CN1965041A - Low refractive index coating composition - Google Patents

Abstract

The present invention provides a coating composition that, upon curing, provides a coating with low refractive index, surface hardness, scratch resistance, abrasion resistance, and good curing performance at a thin film thickness. In one embodiment, a composition is provided comprising active nanoparticles without fluorinated groups, active nanoparticles containing at least one fluorinated group, and an olefinically unsaturated urethane fluorinated component.

Description

Low Refractive Index Coating Composition

technical field

The present invention relates to radiation curable coating compositions, coatings formed by curing these compositions, methods of making these coatings and articles comprising these coatings. One aspect of the invention relates to the use of these coatings on hardcoat layers or display systems.

Background technique

There have been various attempts in the art to develop coating compositions, but there has been much interest in developing coating compositions for producing low-refractive index coatings with good surface properties at thin film thicknesses. Hardness, scratch resistance, abrasion resistance and good curing properties. The object of the present invention consists in the preparation of these coating compositions.

US Patent US 6,391,459 discusses radiation curable compositions comprising fluorinated urethane oligomers. US Patent 6,160,067 mentions activated silica particles containing polymerizable unsaturated groups.

Contents of the invention

Objects of the present invention include providing compositions which, when cured, provide coatings with low refractive index at thin film thicknesses, surface hardness, scratch resistance, abrasion resistance and good cured properties.

One embodiment of the composition of the invention is a radiation curable composition comprising:

a) active nanoparticles without (or absent) fluorinated groups;

b) active nanoparticles containing at least one fluorinated group; and

c) Ethylenically unsaturated urethane fluorinated components.

Another embodiment of the invention is an article comprising:

a) Substrate;

b) hard coating layer;

c) a high refractive index coating on the hardcoat layer; and

d) a low refractive index coating, which is obtained by curing the following composition, the composition comprising:

i) active nanoparticles without fluorinated groups;

ii) active nanoparticles containing at least one fluorinated group; and

iii) Ethylenically unsaturated urethane fluorinated components.

In other embodiments of the present invention, methods of preparing coatings from said compositions are provided. The compositions of the present invention are used to provide coatings for various applications such as in optical fibers, photonic crystal fibers, inks and substrates, optical media and/or displays.

Another aspect of the present invention relates to the use of the compositions of the present invention to form coatings on substrates including, for example, monitors (such as flat screen computer and/or television monitors, for example using the Such as those described in US Pat. Nos. 6,091,184 and 6,087,730), optical discs, touch screens, smart cards, flexible glass, and the like. There is a great deal of interest in the development of plastic substrates for display applications such as LCD (Liquid Crystal Display) and OLED (Organic Light Emitting Diode) displays.

The composition of the present invention can be used as a coating composition. For example, a substrate may be coated with the composition of the invention. Suitable coated substrates include organic substrates. The organic substrate is preferably a polymer ("plastic") substrate, such as a substrate comprising the following polymers: polynorbornene, polyethylene terephthalate, polymethyl methacrylate, polycarbonate, poly Ethersulfones, polyimides, fluorene polyesters (such as polymers mainly composed of homocopolymeric repeating units derived from 9,9-bis(4-hydroxyphenyl)fluorene and isophthalic acid, terephthalic acid or mixtures thereof), cellulose (such as cellulose triacetate) and/or polyether naphthalene. Particularly preferred substrates include polynorbornene substrates, fluorene polyester substrates, cellulose triacetate substrates, polyimide substrates.

Additional objects, advantages and features of the invention are set forth in this specification, and in part, will become apparent to those skilled in the art upon examination of the following description, or may be learned by practice of the invention. The invention disclosed in this application is not limited to any specific set or combination of objects, advantages and features. It is intended that various combinations of the described objects, advantages, and features constitute the present invention disclosed in this application.

Specific embodiments

definition:

"Nanoparticles" refers to a mixture of particles in which the majority of the particles in the mixture have a size of less than 1 micron.

"Nanoparticle size" (or "nanoparticle size"), for spherical particles, refers to the particle diameter. For non-spherical particles, it refers to the distance of the longest straight line drawn from one side of the nanoparticle to the opposite side.

"(Meth)acrylate" means "acrylate and/or methacrylate".

"Reactive nanoparticles" refer to nanoparticles that contain at least one reactive group (eg, a polymerizable group).

In particular, the present invention relates to a radiation curable composition comprising:

a) active nanoparticles in the absence of fluorinated groups;

b) active nanoparticles containing at least one fluorinated group; and

c) Ethylenically unsaturated urethane fluorinated components.

active nanoparticles

Methods of preparing active nanoparticles can vary. In one embodiment, active nanoparticles may comprise metal oxide nanoparticles (A) and component (B) chemically bound thereto, wherein component (B) comprises at least one active group, e.g. polymerizable group.

In one embodiment, the metal oxide nanoparticles (A) comprise nanoparticles selected from the group consisting of oxides of silicon, aluminum, zirconium, titanium, zinc, gallium, indium, tin, antimony and cerium. In one embodiment, nanoparticles (A) are single metal oxides. In another embodiment, nanoparticles (A) are mixtures of different metal oxides. Those skilled in the art will appreciate that, for the purposes of the present invention, the metal oxide nanoparticles of the present invention also include oxides of silicon, although silicon may not be considered a "metal" in common usage.

The metal oxide nanoparticles (A) can be used, for example, in the form of powders or in the form of aqueous or solvent dispersions (sols). When the metal oxide nanoparticles are in the form of a dispersion, an organic solvent is preferable as a dispersion medium from the viewpoint of mutual solubility with other components and dispersibility. The use of solvent dispersions of metal oxides is particularly desirable in applications where excellent clarity of the cured product is required. Examples of organic solvents include: alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl lactate Esters and gamma-butyrolactone, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene and amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

In one embodiment, the nanoparticles (A) comprise colloidal silica nanoparticles. These silica nanoparticles are commercially available under trade names such as: Methanol Silica Sol produced by Nissan Chemical Industries, Ltd., 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. Examples of powdery silica include products available under the following trade names: AEROSIL 130, AEROSIL 300, AEROSIL 380, AEROSIL TT600 and AEROSILOX50 (manufactured by Japan Aerosil Co., Ltd.), Sildex H31, H32, H51, H52, H121, H122 (manufactured by Asahi Glass Co., Ltd.), E220A, E220 (manufactured by Nippon Silica Industrial Co., Ltd.), SYLYSIA470 (manufactured by Fuji Silycia Chemical Co., Ltd.) and SG Flake (manufactured by Nippon Sheet Glass Co. , Ltd. production).

Examples of commercially available alumina dispersions include aqueous dispersions Alumina Sol-100, -200, -520 (trade names, manufactured by Nissan Chemical Industries, Ltd.); isopropanol dispersions of alumina, AS-1501 ( trade name, manufactured by Sumitomo Osaka Cement Co., Ltd.); and a toluene dispersion of alumina, AS-150T (trade name, manufactured by Sumitomo Osaka Cement Co., Ltd.). An example of the zirconia toluene dispersion is HXU-110JC (trade name, produced by Sumitomo OsakaCement Co., Ltd.). An example of an aqueous dispersion product of zinc antimonate powder is Celnax (trade name, manufactured by Nissan Chemical Industries, Ltd.). Examples of powder and solvent dispersion products of aluminum oxide, titanium oxide, tin oxide, indium oxide, zinc oxide are commercially available, for example, under the trade name Nano Tek (trade name, produced by CI Kasei Co., Ltd.). An example of the water-dispersed sol of antimony-doped tin oxide is SN-100D (trade name, produced by Ishihara Sangyo Kaisha, Ltd.). An example of ITO powder is a product produced by Misubishi Material Co., Ltd.; and an example of an aqueous dispersion of cerium oxide is Needral (trade name, produced by Taki Chemical Co., Ltd.).

The shape of the metal oxide nanoparticles (A) can be suitable for the desired application, including spherical, non-spherical, hollow, porous, rod-like, plate-like, fibrous, amorphous and/or combinations of these. For example, nanoparticles can be rod-shaped and hollow or plate-shaped and porous, etc.

In one embodiment, a majority (e.g. at least 60%, at least 75%, at least 90%, at least 94%, at least 96% or at least 98%) of the nanoparticles (A) have a size less than 900 nm, e.g. less than 750 nm, less than 600nm, less than 500nm, less than 300nm or less than 150nm, less than 100nm, or even less than 75nm. In one embodiment, the majority (e.g. at least 60%, at least 75%, at least 90%, at least 94%, at least 96% or at least 98%) of the nanoparticles (A) have a size of at least 0.1 nm, e.g. at least 1 nm, At least 5 nm, at least 10 nm, or at least 20 nm. Methods for determining particle size include, for example, BET adsorption, optical or scanning electron microscopy or atomic force microscopy (AFM) imaging.

In one embodiment, the nanoparticles (A) have an average size of less than 900 nm, such as less than 750 nm, less than 600 nm, less than 500 nm, less than 300 nm, less than 150 nm, less than 100 nm or even less than 75 nm. In one embodiment, the average size of the nanoparticles (A) is at least 0.1 nm, such as at least 1 nm, at least 5 nm, at least 10 nm, or at least 20 nm.

Component (B) can be, for example, an organic component and/or an inorganic-organic component comprising reactive groups. Examples of reactive groups contained in component (B) include, for example, ethylenically unsaturated groups such as (meth)acrylate or vinyl ether groups.

In one embodiment, component (B) further comprises one or more groups represented by the following formula (1):

-X-C(=Y)-NH- (1)

wherein X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. The group represented by formula (1) is, for example, a urethane bond [-O-C(=O)-NH-], -O-C(=S)-NH- or a thiourethane bond [-S-C( =O)-NH-].

Likewise, in one embodiment component (B) comprises silanol groups or groups which form silanol groups by hydrolysis.

Examples of the component (B) include, for example, an alkoxysilane component containing a urethane bond [-O-C(=O)-NH-] and/or A thiourethane linkage [-S-C(=O)NH-] and at least two polymerizable unsaturated groups.

A specific example of component (B) suitable for reacting with nanoparticles (A) is represented by the following structural formula I:

Formula I

Another example is, for example, a component represented by the following formula (2):

Wherein R ¹ represents a methyl group, R ² represents an alkyl group containing 1-6 carbon atoms, R ³ represents a hydrogen atom or a methyl group, m represents 1 or 2, n represents an integer of 1-5, and X represents an alkyl group containing 1-6 A divalent alkylene group containing 3-14 carbon atoms, Y represents a straight-chain, cyclic or branched divalent hydrocarbon group containing 3-14 carbon atoms, Z represents a straight-chain, cyclic or branched chain containing 2-14 carbon atoms divalent hydrocarbon group. Z may contain ether linkages.

For example, the component represented by formula (2) can be prepared by reacting mercaptoalkoxysilane, diisocyanate, and hydroxyl group-containing polyfunctional (meth)acrylate.

An example of a preparation method is, for example, reacting a mercaptoalkoxysilane with a diisocyanate to obtain an intermediate comprising a thiourethane linkage, and reacting the remaining isocyanate with a hydroxyl-containing polyfunctional (Meth)acrylates are reacted to give products containing urethane linkages.

The same product can be obtained by reacting a diisocyanate with a hydroxyl-containing polyfunctional (meth)acrylate to obtain an intermediate containing a urethane linkage, and reacting the remaining isocyanate with a mercaptoalkoxysilane. However, since this method leads to an addition reaction of mercaptoalkoxysilane and (meth)acrylate groups, the purity of the product may be compromised. Additionally, gel formation may occur.

As examples of the mercaptoalkoxysilane used in the preparation of the component represented by the formula (2), there can be given γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyl Tributoxysilane, γ-mercaptopropyldimethylmethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc. Among them, γ-mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane are preferable.

As an example of a commercially available product of mercaptoalkoxysilane, SH6062 (manufactured by Toray-Dow Corning Silicone Co., Ltd.) can be given.

As examples of diisocyanates, 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated bisphenol A diisocyanate, 2,4- Toluene diisocyanate, 2,6-toluene diisocyanate, etc. Among them, 2,4-toluene diisocyanate, isophorone diisocyanate, and hydrogenated xylene diisocyanate are preferable.

As examples of commercially available products of polyisocyanate compounds, TDI-80/20, TDI-100, MDI-CR100, MDI-CR300, MDI-PH, NDI (manufactured by Mitsui Nisso Urethane Co., Ltd.), Coronate T, Millionate MT, Millionate MR, HDI (manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate 600 (manufactured by Takeda Chemical Industries, Ltd.), etc.

As examples of hydroxyl-containing polyfunctional (meth)acrylates, trimethylolpropane di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate ester, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. Among them, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate are preferable. These compounds form at least two polymerizable unsaturated groups in the compound represented by formula (2).

Mercaptoalkoxysilane, diisocyanate, and hydroxyl-containing polyfunctional (meth)acrylate may be used alone or in combination of two or more.

In the preparation of the component represented by formula (2), mercaptoalkoxysilane, diisocyanate and hydroxyl-containing polyfunctional (meth)acrylate are used so that the molar ratio of diisocyanate to mercaptoalkoxysilane is preferably 0.8-1.5, and still more preferably 1.0-1.2. If the molar ratio is less than 0.8, the storage stability of the composition may be reduced. If the molar ratio exceeds 1.5, dispersibility may be reduced.

It is preferable to prepare the component represented by formula (2) in dry air to prevent anaerobic polymerization of acrylate groups and hydrolysis of alkoxysilane. The reaction temperature is preferably 0-100°C, and still more preferably 20-80°C.

In the production of the component represented by formula (2), a conventional catalyst may be used in the urethane forming reaction to reduce the production time. As the catalyst, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin di(2-ethylhexanoate) and octyltin triacetate can be given. In one embodiment, the catalyst is added in an amount of 0.01 to 1% by weight relative to the total amount of catalyst and diisocyanate.

A thermal polymerization inhibitor may be added in the preparation to prevent thermal polymerization of the compound represented by formula (2). As examples of the thermal polymerization inhibitor, p-methoxyphenol, hydroquinone and the like can be given. The thermal polymerization inhibitor is preferably added in an amount of 0.01 to 1% by weight relative to the total amount of the thermal polymerization inhibitor and the hydroxyl group-containing polyfunctional (meth)acrylate.

The component represented by formula (2) can be prepared in a solvent. As the solvent, any solvent that does not react with mercaptoalkoxysilane, diisocyanate, and hydroxyl group-containing polyfunctional (meth)acrylate and has a temperature of 200° C. or less can be appropriately selected. boiling point.

As specific examples of such solvents, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate, butyl acetate and amyl acetate, hydrocarbons such as toluene and xylene, and the like can be given.

As specific examples of alkoxysilane components, there can be provided: components containing unsaturated double bonds in the molecule, such as γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxy Silanes and vinyltrimethoxysilane; components containing epoxy groups in the molecule, such as gamma-glycidoxypropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane; molecule Compounds containing amino groups, such as γ-aminopropyltriethoxysilane and γ-aminopropyltrimethoxysilane; components containing mercapto groups in the molecule, such as γ-mercaptopropyltrimethoxysilane and γ-mercapto propyltriethoxysilane; alkylsilanes such as methyltrimethoxysilane, methyltriethoxysilane, and phenyltrimethoxysilane; and the like. Among them, from the viewpoint of the dispersion stability of the surface-treated oxide particles, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, Methyltriethoxysilane and Phenyltrimethoxysilane.

The reactive groups in component (B) can vary. Reactive groups include, as previously described, for example unsaturated polymerizable groups. Reactive groups include, for example, acrylate, methacrylate, acryl, vinyl, butadienyl, styryl, ethynyl, cinnamoyl, vinyl ether, maleate, acrylamide, epoxy, oxygen Heteretane, amine-ene and thiol-ene groups.

The reactive group in component (B) may also be a polymerizable group in combination with other groups. Examples of such combinations include, for example, carboxylic acids and/or carboxylic anhydrides in combination with epoxy groups, acids in combination with hydroxyl compounds, especially 2-hydroxyalkylamides, with isocyanates such as blocked isocyanates, isocyanate dimers (uretdion) Amines in combination with or carbodiimides, epoxies in combination with amines or dicyandiamides, hydrazineamides in combination with isocyanates, hydroxyl compounds in combination with isocyanates such as blocked isocyanates, isocyanate dimers or carbodiimides, and anhydrides Hydroxyl compounds in combination, hydroxyl compounds in combination with (etherified) methylolamides (“amino-resins”), thiols in combination with isocyanates, thiols in combination with acrylates (optionally radically initiated), and Acrylate combinations of acetoacetate and, when cationic crosslinking is used, epoxy or hydroxyl compounds containing epoxy groups. Thus, for example, part of component (B) may contain amine groups as reactive groups and another part of component (B) may contain isocyanate groups as reactive groups to form a polymerizable combination.

Examples of additional reactive groups that may be used include moisture-curing isocyanates in styrene and/or methacrylates, moisture-curing alkoxy/acyloxy-silanes, alkoxytitanates, alkanes Oxyzirconate or urea-, urea/melamine-, melamine-formaldehyde or phenol-formaldehyde (resole, novolak-type) mixtures, or radically curable (peroxide- or photoinitiated) olefinic bonds Unsaturated mono- and polyfunctional monomers and polymers such as acrylates, methacrylates, maleates/vinyl ethers, or free radical curing (peroxide- or photoinitiated) unsaturated (e.g. maleic acid or fumaric acid) polyester.

As examples of methods for preparing active particles, suitable examples for active nanoparticles and their preparation are mentioned, for example, in U.S. Patent 6,160,067 to Eriyama et al. and WO 00/4766, which are hereby incorporated by reference in their entirety. At the same time, metal oxide nanoparticles (A) often contain moisture as adsorbed water on the nanoparticle surface under usual storage conditions. In addition, there are often components such as hydroxides, hydrates, etc. that react with the silanol group forming component at least on the surface of the oxide nanoparticles. Accordingly, the crosslinkable nanoparticles (A) can be prepared by mixing the silanol group forming component and the metal oxide (A) and heating the mixture while stirring. Suitably, the reaction is carried out in the presence of water to effectively bind the silanol group-forming sites occupied by the organic component (B) and the oxide nanoparticles (A).

A dehydrating agent is preferably added to facilitate the reaction. As the dehydrating agent, inorganic compounds such as zeolite, anhydrous silica and anhydrous alumina, and organic compounds such as methyl orthoformate, ethyl orthoformate, tetraethoxymethane and tetrabutoxymethane can be used. Organic compounds are often used as dehydrating agents; examples are orthoesters such as methyl orthoformate and ethyl orthoformate.

Meanwhile, methods for preparing active nanoparticles in the absence of fluorinated groups and active nanoparticles containing at least one fluorinated group are described in the "Examples" section below.

In one embodiment, the reactive nanoparticles may comprise, in addition to one or more reactive group-containing components (B), one or more reactive group-free organic components. Active nanoparticles in the absence of fluorinated groups and active nanoparticles containing at least one fluorinated group:

"Reactive nanoparticles without fluorinated groups" (or "reactive nanoparticles without fluorinated groups") means that the components chemically bound to the metal oxide nanoparticles do not contain any fluorinated groups. A "active nanoparticle containing at least one fluorinated group" is defined as an active nanoparticle which incorporates a component comprising a fluorinated group, in addition to optionally additionally present components without a fluorinated group. These fluorinated group-containing components may or may not contain reactive groups. In other words, the fluorinated group is located within the reactive group-containing component or is not located within the reactive group-containing component. An example of a fluorinated group-containing component without reactive groups is, for example, a trimethoxysilane material containing a fluoroalkyl moiety. Examples include, for example, perfluorohexylethyltrimethoxysilane, perfluorooctylethyltrimethoxysilane, tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane, heptadecafluoro - 1,1,2,2-tetrahydrodecyltriethoxysilane or perfluorodecylethyltrimethoxysilane.

Examples of fluorinated groups include, but are not limited to: difluoromethyl, trifluoromethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, difluoropropyl, trifluoropropyl , tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl, heptafluoropropyl, difluorobutyl, trifluorobutyl, tetrafluorobutyl, pentafluorobutyl, hexafluorobutyl, heptafluorobutyl , octafluorobutyl, difluoropentyl, trifluoropentyl, tetrafluoropentyl, pentafluoropentyl, hexafluoropentyl, heptafluoropentyl, octafluoropentyl, similar C ₁ -C ₃₀ branched Perfluoro derivatives of chain or linear alkanes or alcohols and 1,1,2,2-tetrahydrofluoro derivatives of C ₁ -C ₃₀ branched or linear alkanes or alcohols, and the above-mentioned fluorinated alkanes/alcohols or Partially ethoxylated or propoxylated forms of 1,1,2,2-tetrahydrofluoroalkanes/alcohols. In one embodiment, the active particles containing fluorinated groups comprise fluoroalkyl groups.

In one embodiment of the invention, the weight ratio of active nanoparticles without fluorinated groups to active nanoparticles containing at least one fluorinated group is from 1:10 to 20:1, for example 1:9 to 9 :1, 1:1 to 15:1, 3:1 to 10:1, 3:1 to about 9:1, or 6:1 to about 8:1.

In one embodiment, the weight ratio of active nanoparticles free of fluorinated groups relative to the total weight of all active particles and ethylenically unsaturated urethane fluorinated components is from 20% to 90%, for example 40% -90%, 60-90%, or 75-90%. In one embodiment, the weight ratio of active nanoparticles containing fluorinated groups relative to the total weight of all active particles and ethylenically unsaturated urethane fluorinated components is 5-50%, such as 5-35% , 5-25% or 10-15%.

Ethylenically Unsaturated Urethane Fluorinated Components:

In one embodiment, the ethylenically unsaturated urethane fluorinated component is a fluorinated oligomer comprising one or more ethylenically unsaturated groups and one or more urethane groups.

The fluorinated urethane oligomer may be the reaction product of at least a fluorinated polyol, a polyisocyanate, and an ethylenically unsaturated reactive monomer. The reactive monomer may contain, for example, (meth)acrylate, vinyl ether, maleate, fumarate, or other ethylenically unsaturated groups in its structure.

In one embodiment, the fluorinated urethane oligomer has a molecular weight in the range of about 700 to about 10,000 g/mol, such as about 1000 to about 5000 g/mol.

Fluorinated polyols that can be used in the preparation of fluorinated urethane oligomers include, for example, fluorinated polyoxymethylene, polyethylene oxide, polypropylene oxide, polybutylene oxide, or copolymers thereof. In one embodiment, the fluorinated polyol is capped with ethylene oxide. Suitable fluorinated polyols include, for example, the Fluorolink fluid line of products sold by Solvay-Solexis Inc. (Fluorolink L, C, D, B, E, B1, T, L10, A10, D10, S10, C10, E10, T10 or F10) or Fomblin Z-Dol TX series products. These polyols are fluorinated poly(ethylene oxide-formaldehyde) copolymers terminated with ethylene oxide. Other potentially suitable fluorinated polyols include acrylic oligomers or telechelic polymers containing pendant or backbone fluorinated functional groups, such as acrylic copolymers of hexafluoropropylene and hydroxybutyl acrylate, or (meth)acrylic acid Acrylic copolymer of trifluoroethyl ester and hydroxybutyl acrylate. Other suitable fluorinated polyols include polyols such as L-12075 sold by 3M Company and the MPD series of polyols sold by Dupont.

Polyisocyanates that can be used in the preparation of fluorinated urethane oligomers include various organic polyisocyanates alone or in mixture. The polyisocyanates can be reacted with fluorinated polyols and ethylenically unsaturated isocyanate reactive compounds to form ethylenically unsaturated urethane fluorinated components: diisocyanates are among the preferred polyisocyanates. Typical diisocyanates include isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), diphenylmethylene diisocyanate, hexamethylene diisocyanate, cyclohexylene diisocyanate, methylene dicyclohexyl Alkane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, m-phenylene diisocyanate, 4-chloro-1,3-benzene diisocyanate, 4,4'-biphenyl diisocyanate, 1,5 -naphthalene diisocyanate, 1,4-butylene diisocyanate, 1,6-hexylene diisocyanate, 1,10-decylene diisocyanate, 1,4-cyclohexane diisocyanate, and polyalkylene oxide and polyester Diol diisocyanates such as polytetramethylene ether glycol end-capped with TDI and polyethylene adipate end-capped with TDI, respectively.

In one embodiment, the fluorinated polyol and polyisocyanate may be combined in a weight ratio of fluorinated polyol to polyisocyanate of from about 1.5:1 to about 7.5:1. Fluorinated polyols and polyisocyanates can be reacted in the presence of a catalyst to facilitate the reaction. Catalysts used for urethane reactions such as dibutyltin dilaurate and the like are suitable for this purpose.

Isocyanate-terminated prepolymers can be terminated by reaction with isocyanate-reactive functional monomers containing ethylenically unsaturated functional groups. The ethylenically unsaturated functional group is preferably acrylate, vinyl ether, maleate, fumarate or other similar compounds.

Suitable monomers for capping the isocyanate-terminated prepolymer with suitable (meth)acrylate functionality include: acrylates containing hydroxyl functionality such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, etc. .

Suitable monomers for capping the isocyanate-terminated prepolymer with suitable vinyl ether functionality include: 4-hydroxybutyl vinyl ether, triethylene glycol monovinyl ether, and 1,4-cyclohexanedimethylol mono vinyl ether. Suitable monomers that can be used to cap the prepolymer with suitable maleate functionality include maleic acid and maleate esters containing hydroxyl functionality.

Suitably, a sufficient amount of isocyanate-reactive functionality in monomers containing acrylate, vinyl ether, maleate, or other ethylenically unsaturated groups reacts with any remaining isocyanate functionality remaining in the prepolymer, And the prepolymer is capped with suitable functional groups. The term "capped" refers to a functional group that caps each of the two ends of the prepolymer.

The isocyanate-reactive ethylenically unsaturated monomer is reacted with the reaction product of a fluorinated polyol and an isocyanate. This reaction preferably takes place in the presence of an antioxidant such as butylated hydroxytoluene (BHT) or the like.

In one embodiment, the ethylenically unsaturated urethane fluorinated component has a viscosity at 23° C. of at least 2500 centipoise (“cps”), such as at least 5000 cps, at least 7500 cps, at least 10,000 cps, at least 25,000 cps, or at least 50,000cps. In one embodiment, the viscosity is at most 10,000,000 cps, such as at most 5,000,000 cps or at most 1,000,0000 cps.

In one embodiment, the percentage of ethylenically unsaturated urethane fluorinated component relative to the total weight of all active particles and ethylenically unsaturated urethane fluorinated component is at least 0.75% by weight, such as at least 1 % by weight, at least 2% by weight, at least 3% by weight or at least 5% by weight. In one embodiment, the percentage of ethylenically unsaturated urethane fluorinated component relative to the total weight of all active particles and ethylenically unsaturated urethane fluorinated component is at most 35% by weight, such as at most 25% by weight. % by weight, up to 15% by weight, up to 10% by weight, or up to 8% by weight.

dilute monomer

In one embodiment, the composition of the invention comprises a diluent monomer, for example in order to reduce the viscosity of the coating composition. Examples of diluting monomers include polymerizable vinyl monomers such as polymerizable monofunctional vinyl monomers containing one polymerizable vinyl group in a molecule and polymerizable vinyl monomers containing two or more polymerizable vinyl groups in a molecule Polymerizable polyfunctional vinyl monomers.

Examples of monofunctional diluting monomers include, for example, monofunctional vinyl monomers such as N-vinylpyrrolidone, N-vinylcaprolactam, vinylpyridine; (meth)acrylates containing an alicyclic structure such as (meth)acrylate base) isobornyl acrylate or (meth)acrylate-4-butylcyclohexyl; (meth)acrylate-2-hydroxyethyl, (meth)acrylate-2-hydroxypropyl, (meth)acrylate-2 -Hydroxybutyl ester, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate Amyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth) Octyl acrylate, Isooctyl (meth)acrylate, 2-Ethylhexyl (meth)acrylate, Nonyl (meth)acrylate, Decyl (meth)acrylate, Isodecyl (meth)acrylate , Lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate.

Examples of polyfunctional diluent monomers include, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, base) acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl diol Alcohol di(meth)acrylate, Trimethylolpropane trioxyethyl(meth)acrylate, Tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, Tris(2- Hydroxyethyl)isocyanurate di(meth)acrylate and bis(hydroxymethyl)tricyclodecane di(meth)acrylate.

The diluent monomers may also be halogenated, for example fluorinated. Examples of fluorinated diluent monomers include fluorinated acrylate monomers such as 2,2,3,3-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate or 1H, 1H, 2H acrylate , 2H-heptadecafluorodecyl ester.

In one embodiment, the coating composition of the invention comprises, relative to the total weight of all active particles and ethylenically unsaturated urethane fluorinated components, 0-20% by weight, such as 0.1-10% by weight, 0.25-5% by weight or 0.5-2.5% by weight of one or more diluents.

additive

Various additives such as antioxidants, ultraviolet absorbers, light stabilizers, adhesion promoters, coating surface modifiers, thermal polymerization inhibitors, leveling agents, surfactants, coloring agents, etc. may be included in the coating composition of the present invention. additives, preservatives, plasticizers, lubricants, solvents, fillers, anti-aging agents and wetting aids. Examples of antioxidants include Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Antigene P, 3C, FR, SumilizerGA-80 (manufactured by Sumitomo Chemical Industries Co., Ltd.), etc.; ultraviolet absorbers Examples include Tinuvin P, 234, 320, 326, 327, 328, 329, 213 (produced by Ciba Specialty Chemicals Co., Ltd.), Seesorb 102, 103, 110, 501, 202, 712, 704 (produced by Sypro Chemical Co., Ltd. . production) etc.; examples of light stabilizers include Tinuvin 292, 144, 622LD (produced by Ciba Specialty Chemicals Co., Ltd.), Sanol LS770 (produced by Sankyo Co., Ltd.), Sumisorb TM-061 (produced by Sumitomo Chemical Industries Co. , Ltd. production) etc.; Examples of silane coupling agents as adhesion promoters include γ-mercaptopropylmethyl monomethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyl Trimethoxysilane, γ-mercaptopropyl monoethoxysilane, γ-mercaptopropyldiethoxysilane, γ-mercaptopropyltriethoxysilane, β-mercaptoethyl monoethoxysilane, β -Mercaptoethyltriethoxysilane, β-mercaptoethyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-amino Ethyl)-3-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyl Dimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane and γ- Methacryloxypropyltrimethoxysilane. Examples of commercially available products of these compounds include SILAACE S310, S311, S320, S321, S330, S510, S520, S530, S610, S620, S710, S810 (manufactured by Chisso Corp.), Silquest A-174NT (manufactured by OSI Specialties-Crompton Corp. .manufactured), SH6062, AY43-062, SH6020, SZ6023, SZ6030, SH6040, SH6076, SZ6083 (manufactured by Toray-Dow Corning Silicone Co., Ltd.), KBM403, KBM503, KBM602, KBM603, KBM803, KBE903 (Shin-Etsu Silicone Co., Ltd.), etc. Acidic adhesion promoters such as acrylic acid can also be used. Phosphate esters such as Eb168 or Eb170 from UCB are useful adhesion promoters; examples of coating surface modifiers include silicone additives such as dimethylsiloxane polyether and commercially available products such as DC-57, DC-190 (manufactured by Dow-Corning), SH-28PA, SH-29PA, SH-30PA, SH-190 (manufactured by Toray-Dow Corning Silicone Co., Ltd.), KF351, KF352, KF353, KF354 (Shin-Etsu Chemical Co. , Ltd.) and L-700, L-7002, L-7500, FK-024-90 (manufactured by Nippon Unicar Co., Ltd.).

In one embodiment, the compositions of the present invention comprise from about 0.01 to about 10 weight percent adhesion promoter relative to the total weight of the ethylenically unsaturated urethane fluorinated component. In one embodiment, the compositions of the present invention comprise from about 0.01 to about 5% by weight antioxidant relative to the total weight of the ethylenically unsaturated urethane fluorinated component.

Photoinitiators include, for example, acetophenone derivatives having hydroxyl or alkoxy functional groups, hydroxyalkyl phenones and/or benzoyldiarylphosphine oxides. Examples of photoinitiators include Irgacure 651 (benzil dimethyl ketal or 2,2-dimethoxy-1,2-diphenylethanone, Ciba-Geigy), Irgacure 184 (1-hydroxy-cyclo Hexyl-phenyl ketone as active ingredient, Ciba-Geigy), Darocur 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one as active ingredient, Ciba-Geigy), Irgacure 907 (2 -Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, Ciba-Geigy), Irgacure 369 (2-benzyl-2-dimethylamino-1- (4-Morpholinophenyl)-butan-1-one as active ingredient, Ciba-Geigy), Esacure KIP 150 (poly{2-hydroxy-2-methyl-1-[4-(1-methyl Vinyl)phenyl]propan-1-one}, Fratelli Lamberti), Esacure KIP 100F (poly{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane -1-ketone} and 2-hydroxy-2-methyl-1-phenyl-propan-1-one mixture, FratelliLamberti), Esacure KTO 46 (poly{2-hydroxy-2-methyl-1-[4 -Mixture of (1-methylvinyl)phenyl]propan-1-one}, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and methylbenzophenone derivatives, Fratelli Lamberti ), Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide, BASF), Irgacure 819 (bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine- Oxide, Ciba-Geigy), Irgacure 1700 (25:75% bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2 -Methyl-1-phenyl-propan-1-one mixtures, Ciba-Geigy) and the like.

Oligomers containing two different types of ethylenic unsaturation, a vinyl ether group and another type of ethylenic unsaturation, can be rapidly copolymerized in the presence of these photoinitiators to provide fast photocuring, and in the absence of Polymerization initiators rapidly react with each other upon exposure to various energies.

In one embodiment, the photoinitiator is present in the range of about 0.01% to 20.0% by weight, such as about 1-15% by weight relative to the total weight of all active particles and ethylenically unsaturated fluorinated urethane components , 4-12% by weight, or 5-10% by weight, are present in the composition of the invention.

In one embodiment, the amount of photoinitiator is at least 2% by weight, such as at least 5% by weight, based on the total weight of the coating composition.

In one embodiment, the present invention relates to a radiation curable composition comprising:

a). From 50% to 90% by weight of active nanoparticles without fluorinated groups, relative to the total weight of all active particles and ethylenically unsaturated urethane fluorinated components;

b). 5% to 20% by weight of active nanoparticles containing at least one fluorinated group, relative to the total weight of all active particles and ethylenically unsaturated urethane fluorinated components;

and

c). From 1% to 10% by weight of one or more ethylenically unsaturated urethane fluorinated components relative to the total weight of all active particles and ethylenically unsaturated urethane fluorinated components;

In one embodiment, the present invention relates to a composition comprising:

a) active nanoparticles in the absence of fluorinated groups; and

b) active nanoparticles containing at least one fluorinated group;

wherein the ratio of particles (a) to particles (b) is at least 1:1.

In one embodiment, the present invention relates to a composition comprising:

a) active nanoparticles in the absence of fluorinated groups; and

b) active nanoparticles containing at least one fluorinated group;

wherein the ratio of particles (a) to particles (b) is less than 0.95:1.

In one embodiment, the present invention relates to a composition comprising:

a) active nanoparticles; and

b) one or more ethylenically unsaturated urethane fluorinated components;

wherein the ratio of said reactive nanoparticles to said ethylenically unsaturated urethane fluorinated component is at least 6:1.

Coating and Performance

In one embodiment of the invention, the composition is spin coated on the substrate using a standard Headway Research model EC101DT spin coater. 1 ml of the liquid composition was then deposited on a 3"x3" substrate fixedly placed on the chuck platform of the spin coater. The coating liquid/substrate was spin-coated at 7500 rpm for 12 seconds with a spin-coating acceleration of 3000 rpm/s. The resulting thin wet film was further evaporated at room temperature for 60 seconds after spin coating. The evaporated films were subjected to a UV dose of 2.0 J/ ^cm2 using a Fusion D-lamp in the nitrogen atmosphere used. UV dose was verified using an International Light Model IL 390B Light Bug UV Radiometer. The liquid coatings were diluted in solvent to 5% total solids prior to coating to form a cured film thickness of 0.10-0.15 μm after coating and curing.

In one embodiment, the compositions of the present invention, when cured, provide coatings having a low refractive index. In one embodiment, the coating has a refractive index of less than 1.50, such as in the range of 1.35-1.50, such as 1.40-1.48, 1.42-1.46 or 1.432-1.50.

In one embodiment, the compositions of the present invention when cured provide coatings with good surface hardness and abrasion resistance. These were characterized by film hardness pencil test and abrasion test. In one embodiment, the coating has a pencil hardness of at least F, such as at least H or at least 2H. In one embodiment, the coating is undamaged when tested by an abrasion test. These experiments are described in the Examples section.

The degree of cure of the composition can be expressed as percent reacted acrylated saturation (%RAU). The test method for measuring %RAU is mentioned in the Examples section of the present description. In one embodiment, the composition of the invention has a %RAU when cured of at least 40%, such as 45% to 98% or 55% to 70%.

The composition in the present invention can be used as a low refractive index layer for an anti-reflection display system. An antireflective display system may comprise a substrate, a hardcoat layer on the substrate, a high refractive index layer coated on the hardcoat layer, followed by a low refractive index layer.

Substrates suitable for use in displays include organic substrates, such as plastic substrates such as those comprising the following plastics: polynorbornene, polyethylene terephthalate, polymethyl methacrylate, polycarbonate, Polyethersulfone, polyimide, cellulose, cellulose triacetate, fluorene polyester and/or polyether naphthalene. Examples of other substrates include, for example, inorganic substrates such as glass or ceramic substrates.

The substrate may be pretreated prior to coating. For example, the substrate can be corona or high energy treated. The substrate may also be chemically treated, such as by emulsion coating.

In one embodiment, the substrate comprises functional groups such as hydroxyl groups, carboxylic acid groups and/or trialkoxysilyl groups such as trimethoxysilane. The presence of these functional groups can enhance the adhesion of the coating to the substrate.

In one embodiment, the compositions of the present invention can also be used as optical fiber primer coatings, optical fiber secondary coatings, substrate coatings, bundling materials, ink coatings, photonic crystal fiber coatings, optical disc adhesives, hard Film coating or lens coating.

The invention also relates to articles comprising:

(a) the substrate;

(b) hard coating layer;

(c) a high refractive index coating on said hardcoat layer; and

(d) a low refractive index coating obtained by curing a composition comprising:

i) active nanoparticles without fluorinated groups reactive with nanoparticles having fluorinated functional groups;

ii) reactive nanoparticles containing at least one fluorinated group reactive with nanoparticles without fluorinated functional groups; and

iii) Ethylenically unsaturated urethane fluorinated components.

Method for preparing low refractive index coatings

The invention also relates to a method for preparing a low-refractive-index coating, said method comprising mixing at least the following components:

a) active nanoparticles without fluorinated groups;

b) active nanoparticles containing at least one fluorinated group; and

c) Ethylenically unsaturated urethane fluorinated components.

The invention also relates to a method of preparing a coating for an object, said method comprising:

a) Preparation of a radiation curable composition comprising:

i) active nanoparticles without fluorinated groups;

ii) active nanoparticles containing at least one fluorinated group; and

iii) ethylenically unsaturated urethane fluorinated components,

b) coating said radiation curable composition on said object.

Example

The following examples are given as specific embodiments of the invention and to illustrate its practice and advantages. It should be understood that the examples are given by way of illustration and are not intended to limit the specification or the appended claims in any way.

Preparation of Composition I (comprising active nanoparticles in the absence of fluorinated groups):

The components and their relative amounts used to prepare Composition I are shown in Table 1 below. By adding a trimethoxysilane compound (Int-12A) containing acrylate groups together with a compound HQMME that inhibits the polymerization of acrylate groups into a suspension of nano-silica oxide particles in MEK (MEK-ST), the Nano silica oxide particles are surface grafted. A small amount of water was added to the MEK-ST suspension (1.7% by weight of total MEK-ST) to catalyze the silane grafting reaction. The mixture was refluxed at 60°C for at least three hours while stirring. Subsequently, the alkoxysilane compound MTMS was added, and the resulting mixture was stirred and refluxed at 60° C. for at least one hour. The dehydrating agent OFM was added and the resulting mixture was stirred and refluxed at 60 °C for at least one hour.

Table 1. Materials (percentage by weight) used to prepare Composition I: about 33% by weight of active nanoparticle composition

Material weight% MEK-ST (nano silica oxide particles in MEK [30% by weight solid particles relative to the total weight of particles and methyl ethyl ketone]) 82.50% Int-12A (trimethoxysilane acrylate coupling agent) 7.84% HQMME (hydroquinone monomethyl ether, stabilizer) 0.14% MTMS (methyltrimethoxysilane, surface derivatizer) 1.23% OFM (trimethyl orthoformate, dehydrating agent) 8.29% total 100%

Preparation of Composition II (comprising active nanoparticles containing at least one fluorinated group):

The components and their relative amounts used to prepare the fluorinated acrylated MTST are shown in Table 2 below. The nanoparticles were stabilized by adding trimethoxysilane compound (Int-12A) containing acrylate groups and HQMME, a compound that inhibits the polymerization of acrylate groups, to a suspension of nano-silica oxide particles in methanol (MT-ST). Silica oxide particles. The small amount of water present in the MT-ST suspension (1.7% by weight of the total MT-ST) facilitated the silane grafting reaction. The mixture was refluxed at 60°C for at least three hours while stirring. Subsequently, the fluorinated alkoxysilane compound TDFTEOS was added, and the resulting mixture was stirred and refluxed at 60° C. for at least one hour. Subsequently, the alkoxysilane compound MTMS was added, and the resulting mixture was stirred and refluxed at 60° C. for at least one hour. The dehydrating agent OFM was added and the resulting mixture was stirred and refluxed at 60 °C for at least one hour.

Table 2. Materials (weight percent) used to prepare Composition II: about 35% by weight solid fluorinated active nanoparticle composition

Material weight% MT-ST (nano silica particles in methanol [30% by weight solid particles relative to the total weight of particles and methanol]) 81.14% Int-12A (trimethoxysilane acrylate coupling agent) 7.68% HQMME (hydroquinone monomethyl ether, stabilizer) 0.14% TDFTEOS (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, surface derivatizing agent) 2.28% MTMS (methyltrimethoxysilane, surface derivatizer) 0.61% OFM (trimethyl orthoformate, dehydrating agent) 8.15% total 100%

Preparation of fluorinated components of ethylenically unsaturated urethanes

The ethylenically unsaturated urethane fluorinated components were prepared by reacting the components in Table 3 below:

Table 3. Ethylenically Unsaturated Urethane Fluorinated Components

components weight% 2-Hydroxyethyl Acrylate 8.18 Isophorone diisocyanate 15.70 BHT 0.07 Dibutyltin dilaurate 0.04 Fluorolink E (fluorinated polyether) 76.01

The ethylenically unsaturated urethane fluorinated component thus prepared (hereinafter also referred to as H-I-FluorolinkE-I-H) was mixed with the components in Table 4 below to form Intermediate Composition A:

Table 4. Intermediate Composition A

components weight% H-I-Fluorolink E-I-H 80.7 Lucirin TPO 0.5 Irgacure 184 1.5 Irganox 1035 0.3 Hexylene glycol diacrylate 16.0 Mercaptopropyltrimethoxysilane 1.0

Finally, "Composition III" was prepared by mixing the components in Table 5 below:

Table 5. Composition III (comprising about 7% by weight ethylenically unsaturated urethane fluorinated component)

components weight% Composition A 8.8 Darocur 1173 1.2 methyl ethyl ketone 90.0

Compositions of Example 1 and Comparative Examples 1-10 were prepared by mixing the components in Table 6A below (% by weight are relative to the total weight of the composition). The experimental performance is illustrated in Table 6B.

Table 6A: Example 1 and Comparative Examples 1-10:

Element Example 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 (≈33% by weight of active nanoparticle composition) 68.0 49.0 49.0 98.0 68.0 68.0 Composition III (comprising ≈7% by weight of fluorinated urethane acrylate) 20.0 49.0 49.0 98.0 Composition II (≈35% by weight of fluorinated active nanoparticle composition) 10.0 49.0 49.0 98.0 10.0 10.0 Tosoh TFEMA (Fluorinated Monomethacrylate 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 is commercially available from Tosoh.

NTX5847 is commercially available from Sartomer.

Irgacure 184 and Irgacure 907 are commercially available from Ciba.

Table 6B. Film properties after curing

performance Example 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 Refractive Index (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

Evaluation of coating performance (test method):

Film hardness was measured by pencil test (pencil hardness):

Pencil hardness was measured according to standard method ASTM D3363: The composition was cured on a glass substrate and the coated substrate was placed on a firm level surface. Hold the pencil firmly on the film at a 45° angle (point away from the operator) and draw it 6.5 mm (1/4 inch) away from the operator. Begin the process with the hardest pencil and continue decreasing the hardness scale to either of two endpoints: 1, a pencil that will not poke or gouge through the membrane (pencil hardness), or 2, a pencil that will not scratch the membrane (scratch hardness).

The pencil hardness of the film is represented by letters in the following sequence: (film hardness increases from left to right):

4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H

A film was considered sufficiently hard if its hardness was represented by any letter in the group (F, H, 2H, 3H, 4H).

Measurement of Refractive Index of Cured Film

Glass microscope slides were coated with the test coatings and the coatings were cured by UV exposure. (Standard curing conditions: solvent evaporation, curing at 1.0 J/cm ² , Fusion 300 W D-lamp, air atmosphere). The cured film was cut into 2 mm x 2 mm squares using a blade, and alternate squares were removed from the cured film. The slide is then placed under a 10X microscope equipped with axially transmitted illumination for calibration and configured with an objective lens no larger than at least 0.70 numerical aperture. Use monochromatic illumination by placing a narrow bandwidth interference filter in the optical path of the microscope's built-in illumination system. If an external illumination source is provided, a monochromator can also be used to provide a continuously variable source. The normal wavelength used is 589 nm or the sodium D-line, from where the refractive index number is denoted "n". The cured film was then compared to a standard liquid of known refractive index (Cargill Index Liquid, StandardGroup available from McCrone Microscopy Inc.). Using a bottle coater bar, a small droplet of refractive index liquid is applied to the portion adjacent to the cover slip, capillary action driving it under the cover slip to fill the space around the coated square. As the microscope focus is adjusted such that the distance between the sample and the objective increases, the Baker lines shift towards the higher refractive index medium. If the coating has a higher index of refraction than the liquid placed inside, the Baker's line moves into the square profile as the focal point moves "up". The procedure is repeated for new coated squares until the outline of the square disappears or the Baker's line reverses the viewing direction from the previous viewing. A higher or lower index liquid is selected according to the direction of index mismatch revealed by initial observation. If the outline of the coated square cannot disappear and two liquids next to each other in the group are found to give opposite signals of shifting of the Baker's line, then the refractive index of the material lies between two values, most likely in the middle of the range.

wear test

Place the coated substrate on a firm, level surface. A paper lab wipe (Kimwipes(R) EX-L available from Kimberly Clark Co.) was wrapped around one of the tester's fingers. The paper was rubbed back and forth on the cured film 2-3 times using moderate manual pressure. Then check the wear of the cured film. The damage is then quantified by the following scale:

0 = No damage observed

1 = Minor damage observed

2 = The cured film was observed to be moderately damaged

3 = Cured film is completely removed or damaged

Damage from rubbing with a paper lab wipe indicates poor hardness of the cured film, and/or low crosslink density of the cured film, and/or incomplete cure of the photopolymerizable groups, and/or adhesion of the cured film to the substrate. Slip.

Measurement of degree of cure (%RAU) of UV-cured coatings

A drop of liquid paint was spin-coated onto the KBr crystals until completely covered with a coating thickness of approximately 0.1 μm. Samples were scanned using 100 co-added scans and spectra were converted to absorbance. The net peak area of the acrylate absorbance of the liquid coating is then measured. For most acrylate based coatings an absorbance at 810 cm ^-1 should be used. Alternate acrylate absorbance should be used if the coating contains silicones or other components that absorb strongly at or near 810 cm ^-1 .

The net peak area should be measured using the "baseline" technique, where the baseline is drawn as a tangent to the absorbance minima on either side of the peak. The area below the peak and above the baseline is then determined.

Samples were cured at 1.0 J/ ^cm2 using a 300W Fusion D-lamp in an air atmosphere. Repeat the FTIR scan of the sample and measure the net peak absorbance of the cured coating spectrum. The baseline frequency does not have to be the same as the liquid coating, but the baseline should be chosen such that it is also tangential to the absorbance minima on either side of the analytical wavelength band. Repeat the measurement of the peak area of the non-acrylate reference peak for the liquid and cured coating spectra. For each subsequent analysis of the same formulation, the same reference peak with the same baseline point should be used.

Determine the ratio of the acrylate absorbance to the reference absorbance of the liquid coating using the following equation:

R _L =A _AL /A _RL

where _AAL = the area of the acrylate absorbance of the liquid

A _RL = the area of the reference absorbance of the liquid

_RL = area ratio of liquid

In a similar manner, determine the ratio of the acrylate absorbance to the reference absorbance of the cured coating using the following equation:

R _F =A _AF /A _RF

where _AAF = area of acrylate absorbance of cured coating

A _RF = area of the reference absorbance of the cured coating

R _F = area ratio of cured coating

Finally, the degree of cure as percent-responsive acrylate unsaturation (%RAU) was calculated using the following equation:

%RAU=(R _L -R _F )×100/R _L

where _RL = area ratio of liquid

R _F = area ratio of cured coating

Compositions containing appreciable amounts of multifunctional acrylates are known to have lower %RAU values when fully cured, typically on the order of 55-70% RAU. It is believed that this is due to vitrification of the acrylate network such that unreacted acrylate does not have sufficient mobility within the network to reach propagating free radicals, and vice versa.

Having described specific embodiments of the invention, it is to be understood that many modifications of the invention will be apparent or suggested to those skilled in the art, and it is therefore intended that the invention be limited only by the spirit and spirit of the appended claims Limited scope.

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.