably with total amount with respect to multi-functional (methyl) acrylate of thermal polymerization inhibitor and hydroxyl.
Can in solvent, prepare component by formula (2) expression.As described solvent, can suitably select any such solvent, described solvent not with multi-functional (methyl) acrylate reactions of sulfydryl organoalkoxysilane, vulcabond and hydroxyl, and have and be equal to or less than 200 ℃ boiling point.
As the specific examples of this solvent, can provide ketone such as methylethylketone, methyl iso-butyl ketone (MIBK) and pimelinketone, ester such as ethyl acetate, butylacetate and pentyl acetate, hydrocarbon such as toluene and dimethylbenzene etc.
As the specific examples of organoalkoxysilane component, can provide: contain the component of unsaturated double-bond in the molecule, for example gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-acryloyl-oxy propyl trimethoxy silicane and vinyltrimethoxy silane; The component that contains epoxy group(ing) in the molecule, for example γ-glycidoxy propyl-triethoxysilicane and γ-glycidoxypropyltrime,hoxysilane; Contain amino compound in the molecule, for example γ-An Jibingjisanyiyangjiguiwan and gamma-amino propyl trimethoxy silicane; The component that contains sulfydryl in the molecule, for example γ-Qiu Jibingjisanjiayangjiguiwan and γ-sulfydryl propyl-triethoxysilicane; Alkyl silane, for example methyltrimethoxy silane, Union carbide A-162 and phenyltrimethoxysila,e; Or the like.Wherein, the viewpoint of the dispersion stabilization of the oxide particle after the surface treatment, preferred γ-Qiu Jibingjisanjiayangjiguiwan, γ-glycidoxypropyltrime,hoxysilane, methyltrimethoxy silane, Union carbide A-162 and phenyltrimethoxysila,e.
Active group in component (B) can change.Active group comprises, and is foregoing, for example undersaturated polymerizable groups.Active group comprises, for example acrylate, methacrylic ester, propenyl, vinyl, butadienyl, styryl, ethynyl, cinnyl, Vinyl Ether, maleic acid ester, acrylamide, epoxy, trimethylene oxide, amine-alkene and mercaptan-alkene group.
Active group in component (B) can also be the polymerizable groups with other moiety combinations.The example of these combinations comprises, for example with the carboxylic acid and/or the carboxylic acid anhydride of epoxy group(ing) combination, with the particularly acid of 2-hydroxyalkylamides combination of oxy-compound, with isocyanic ester blocked isocyanate for example, the amine of uretdione (uretdion) or carbodiimide combination, epoxy with amine or Dyhard RU 100 combination, hydrazine acid amides with the isocyanic ester combination, with isocyanic ester blocked isocyanate for example, the oxy-compound of uretdione or carbodiimide combination, oxy-compound with the acid anhydrides combination, oxy-compound with (etherificate) methylol amide (" amino-resin ") combination, mercaptan with the isocyanic ester combination, mercaptan with acrylate (optionally free radical causes) combination, acetylacetic ester with the acrylate combination, with when use is cationic crosslinked, contain the epoxy compounds or the oxy-compound of epoxy group(ing).Therefore, for example, the part of component (B) can contain another part as the amido of active group and component (B) can contain isocyanate group as active group to form polymerisable combination.
The example of operable active group in addition is included in the isocyanic ester of moisture-curable in vinylbenzene and/or the methacrylic ester, alkoxyl group/the acyloxy of moisture-curable-silane, the titan-alkoxide acid esters, alkoxy zirconium ester or urea-, urea/trimeric cyanamide-, carbamide or P-F (soluble phenolic resin, phenolic varnish type) mixture, the perhaps undersaturated list of ethylene linkage of radically curing (superoxide-or light-initiated) and multi-functional monomer and polymkeric substance acrylate for example, methacrylic ester, maleic acid ester/Vinyl Ether, perhaps unsaturated (for example toxilic acid or fumaric acid) polyester of radically curing (superoxide-or light-initiated).
About the example of the method for preparing active particle, for example in the United States Patent (USP) 6,160,067 of the Eriyama that is combined in this by reference and in full etc. and WO 00/4766, mentioned the example that is used for active nano particle and preparation thereof that is fit to.Simultaneously, metal oxide nanoparticles (A) usually contains the moisture as planar water on nano grain surface under common condition of storage.In addition, on the surface of oxide nano particles, usually there are component such as oxyhydroxide, the hydrate etc. that form component reaction with silanol group at least.Therefore, crosslinkable nano particle (A) can mix when being incorporated in stirring mixture heating up is prepared by silanol group being formed component and metal oxide (A).Suitable is that the silanol group that reacts in the presence of water effectively organic constituent (B) is occupied forms position and oxide nano particles (A) combination.
The preferred dewatering agent that adds is to promote described reaction.As dewatering agent, can use mineral compound such as zeolite, anhydride silica and anhydrous alumina and organic compound such as original acid A ester, ethyl orthoformate, tetra ethoxy methane and four butoxy-methanes.Usually use organic compound as dewatering agent; Example is ortho ester such as original acid A ester and ethyl orthoformate.
Simultaneously, in " embodiment " part hereinafter the active nano particulate method that is used to prepare the active nano particle that does not have fluorinated groups and contains at least one fluorinated groups has been described.
In one embodiment, except that one or more contained the component (B) of active group, the active nano particle can also comprise one or more organic constituents that does not contain active group.The active nano particle and the active nano particle that contains at least one fluorinated groups that do not have fluorinated groups:
The component that " the active nano particle that does not have fluorinated groups " (or " the active nano particle that does not have fluorinated groups ") refers to chemically be attached on the metal oxide nanoparticles does not contain any fluorinated groups." the active nano particle that contains at least one fluorinated groups " is defined as except that the optional component that does not have fluorinated groups that exists in addition, also in conjunction with the active nano particle that comprises the component of fluorinated groups.The component of these fluorinated groups can comprise or not comprise active group.In other words, fluorinated groups is positioned at the component that comprises active group or is not positioned at the component that comprises active group.Not having the example of component of the fluorinated group of active group is for example to contain the Trimethoxy silane material of fluoroalkyl molecular moiety.Example comprises, for example perfluoro hexyl ethyl trimethoxy silane, perfluoro capryl ethyl trimethoxy silane, 13 fluoro-1,1,2,2-tetrahydrochysene octyltri-ethoxysilane, 17 fluoro-1,1,2,2-tetrahydrochysene decyl triethoxyl silane or perfluor decyl ethyl trimethoxy silane.
The example of fluorinated groups includes but not limited to: difluoromethyl, trifluoromethyl, two fluoro ethyls, trifluoroethyl, tetrafluoro ethyl, pentafluoroethyl group, two fluoropropyls, trifluoro propyl, tetrafluoro propyl group, five fluoropropyls, hexafluoro propyl group, seven fluoropropyls, difluoro butyl, trifluoro butyl, tetrafluoro butyl, five fluorine butyl, hexafluoro butyl, seven fluorine butyl, octafluoro butyl, difluoro amyl group, trifluoro amyl group, tetrafluoro amyl group, five fluorine amyl groups, hexafluoro amyl group, seven fluorine amyl groups, octafluoro amyl group, similarly C
1-C
30Side chain straight-chain paraffin or alcohol perfluor derivative and C
1-C
30Side chain straight-chain paraffin or alcohol 1,1,2,2-tetrahydrochysene fluorine derivative, and above-mentioned fluor alkaline/alcohol or 1,1,2, the part ethoxylation or the propoxylation form of 2-tetrahydrochysene fluothane hydrocarbon/alcohol.In one embodiment, the active particle that contains fluorinated groups comprises fluoroalkyl.
In one embodiment of the invention, not having the active nano particle of fluorinated groups is from 1: 10 to 20: 1 with the active nano particulate weight ratio that contains at least one fluorinated groups, for example 1: 9 to 9: 1,1: 1 to 15: 1,3: 1 to 10: 1,3: 1 to about 9: 1, perhaps 6: 1 to about 8: 1.
In one embodiment, the active nano particle that does not have a fluorinated groups is from 20% to 90% with respect to the weight ratio of the gross weight of all active particles and ethylene linkage unsaturated urethane fluorinated component, for example 40-90%, 60-90% or 75-90%.In one embodiment, the active nano particle that contains fluorinated groups is 5-50% with respect to the weight ratio of the gross weight of all active particles and ethylene linkage unsaturated urethane fluorinated component, for example 5-35%, 5-25% or 10-15%.
Ethylene linkage unsaturated urethane fluorinated component:
In one embodiment, ethylene linkage unsaturated urethane fluorinated component is the fluorinated oligomeric thing that comprises one or more ethylene linkage unsaturated groups and one or more carbamate groups.
Fluoridizing oligourethane can be the reaction product of fluoridizing polyvalent alcohol, polymeric polyisocyanate at least and containing the reactive monomer of unsaturated ethylene linkage.Described reactive monomer for example can comprise (methyl) acrylate, Vinyl Ether, maleic acid ester, fumarate or other ethylene linkage unsaturated group in its structure.
In one embodiment, fluoridize oligourethane and have about 700 to about 10, the molecular weight of 000g/mol for example about 1000 to about 5000g/mol scope.
The operable polyvalent alcohol of fluoridizing comprises in the preparation of fluoridizing oligourethane, for example fluoridizes polyoxymethylene, polyethylene oxide, poly(propylene oxide), polybutylene oxide or its multipolymer.In one embodiment, fluoridizing polyvalent alcohol adopts ethylene oxide-capped.The polyvalent alcohol of fluoridizing that is fit to comprises, for example the Fluorolink fluid series product (Fluorolink L, C, D, the B that sell of Solvay-Solexis Inc., E, B1, T, L10, A10, D10, S10, C10, E10, T10 or F10) or Fomblin Z-Dol TX series product.These polyvalent alcohols are to adopt ethylene oxide-capped poly-(oxyethane-formaldehyde) multipolymer of fluoridizing.Other may be fit to fluoridizes polyvalent alcohol and comprises and contain side chain or main chain is fluoridized the acrylic acid or the like oligopolymer or the telechelic polymer of functional group, as the acrylic copolymer of R 1216 and vinylformic acid hydroxyl butyl ester, the perhaps acrylic copolymer of (methyl) vinylformic acid trifluoro ethyl ester and vinylformic acid hydroxyl butyl ester.Other is fit to fluoridizes the polyvalent alcohol of the MPD series polyvalent alcohol that L-12075 that polyvalent alcohol comprises that 3M company for example sells and Dupont sell.
Operable polymeric polyisocyanate comprises separately or multiple organic polymeric polyisocyanate of form of mixtures in the preparation of fluoridizing oligourethane.Described polymeric polyisocyanate can with fluoridize the reaction of the undersaturated isocyanate activity compound of polyvalent alcohol and ethylene linkage, form ethylene linkage unsaturated urethane fluorinated component: vulcabond is in preferred polymeric polyisocyanate.Typical vulcabond comprises isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), MDI, hexamethylene diisocyanate, the cyclohexylidene vulcabond, methylene radical bicyclohexane vulcabond, 2,2, the 4-trimethyl hexamethylene diisocyanate, m-benzene diisocyanate, 4-chloro-1, the 3-phenylene diisocyanate, 4,4 '-biphenyl diisocyanate, 1, the 5-naphthalene diisocyanate, 1,4-butylidene vulcabond, 1, the 6-hexylidene diisocyanate, 1, the inferior decyl vulcabond of 10-, 1,4-hexamethylene vulcabond and polyalkylene oxide and polyester glycol vulcabond are as adopting the end capped polytetramethylene ether diol of TDI respectively and adopting the end capped polyethylene glycol adipate of TDI.
In one embodiment, can be to fluoridize polyvalent alcohol and polymeric polyisocyanate to about 7.5: 1 weight ratio combination in about 1.5: 1 than polymeric polyisocyanate to fluoridize many alcohol.Fluoridizing polyvalent alcohol and polymeric polyisocyanate can react in the presence of catalyzer to promote reaction.Be used for the catalyzer of urethane reaction such as dibutyl tin laurate etc. and be applicable to this purpose.
Isocyanate-terminated prepolymer can be by reacting end-blocking with the isocyanate-reactive function monomer that contains the ethylene linkage unsaturated functional group.The undersaturated functional group of described ethylene linkage is preferably acrylate, Vinyl Ether, maleic acid ester, fumarate or other similar compound.
Being used for suitable (methyl) acrylate-functional groups comprises the end capped suitable monomers of isocyanate-terminated prepolymer: the acrylate such as 2-Hydroxy ethyl acrylate, the vinylformic acid-2-hydroxy propyl ester etc. that contain hydroxy functional group.
Being used for suitable Vinyl Ether functional group comprises the end capped suitable monomers of isocyanate-terminated prepolymer: 4-hydroxyl butyl vinyl ether, triglycol list Vinyl Ether and 1,4-hexanaphthene dihydroxymethyl list Vinyl Ether.Can be used for the end capped suitable monomers of prepolymer being comprised: toxilic acid and the maleic acid ester that contains hydroxy functional group with suitable maleic acid ester functional group.
Suitable is, the isocyanate-reactive functional group of the q.s in the monomer that comprises acrylate, Vinyl Ether, maleic acid ester or other ethylene linkage unsaturated group and any residual isocyanate functional group reactions that is retained in the prepolymer, and with suitable functional group with the prepolymer end-blocking.Term " end-blocking " refers to that functional group seals in the prepolymer two ends each.
Described isocyanate-reactive ethylene linkage unsaturated monomer and the reaction of fluoridizing polyvalent alcohol and isocyanic ester.This reaction preferably takes place in the presence of antioxidant such as Butylated Hydroxytoluene (BHT) etc.
In one embodiment, ethylene linkage unsaturated urethane fluorinated component is at least 2500 centipoises (" cps ") 23 ℃ viscosity, for example 5000cps, 7500cps, at least 10 at least at least, 000cps, at least 25,000cps or at least 50,000cps.In one embodiment, described viscosity is at the most 10,000,000cps, for example at the most 5,000,000cps or at the most 1,000,0000cps.
In one embodiment, ethylene linkage unsaturated urethane fluorinated component is at least 0.75 weight % with respect to the per-cent of the gross weight of all active particles and ethylene linkage unsaturated urethane fluorinated component, for example at least 1 weight %, at least 2 weight %, at least 3 weight % or at least 5 weight %.In one embodiment, ethylene linkage unsaturated urethane fluorinated component is 35 weight % at the most with respect to the per-cent of the gross weight of all active particles and ethylene linkage unsaturated urethane fluorinated component, for example 25 weight %, 15 weight %, 10 weight % or 8 weight % at the most at the most at the most at the most.
Diluting monomer
In one embodiment, for example in order to reduce the viscosity of coating composition, composition of the present invention comprises diluting monomer.The example of diluting monomer comprises polymerisable vinyl monomer, for example in molecule, comprise a polymerizable vinyl polymerisable simple function group vinyl monomer and in molecule, comprise the polymerisable multi-functional vinyl monomer of two or more polymerizable vinyl.
The example of the diluting monomer of simple function group comprises, for example the vinyl monomer of simple function group such as N-vinyl pyrrolidone, N-caprolactam, vinyl pyridine; (methyl) acrylate that comprises alicyclic structure is as (methyl) isobornyl acrylate or (methyl) vinylformic acid-4-butyl cyclohexyl; (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) vinylformic acid-2-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxy butyl ester, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) ethyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid dodecane ester, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester.
The example of multi-functional diluting monomer comprises, trimethylolpropane tris (methyl) acrylate for example, tetramethylolmethane three (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, Tetraglycol 99 two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris oxygen ethyl (methyl) acrylate, three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, three (2-hydroxyethyl) isocyanuric acid ester two (methyl) acrylate and two (methylol) tristane two (methyl) acrylate.
Diluting monomer can also for example be fluoridized by halogenation.The example of fluoridizing diluting monomer comprises for example vinylformic acid-2,2,3 of fluorinated acrylic ester monomer, 3-tetrafluoro propyl ester, vinylformic acid-1H, 1H, 5H-octafluoro pentyl ester or vinylformic acid-1H, 1H, 2H, 2H-17 fluorine esters in the last of the ten Heavenly stems.
In one embodiment, coating composition of the present invention comprises, with respect to the gross weight of all active particles and ethylene linkage unsaturated urethane fluorinated component, be 0-20 weight % one or more thinners of 0.1-10 weight %, 0.25-5 weight % or 0.5-2.5 weight % for example.
Additive
In coating composition of the present invention, can comprise various additives for example antioxidant, UV light absorber, photostabilizer, adhesion promotor, coatingsurface modifying agent, thermal polymerization inhibitor, levelling agent, tensio-active agent, tinting material, sanitas, softening agent, lubricant, solvent, weighting agent, protective agent and help wetting agent.The example of antioxidant comprises Irganox 1010,1035,1076,1222 (CibaSpecialty Chemicals Co., Ltd. produce), Antigene P, 3C, FR, SumilizerGA-80 (Sumitomo Chemical Industries Co., Ltd. produces) etc.; The example of UV light absorber comprises Tinuvin P, 234,320,326,327,328,329,213 (Ciba Specialty ChemicalsCo., Ltd. produce), Seesorb 102,103,110,501,202,712,704 (Sypro ChemicalCo., Ltd. produces) etc.; The example of photostabilizer comprises Tinuvin 292,144,622LD (CibaSpecialty Chemicals Co., Ltd. produce), Sanol LS770 (Sankyo Co., Ltd. produces), Sumisorb TM-061 (Sumitomo Chemical Industries Co., Ltd. produces) etc.; Example as the silane coupling agent of adhesion promotor comprises γ-sulfydryl propyl group methyl mono methoxy silane, γ-sulfydryl propyl group methyl dimethoxysilane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl group monosubstituted ethoxy silane, γ-sulfydryl propyl group diethoxy silane, γ-sulfydryl propyl-triethoxysilicane, β-mercaptoethyl monosubstituted ethoxy silane, β-mercaptoethyl triethoxyl silane, β-mercaptoethyl triethoxyl silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, γ-An Jibingjisanyiyangjiguiwan, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, gamma-chloropropylmethyldimethoxysilane, γ-r-chloropropyl trimethoxyl silane and gamma-methyl allyl acyloxypropyl trimethoxysilane.The example of the commercially available product of these compounds comprises SILAACE S310, S311, S320, S321, S330, S510, S520, S530, S610, S620, S710, S810 (ChissoCorp. production), Silquest A-174NT (OSI Specialties-Crompton Corp. production), SH6062, AY43-062, SH6020, SZ6023, SZ6030, SH6040, SH6076, SZ6083 (Toray-Dow Corning Silicone Co., Ltd. produce), KBM403, KBM503, KBM602, KBM603, KBM803, KBE903 (Shin-Etsu Silicone Co., Ltd. produces) etc.Can also use acid adhesion promotor such as vinylformic acid.Phosphoric acid ester is the available adhesion promotor from Eb168 or the Eb170 of UCB for example; The example of coatingsurface modifying agent comprises silicone additives such as dimethyl siloxane polyethers and commercially available product such as DC-57, DC-190 (Dow-Corning production), SH-28PA, SH-29PA, SH-30PA, SH-190 (Toray-Dow Corning Silicone Co., Ltd. produce), KF351, KF352, KF353, KF354 (Shin-Etsu Chemical Co., Ltd. produce) and L-700, L-7002, L-7500, FK-024-90 (Nippon Unicar Co., Ltd. production).
In one embodiment, to comprise the gross weight with respect to ethylene linkage unsaturated urethane fluorinated component be about 0.01 adhesion promotor to about 10 weight % to composition of the present invention.In one embodiment, to comprise the gross weight with respect to ethylene linkage unsaturated urethane fluorinated component be about 0.01 antioxidant to about 5 weight % bases to composition of the present invention.
Light trigger comprises for example having acetophenone derivs, hydroxyalkyl phenyl ketone and/or the benzoyl diaryl phosphine oxide of hydroxyl or alkoxy-functional.The example of light trigger comprises Irgacure 651 (benzil dimethyl ketone acetal or 2,2-dimethoxy-1,2-phenylbenzene ethyl ketone, Ciba-Geigy), (1-hydroxyl-cyclohexyl-phenyl ketone is as active ingredient for Irgacure184, Ciba-Geigy), (2-hydroxy-2-methyl-1-phenyl-propane-1-ketone is as active ingredient for Darocur 1173, Ciba-Geigy), Irgacure 907 (2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone, Ciba-Geigy), (2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone is as active ingredient for Irgacure 369, Ciba-Geigy), Esacure KIP 150 (poly-2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] propane-1-ketone }, Fratelli Lamberti), the Esacure KIP 100F (mixture of poly-{ 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] propane-1-ketone } and 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, FratelliLamberti), Esacure KTO 46 (poly-2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] propane-1-ketone }, 2,4, the mixture of 6-Three methyl Benzene formyl diphenyl phosphine oxide and methyldiphenyl ketone derivatives, Fratelli Lamberti), Lucirin TPO (2,4,6-Three methyl Benzene formyl diphenyl phosphine oxide, BASF), Irgacure 819 (two (2,4,6-Three methyl Benzene formyl)-phenyl-phosphine-oxide compound, Ciba-Geigy), Irgacure 1700 (two (2 of 25:75%, 6-dimethoxy benzoyl)-2,4, the mixture of 4-tri-methyl-amyl phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, Ciba-Geigy) etc.
The oligopolymer that to contain two kinds of dissimilar unsaturated ethylene linkages be vinyl ether and another kind of ethylene linkage unsaturated group can be in the presence of these light triggers rapidly copolymerization and when not having polymerization starter, react to each other rapidly so that quick photocuring to be provided by being exposed to various energy.
In one embodiment, light trigger with respect to all active particles and the unsaturated gross weight of urethane component of fluoridizing of ethylene linkage in the scope of about 0.01% to 20.0 weight %, the amount of for example about 1-15 weight %, 4-12 weight % or 5-10 weight % is present in the composition of the present invention.
In one embodiment, the amount of light trigger is at least 2 weight %, for example at least 5 weight % based on the gross weight of coating composition.
In one embodiment, the present invention relates to comprise following radiation-hardenable composition:
A). with respect to the gross weight of all active particles and ethylene linkage unsaturated urethane fluorinated component, the active nano particle that does not have fluorinated groups of 50 weight % to 90 weight %;
B). with respect to the gross weight of all active particles and ethylene linkage unsaturated urethane fluorinated component, the active nano particle that contains at least one fluorinated groups of 5 weight % to 20 weight %;
With
C). with respect to the gross weight of all active particles and ethylene linkage unsaturated urethane fluorinated component, one or more ethylene linkage unsaturated urethane fluorinated component of 1% to 10 weight %;
In one embodiment, the present invention relates to comprise following composition:
A) there is not the active nano particle of fluorinated groups; With
B) contain the active nano particle of at least one fluorinated groups;
Wherein particle (a) is at least 1: 1 with the ratio of particle (b).
In one embodiment, the present invention relates to comprise following composition:
A) there is not the active nano particle of fluorinated groups; With
B) contain the active nano particle of at least one fluorinated groups;
Wherein the ratio of particle (a) and particle (b) was less than 0.95: 1.
In one embodiment, the present invention relates to comprise following composition:
A) active nano particle; With
B) one or more ethylene linkage unsaturated urethane fluorinated component;
The ratio of wherein said active nano particle and described ethylene linkage unsaturated urethane fluorinated component is at least 6: 1.
Coating and performance
In one embodiment of the invention, use standard Headway Reserch type EC101DT spin coating instrument that composition is spin-coated on the substrate.Then in fixed placement in 3 on the spin coating instrument chuck platform " * 3 " liquid composition of deposition 1ml on the substrate.With the spin coating acceleration of 3000rpm/s at 7500rpm with coating liquid/substrate spin coating 12 seconds.The thin wet film of generation was at room temperature further evaporated 60 seconds.In the nitrogen atmosphere that uses, use Fusion D-lamp to make the film that has evaporated stand 2.0J/cm
2Ultraviolet dosage.Use International Light type IL 390B Light Bug ultraviolet radiation meter verification ultraviolet dosage.Before coating, liquid coating is diluted in solvent 5% total solids be formed on coating and solidify after be the curing thickness of 0.10-0.15 μ m.
In one embodiment, composition of the present invention provides the coating with low-refraction when solidifying.In one embodiment, described coating has the specific refractory power less than 1.50, for example in the scope of 1.35-1.50, and for example 1.40-1.48,1.42-1.46 or 1.432-1.50.
In one embodiment, composition of the present invention provides the coating with surface of good hardness and wear resistance when solidifying.These characterize by film hardness pencil test and wearing test.In one embodiment, described coating has F at least, for example H or the pencil hardness of 2H at least at least.In one embodiment, described coating is not also damaged when testing by wearing test.In the embodiment part, these tests have been described.
The degree of cure of described composition can be by per-cent (%RAU) expression of the acroleic acid esterification saturation ratio of having reacted.In the embodiment of specification sheets of the present invention part, mentioned the test method of measuring %RAU.In one embodiment, composition of the present invention has at least 40% when solidifying, for example 45% to 98% or 55% to 70% %RAU.
Composition in the present invention can be used as the low-index layer that is used for the antireflection indicating system and uses.The antireflection indicating system can comprise substrate, at the hard coat film layer on the described substrate, be coated on high refractive index layer on the described hard coat film layer, follow by low-index layer.
The substrate that is suitable for indicating meter comprises organic substrate, and for example plastic is as comprising the substrate of following plastics: polynorbornene, polyethylene terephthalate, polymethylmethacrylate, polycarbonate, polyethersulfone, polyimide, Mierocrystalline cellulose, cellulosetri-acetate, fluorenes polyester and/or polyethers naphthalene.The example of other substrate comprises, for example inorganic substrate such as glass or ceramic substrate.
Can before coating, substrate be carried out pre-treatment.For example, substrate can be carried out corona or high power treatment.Substrate can also be carried out chemical treatment, as being coated with by emulsion.
In one embodiment, substrate comprises functional group, for example hydroxyl, carboxylic acid group and/or trialkoxy silane base such as Trimethoxy silane.The existence of these functional groups can strengthen the adhesion of coating and substrate.
In one embodiment, composition of the present invention can also be used as optical fiber undercoat, optical fiber secondary coating, basal body coating layer, one-tenth beam material, ink coating, photonic crystal fiber coating, CD tackiness agent, hard coat film coating or lens coating.
The invention still further relates to and comprise following object:
(a) substrate;
(b) hard coat film layer;
(c) high refractive index coating on described hard coat film layer; With
(d) low refractive index coating, described low refractive index coating obtains by comprising following composition curing:
I) do not have can with the active nano particle of fluorinated groups with the nano particle reaction of fluoridizing functional group;
Ii) contain at least one can with the active nano particle of the fluorinated groups of the nano particle reaction of not fluoridizing functional group; With
Iii) ethylene linkage unsaturated urethane fluorinated component.
Be used to prepare the method for low refractive index coating
The invention still further relates to the method that is used to prepare low refractive index coating, described method comprises mixes following at least component:
A) there is not the active nano particle of fluorinated groups;
B) contain the active nano particle of at least one fluorinated groups; With
C) ethylene linkage unsaturated urethane fluorinated component.
The invention still further relates to the method for preparing the coating that is used for object, described method comprises:
A) preparation comprises following radiation-hardenable composition:
I) there is not the active nano particle of fluorinated groups;
The active nano particle that ii) contains at least one fluorinated groups; With
Iii) ethylene linkage unsaturated urethane fluorinated component,
B) the described radiation-hardenable composition of coating on described object.
Embodiment
The following examples provide as specific embodiments of the present invention and in order to its practice and advantage to be described.Should understand embodiment is to provide for explanation, and is intended to not lie in limit this specification sheets or accompanying Claim by any way.
The preparation of composition I (comprising the active nano particle that does not have fluorinated groups):
The component and the relative quantity thereof that are used for preparing composition I are shown in following table 1.Join together in the suspensoid (MEK-ST) of nanometer titanium dioxide silicon oxide particles in MEK by comprising acrylate-based Trimethoxy silane compound (Int-12A) and suppressing acrylate-based polymeric compounds HQMME, the nanometer titanium dioxide silicon oxide particles is carried out surface grafting.Less water is joined in the MEK-ST suspensoid (total MEK-ST of 1.7 weight %) with catalysis silane graft reaction.In whipping process with mixture 60 ℃ of backflows at least three hours.Subsequently, add alkoxysilane compound containing trialkylsilyl group in molecular structure MTMS, stir the mixture that forms and reflux at least one hour at 60 ℃.Add dewatering agent OFM, stir the mixture that forms and reflux at least one hour at 60 ℃.
Table 1. is used to prepare the material (weight percent) of composition I: the active nano particulate composition of about 33 weight %
| Material | Weight % |
| MEK-ST (the nanometer titanium dioxide silicon oxide particles in MEK [gross weight with respect to particle and methyl ethyl ketone is the solid particulate of 30 weight %]) | 82.50％ |
| Int-12A (Trimethoxy silane acrylate coupling agent) | 7.84％ |
| HQMME (hydroquinone monomethyl ether, stablizer) | 0.14％ |
| MTMS (methyltrimethoxy silane, surperficial derivating agent) | 1.23％ |
| OFM (trimethyl orthoformate, dewatering agent) | 8.29％ |
| Amount to | 100％ |
The preparation of composition I I (comprising the active nano particle that contains at least one fluorinated groups):
The component and the relative quantity thereof that are used for preparing the MTST of fluorate acrylic acid esterification are shown in following table 2.Join stabilized nanoscale silica oxides particle in the suspensoid (MT-ST) of nanometer titanium dioxide silicon oxide particles in methyl alcohol together by comprising acrylate-based Trimethoxy silane compound (Int-12A) and suppressing acrylate-based polymeric compounds HQMME.The less water that exists in the MT-ST suspensoid (the 1.7 weight % of total MT-ST) has promoted the silane graft reaction.In whipping process with mixture 60 ℃ of backflows at least three hours.Subsequently, add fluorinated alkoxysilanes compound TDFTEOS, stir the mixture that forms and reflux at least one hour at 60 ℃.Subsequently, add alkoxysilane compound containing trialkylsilyl group in molecular structure MTMS, stir the mixture that forms and reflux at least one hour at 60 ℃.Add dewatering agent OFM, stir the mixture that forms and reflux at least one hour at 60 ℃.
Table 2. is used to prepare the material (weight percent) of composition I I: about 35 weight % solids are fluoridized the active nano particulate composition
| Material | Weight % |
| MT-ST (nanometer silicon dioxide particle in methyl alcohol [gross weight with respect to particle and methyl alcohol is the solid particulate of 30 weight %]) | 81.14％ |
| Int-12A (Trimethoxy silane acrylate coupling agent) | 7.68％ |
| HQMME (hydroquinone monomethyl ether, stablizer) | 0.14％ |
| TDFTEOS (13 fluoro-1,1,2,2-tetrahydrochysene octyl group) triethoxyl silane, surperficial derivating agent) | 2.28％ |
| MTMS (methyltrimethoxy silane, surperficial derivating agent) | 0.61％ |
| OFM (trimethyl orthoformate, dewatering agent) | 8.15％ |
| Amount to | 100％ |
The preparation of ethylene linkage unsaturated urethane fluorinated component
By making the component reaction in following table 3 prepare ethylene linkage unsaturated urethane fluorinated component:
Table 3. ethylene linkage unsaturated urethane fluorinated component
| Component | Weight % |
| Vinylformic acid-2-hydroxyl ethyl ester | 8.18 |
| Isophorone diisocyanate | 15.70 |
| BHT | 0.07 |
| Dibutyl tin laurate | 0.04 |
| Fluorolink E (fluorinated polyether) | 76.01 |
The ethylene linkage unsaturated urethane fluorinated component (the following H-I-FluorolinkE-I-H that also is called) of preparation is thus mixed with the component in the following table 4 to form midbody composite A:
Table 4. midbody composite A
| Component | Weight % |
| H-I-FluorolinkE-I-H | 80.7 |
| Lucirin TPO | 0.5 |
| Irgacure 184 | 1.5 |
| Irganox 1035 | 0.3 |
| Hexanediol diacrylate | 16.0 |
| The sulfydryl propyl trimethoxy silicane | 1.0 |
At last, by will being mixed with " composition I II " in the component in the following table 5:
Table 5. composition I II (the ethylene linkage unsaturated urethane fluorinated component that comprises about 7 weight %)
| Component | Weight % |
| Composition A | 8.8 |
| Darocur 1173 | 1.2 |
| Methyl ethyl ketone | 90.0 |
By the composition (weight % is for the gross weight of composition) that will be mixed with embodiment 1 and comparative example 1-10 in the component among the following table 6A.In table 6B, experimental performance has been described.
Table 6A: embodiment 1 and comparative example 1-10:
| Composition | Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 |
| Composition I (the active nano particulate compositions of ≈ 33 weight %) | 68.0 | 49.0 | 49.0 | 98.0 | 68.0 | 68.0 | |||||
| Composition I II (urethane acrylate of fluoridizing that comprises ≈ 7 weight %) | 20.0 | 49.0 | 49.0 | 98.0 | |||||||
| Composition I I (≈ 35 weight % fluoridize active nano particulate composition) | 10.0 | 49.0 | 49.0 | 98.0 | 10.0 | 10.0 | |||||
| Tosoh TFEMA (fluoridizing the monomethacrylates monomer) | 98.0 | 2.0 | |||||||||
| NTX5847 (perfluorinated polyether diacrylate) | 98.0 | 2.0 | |||||||||
| Methyl ethyl ketone (solvent) | 18.0 | 18.0 | |||||||||
| Irgacure 184 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Irgacure 907 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
Tosoh TFEMA can be purchased from Tosoh.
NTX5847 can be purchased from Sartomer.
Irgacure 184 and Irgacure 907 can be purchased from Ciba.
Film properties after table 6B. solidifies
| Performance | Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 |
| Cured film specific refractory power (RI) | 1.469 | 1.467 | 1.474 | 1.475 | 1.483 | 1.437 | 1.473 | 1.497 | 1.357 | 1.477 | 1.481 |
| Pencil hardness | 2H | ≤4B | 2B | ≤4B | ≤4B | 4B | ≤4B | 2B | ≤4B | B | B |
| Wear test | 0 | 2 | 2 | 1 | 1 | 1 | 2 | 3 | 2 | 1 | 1 |
| ％RAU | 68.1 | 71.2 | 66.1 | 51.1 | 44.9 | 100 | 39.9 | N/D | 0.1 | 50.7 | 56.3 |
The evaluation of coating performance (test method):
Measure film hardness (pencil hardness) by pencil test:
Measure pencil hardness according to standard method ASTM D3363: on glass substrate, composition is solidified, the substrate that has been coated with is placed on the firm horizontal surface.Pencil is remained on the film tightly with 45 (away from operator's point), and it is marked of 6.5mm (1/4 inch) from the operator.Use the hardest pencil to begin this process, continue to reduce in scale to two terminal point of hardness any then: one, can not protrude into or cut a hole the pencil (pencil hardness) of wearing film, perhaps two, pencil (scratch hardness) that can scratching film.
Pencil hardness by the letter representation film in the following sequences: (film hardness increases from left to right):
4B，3B，2B，B，HB，F，H，2H，3H，4H
If the hardness of film, thinks so that film is enough hard by any letter representation in the group of (F, H, 2H, 3H, 4H).
The measurement of cured film specific refractory power
With testing coating coated glass microslide, and by ultraviolet exposure with coating curing.(the standard condition of cure: solvent evaporation, with 1.0J/cm
2Solidify Fusion 300 W D-lamps, air atmosphere).Use blade that cured film is downcut 2mm * 2mm square, and from cured film, take out the alternative square.Then slide glass is placed on axial transillumination that is used to calibrate and the 10 * microscopically that disposes the object lens that are not more than at least 0.70 numerical aperture are installed.The narrow bandwidth interference filter is placed on the light path of microscope internal illumination system and uses monochromatic illumination.If the exterior lighting light source is provided, can also use monochromator so so that the light source of continuous variable to be provided.The normal wavelength that uses is 589nm or sodium D-line, locates for " n " from the specific refractory power numeral.Then relatively with the standardized liquid of cured film and known specific refractory power (Cargill specific refractory power liquid, the StandardGroup that can obtain from McCrone Microscopy Inc.).Use ampuliform coating machine rod, partly be coated with the specific refractory power liquid of droplet, be sent to below the cover plate to fill the space around the coating square by wicking action at contiguous cover plate.When adjusting the microscope focus and make distance between sample and the object lens increase, Becke line moves to the higher medium of specific refractory power.If coating has than the higher specific refractory power of liquid that is placed in the inside, then " making progress " in focus, Becke line moves on in the square profile when mobile.To new coating square repeating said steps until the profile of square disappear or Becke line from formerly observation reversing direction of observation.Direction according to the refractive index mismatch that shows by original observed is selected higher or lower specific refractory power liquid.If the profile of coating square can not disappear and find two kinds of liquid adjacent one another are in this group and provide opposite Becke line movable signal that then the specific refractory power of material most possibly is positioned at the centre of this scope between two values.
Wearing test
The substrate that has been coated with is placed on the firm horizontal surface.On trier's the finger around on a kind of master mode laboratory wiping cloth (rags) (the Kimwipes EX-L that can obtain from Kimberly Clark Co.).Use medium Manual pressure that described paper is rubbed 2-3 time on cured film back and forth.Check the wearing and tearing of cured film then.To damage quantification by following scale then:
0=does not observe damage
1=observes slight damage
2=observes cured film and is damaged to moderate
The 3=cured film is removed fully or is damaged
Represent the cured film difference of hardness with the damage due to the friction of master mode laboratory wiping cloth (rags), and/or the cured film cross-linking density is low, and/or photopolymerizable group curing is not exclusively, and/or the poor adhesion of cured film and substrate.
The measurement of the degree of cure of ultra-violet curing coating (%RAU)
One drop of liquid coating is spin-coated on the KBr crystal, until covering about 0.1 micron coat-thickness fully.Use 100 to be total to adduction scanning (co-added scan) scanning samples and spectral translation is specific absorption.Measure the net peak area of the acrylate absorbancy of liquid coating then.For most of acrylate-based coatings, should use 810cm
-1The absorbancy at place.If coating is included in or close 810cm
-1Organosilicon or other component of strong absorption are arranged, should use alternative acrylate absorbancy so.
Should use " baseline " commercial measurement net peak area, wherein baseline is depicted as the tangent line of absorbancy minimum value on the either side at this peak.Determine then below described peak and the area above the baseline.
In air atmosphere, use 300W Fusion D-lamp with 1.0J/cm
2With sample solidifies.The FTIR scanning of repeat samples and the measurement of the clean peak of solidified coating spectrographic absorbancy.Bareline heart rate there is no need identical with liquid coating, but should select baseline to make it still with tangent in the absorbancy minimum value of analyzing on the wave band either side.The peak area at replicate measurement liquid and solidified coating spectrographic non-acrylate reference peak.For every kind of subsequent analysis of same recipe, should use identical reference peak with identical baseline point.
Use following equation to determine the ratio of the acrylate absorbancy and the reference absorbancy of liquid coating:
R
L＝A
AL/A
RL
A wherein
ALThe area of the acrylate absorbancy of=liquid
A
RLThe area of the reference absorbancy of=liquid
R
LThe area ratio of=liquid
In a similar fashion, use following equation to determine the ratio of the acrylate absorbancy and the reference absorbancy of solidified coating:
R
F＝A
AF/A
RF
A wherein
AFThe area of the acrylate absorbancy of=solidified coating
A
RFThe area of the reference absorbancy of=solidified coating
R
FThe area ratio of=solidified coating
At last, use the degree of cure of following equation calculating as the acrylate degree of unsaturation (%RAU) of per-cent-reaction:
％RAU＝(R
L-R
F)×100/R
L
R wherein
LThe area ratio of=liquid
R
FThe area ratio of=solidified coating
Known, the composition that comprises the appreciable amount multi-functional acrylate has lower %RAU value when completely solidified, common rank at 55-70%RAU.It is believed that this is that vice versa because the vitrifying of acrylate reticulation causes unreacted acrylate can not have enough mobilities to reach the free radical that increases in reticulation.
After having described specific embodiments of the present invention, should be appreciated that, to those skilled in the art, many modifications of the present invention are conspicuous or have hint, so its intention is that the present invention is only limited by the spirit and scope of appended claim.
Claims (33)
1. radiation-hardenable composition, it comprises:
A) there is not the active nano particle of fluorinated groups;
B) contain the active nano particle of at least one fluorinated groups; With
C) one or more ethylene linkage unsaturated urethane fluorinated component.
2. composition according to claim 1, wherein two kinds of described active nano particles all comprise metal oxide.
3. radiation-hardenable composition according to claim 2, the wherein said active nano particle that contains at least one fluorinated groups comprises the organic constituent that is attached to described metal oxide.
4. radiation-hardenable composition according to claim 3, wherein said organic constituent comprises undersaturated polymerizable groups.
5. composition according to claim 4, wherein said undersaturated polymerizable groups is acrylate, methacrylic ester, propenyl, vinyl, butadienyl, styryl, ethynyl, cinnyl, Vinyl Ether, maleic acid ester, acrylamide, epoxy, trimethylene oxide, amine-alkene or mercaptan-alkene.
6. according to each described radiation-hardenable composition among the claim 4-5, wherein said fluorinated groups is arranged in the organic constituent that comprises undersaturated polymerizable groups.
7. according to each described radiation-hardenable composition among the claim 4-5, wherein said fluorinated groups is not arranged in the organic constituent that comprises undersaturated polymerizable groups.
8. according to each described composition among the claim 1-7, wherein said not have the active nano particle of fluorinated groups and the described active nano particulate ratio that contains at least one fluorinated groups be 1: 9 to 9: 1.
9. according to each described composition among the claim 1-8, the described fluorinated groups of wherein said active particle is a fluoroalkyl.
10. according to each described composition among the claim 1-9, wherein said composition has the specific refractory power less than 1.50 when solidifying.
11. according to each described composition among the claim 1-10, wherein said composition has the pencil hardness that is not less than F when solidifying.
12. according to each described composition among the claim 1-11, wherein said composition has at least 40% %RAU.
13. according to each described composition among the claim 1-12, wherein said composition shows not damage when testing by wearing test when solidifying.
14. a radiation-hardenable composition, it comprises:
A) with respect to described component (a) and (b) and gross weight (c), the active nano particle that does not have fluorinated groups of 50 weight % to 90 weight %;
B) with respect to described component (a) and (b) and gross weight (c), the active nano particle that contains at least one fluorinated groups of 5 weight % to 20 weight %; With
C) with respect to described component (a) and (b) and gross weight (c), one or more ethylene linkage unsaturated urethane fluorinated component of 1 weight % to 10 weight %.
15. a radiation-hardenable composition, it comprises:
A) there is not the active nano particle of fluorinated groups;
B) contain the active nano particle of at least one fluorinated groups;
C) ethylene linkage unsaturated urethane fluorinated component; With
D) one or more light triggers,
Wherein said composition has RI less than 1.50, when solidifying greater than the pencil hardness of F and 55% to 70% %RAU.
16. a radiation-hardenable composition, it comprises:
A) comprise the active nano particle of the organic constituent that is attached on the described active particle, wherein said organic constituent comprises undersaturated polymerizable groups and fluorinated groups in its structure; With
B) ethylene linkage unsaturated urethane fluorinated component.
17. radiation-hardenable composition according to claim 16, wherein said active particle also comprises the organic constituent that does not have fluorinated groups.
18., wherein described composition is made prescription after curing so that optical fiber undercoat, optical fiber secondary coating, basal body coating layer, one-tenth beam material, ink coating, photonic crystal fiber coating, CD tackiness agent, hard coat film coating, indicating meter coating or lens coating to be provided according to each described composition among the claim 16-17.
19. a method that is used to prepare low refractive index coating, described low refractive index coating comprises:
A) there is not the active nano particle of fluorinated groups;
B) contain the active nano particle of at least one fluorinated groups; With
C) ethylene linkage unsaturated urethane fluorinated component.
20. a method that is used to prepare the object with low refractive index coating comprises:
To be applied on the surface of applied substrate according to each described composition among the claim 1-17.
21. a method for preparing the coating that is used for object, it comprises:
A) preparation radiation-hardenable composition, this radiation-hardenable composition comprises:
I) there is not the active nano particle of fluorinated groups;
The active nano particle that ii) contains at least one fluorinated groups; With
Iii) ethylene linkage unsaturated urethane fluorinated component; With
B) the described radiation-hardenable composition of coating on described object.
22. method according to claim 21, wherein said object be optical fiber, photonic crystal fiber, CD, optical-fiber-belt, hard coat film layer, be used for the anti-reflecting layer of indicating meter or lens.
23. a low refractive index coating, described low refractive index coating obtains by solidifying according to each radiation-hardenable composition among the claim 1-18.
24. a watch-dog, it comprises to scribble to small part and will solidify the plastic of the coating that obtains according to each described composition among the claim 1-17.
25. an antireflection system, it comprises by each described composition among the claim 1-17 is solidified the coating that obtains.
26. an object, it comprises:
A) substrate;
B) hard coat film layer;
C) high refractive index coating on described hard coat film layer; With
D) low refractive index coating, described low refractive index coating obtains by following composition is solidified, and described composition comprises:
I) there is not the active nano particle of fluorinated groups;
The active nano particle that ii) contains at least one fluorinated groups; With
Iii) ethylene linkage unsaturated urethane fluorinated component.
27. object according to claim 26, wherein said object are the antireflection indicating meters.
28. according to each described object among the claim 26-27, wherein said substrate is polynorbornene, polyethylene terephthalate, polymethylmethacrylate, polycarbonate, polyethersulfone, polyimide, Mierocrystalline cellulose, cellulosetri-acetate, fluorenes polyester or polyethers naphthalene.
29. a composition, it comprises:
A) there is not the active nano particle of fluorinated groups; With
B) contain the active nano particle of at least one fluorinated groups;
Wherein particle (a) is at least 1: 1 with the ratio of particle (b).
30. a radiation-hardenable composition, it comprises:
A) active nano particle; With
B) one or more ethylene linkage unsaturated urethane fluorinated component;
The ratio of wherein said active nano particle and described ethylene linkage unsaturated urethane fluorinated component is at least 6: 1.
31. a radiation-hardenable composition, wherein said composition has when solidifying
A) less than 1.5 specific refractory power; With
B) be not less than the pencil hardness of F.
32. the described radiation-hardenable composition of claim 31, wherein said composition have at least 40 %RAU when solidifying.
33. a display pannel, it comprises radiation curable coating composition, and wherein said composition has when solidifying
A) less than 1.5 specific refractory power; With
B) be not less than the pencil hardness of F.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US56429404P | 2004-04-22 | 2004-04-22 | |
| US60/564,294 | 2004-04-22 | ||
| US60/578,902 | 2004-06-14 | ||
| US60/580,137 | 2004-06-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1965041A true CN1965041A (en) | 2007-05-16 |
Family
ID=38045499
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200580012466 Pending CN1965041A (en) | 2004-04-22 | 2005-04-19 | Low refractive index coating composition |
| CN 200580012467 Pending CN1946818A (en) | 2004-04-22 | 2005-04-19 | Low refractive index coating composition |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200580012467 Pending CN1946818A (en) | 2004-04-22 | 2005-04-19 | Low refractive index coating composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1965041A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102789006A (en) * | 2008-11-17 | 2012-11-21 | 大日本印刷株式会社 | Optical sheet and method for producing the same |
| CN103261924A (en) * | 2010-12-24 | 2013-08-21 | 大日本印刷株式会社 | Hard coat film, polarizing plate and image display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170051164A1 (en) * | 2014-05-09 | 2017-02-23 | 3M Innovative Properties Company | Article with hardcoat and method of making the same |
| EP3269780A1 (en) | 2016-06-27 | 2018-01-17 | Viavi Solutions Inc. | High chroma flakes |
| JP6716500B2 (en) | 2016-06-27 | 2020-07-01 | ヴァイアヴィ・ソリューションズ・インコーポレイテッドＶｉａｖｉ Ｓｏｌｕｔｉｏｎｓ Ｉｎｃ． | Optical device |
| US10207479B2 (en) | 2016-06-27 | 2019-02-19 | Viavi Solutions Inc. | Magnetic articles |
| US20170368866A1 (en) * | 2016-06-27 | 2017-12-28 | Viavi Solutions Inc. | High chromaticity pigment flakes and foils |
| CN106601340A (en) * | 2016-12-21 | 2017-04-26 | 张家港康得新光电材料有限公司 | Refractive index coupling film and ITO conductive film |
| CN116655985A (en) * | 2023-05-19 | 2023-08-29 | 太仓斯迪克新材料科技有限公司 | Wear-resistant reflective film |
-
2005
- 2005-04-19 CN CN 200580012466 patent/CN1965041A/en active Pending
- 2005-04-19 CN CN 200580012467 patent/CN1946818A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102789006A (en) * | 2008-11-17 | 2012-11-21 | 大日本印刷株式会社 | Optical sheet and method for producing the same |
| CN102789006B (en) * | 2008-11-17 | 2015-11-18 | 大日本印刷株式会社 | The manufacture method of optical sheet and optical sheet |
| CN103261924A (en) * | 2010-12-24 | 2013-08-21 | 大日本印刷株式会社 | Hard coat film, polarizing plate and image display device |
| US8993114B2 (en) | 2010-12-24 | 2015-03-31 | Dai Nippon Printing Co., Ltd. | Hard coat film, polarizer and image display device |
| CN103261924B (en) * | 2010-12-24 | 2016-04-20 | 大日本印刷株式会社 | Hard coat film, polaroid and image display device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1946818A (en) | 2007-04-11 |
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