CN100594222C - Stain repellent optical hard coating - Google Patents
Stain repellent optical hard coating Download PDFInfo
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- CN100594222C CN100594222C CN200580018583A CN200580018583A CN100594222C CN 100594222 C CN100594222 C CN 100594222C CN 200580018583 A CN200580018583 A CN 200580018583A CN 200580018583 A CN200580018583 A CN 200580018583A CN 100594222 C CN100594222 C CN 100594222C
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Abstract
The invention provides a hard coating composition for use as a stain repellent single layer on an optical display. The coating composition adds a monomer of a mono or multi(methyl)acrylate bearing atleast one monovalent hexafluoropolypropylene oxide derivative and a free radically reactive compatibilizer consisting of either a fluoroalkyl-group containing acrylate compatibilizer or a fluoroalkylene-group containing acrylate compatibilizer to a conventional hydrocarbon-based hard coat formulation. The resultant coating is substantially smooth and forms a durable surface layer that has low surface energy that is stain and ink repellent.
Description
TECHNICAL FIELD OF THE INVENTION and industrial usability
The present invention relates to optical hard coating, more particularly, the present invention relates to stain repellent optical hard coating.
Background of invention
In display unit industry, the hard coating polymer film of optics is just becoming more and more important.People continually develop the new purposes of hard paint film, and it is used in (for example) computer, on the optical display in TV, utensil, mobile telephone, aerospace and the automotive industry.
People on the optical display surface, wear hard applying coating and form vestige to prevent its surface.Optical hard coating ideal product feature is: with low luminous reflectance factor (for example, 1.5% or lower), scratch resistance and wear resistance and ink repellent and pollution resistance.
The material that has been used at present surfacecti proteon comprises fluorinated polymer or fluoropolymer.Fluoropolymer is better than conventional hydrocarbon materials in following properties, and described character is: strong unreactiveness (resistance to acids and bases), dirt resistance and pollution resistance (this is because the surface energy of fluoropolymer is low), agent of low hygroscopicity, weathering resistance and sunlight resistance.
Because low surface energy characteristic that fluoropolymer coating had is unfavorable for reaching gratifying bond properties, and its inherent flexibility is unfavorable for reaching the favorable mechanical weather resistance, and therefore, it is not preferred using fluoropolymer coating separately.Therefore, people have worked out such fluoropolymer, and the hard coating formulation of this fluoropolymer and hydro carbons is crosslinked, thereby improve its hardness and improve it and the binding property of substrate interface.For example, people are known: in the time of in the PFPE of free-radical curable being added to ceramic polymer (ceramer) hard coating composition, described PFPE can provide the strong repellency to fountain pen ink and permanent mark pen ink, wherein said ceramic polymer hard coating composition contains the binder precursor of multiple colloidal inorganic oxide particle and free-radical curable, the U.S. Patent No. 6 of Kang for example, 238,798 is described.Yet perfluoro polyether derivant and the hard coating of ceramic polymer can not be fully compatible, therefore tend to cause the coating dewetting and form coarse surface.
Therefore, wish to form a kind of fluoropolymer based hard coating that has gratifying planarization, weather resistance, ink repellent and pollution resistance and have the good optical quality.
Summary of the invention
The invention provides that a kind of mode with individual layer applies, easy to clean and have the optical hard coating of pollution resistance and ink repellent.
In a preferred embodiment of the invention; composition as the curing hard coat on the optical display is formed by a kind of like this mixture, and this ingredients of a mixture is: contain the hydro carbons hard coating composition the free radical reaction material, have at least one univalent poly-(oxidation hexafluoro propylidene) partly monobasic or polynary (methyl) acryl compound and be selected from the compatilizer that contains fluoroalkyl and contain free radical reaction compatilizer in the compatilizer of fluorine alkylidene group.Described composition can randomly contain inorganic particle (the hard coating of ceramic polymer).In this article, term " (methyl) acryl " is meant the functional group that comprises acrylate, methacrylic ester, acrylamide, Methacrylamide, alpha-fluoro acrylic ester, sulfo-acrylate and sulphomethyl acrylate.In addition, all (methyl) acryl functional groups contained in term " acrylate ".
In addition, term " ceramic polymer " is meant that such composition, said composition contain the inorganic oxide particles of the submicron order size that is dispersed in the binder substrate (for example silicon-dioxide).Term " ceramic polymer composition " but be meant also not by partly solidified at least, therefore be the of the present invention ceramic polymer preparation of mobile application of liquid state.Term " ceramic polymer matrix material " or " coating " be meant by partly solidified at least, therefore become the of the present invention ceramic polymer preparation of immobilising substantially solid state.In addition, term " free radical reaction " is meant that it participates in the ability of crosslinking reaction when being exposed to suitable curing energy source for monomer, oligopolymer, polymkeric substance or analogue.
The gained coating has gratifying planarization, weather resistance, ink repellent and pollution resistance, and has the good optical quality.
By considering the following detailed description and appending claims and with reference to accompanying drawing, other purpose of the present invention and advantage will become apparent.
Brief Description Of Drawings
Fig. 1 illustrates the goods with the optical display that has applied hard coat, and these goods form according to the preferred embodiments of the invention.
Detailed Description Of The Invention and preferred embodiment
About following defined term, should adopt these definition, unless provided different definition in other place of claims or specification sheets.
Term " polymer " " be interpreted as: comprise polymkeric substance, multipolymer (for example adopt two or more different monomers and form polymkeric substance), oligopolymer and combination thereof, and polymkeric substance, oligopolymer or the multipolymer that can make with the form of compatible blend.
The numerical range of describing by end points comprises all numerical value (for example, numerical range 1-10 comprises 1,1.5,3.33 and 10) that comprised in this scope.
In this specification sheets and appending claims, used " a kind of ", " being somebody's turn to do ", " described " or the situation that do not indicate quantity comprise that referent is more than one situation, unless described content is explicitly shown as other implication before a certain noun.Therefore, the mixture that for example, contains " a kind of compound " is meant the mixture that comprises two or more compounds.In this specification sheets and appending claims, used word " perhaps " generally include " and/or " the meaning, unless described content is explicitly shown as other implication.
Except as otherwise noted, otherwise be used for representing all numerals of composition consumption, performance (for example contact angle) metering etc. in specification sheets and claims, all be interpreted as in all cases modifying with word " approximately ".Therefore, unless make opposite explanation, otherwise listed digital parameters all is an approximation in above-mentioned specification sheets and appending claims, the difference of the desirable properties that it may attempt to obtain along with those of ordinary skill in the art's instruction according to the present invention and change.Do not attempt the application of the doctrine of equivalents of claims scope is limited, each digital parameters should be counted as at least at least according to the numerical value of the significant figure of being reported and by using the routine method of rounding up to obtain.Although digital scope and parameter cited in wide region of the present invention all are approximations, listed numerical value is all reported accurately as far as possible in object lesson.Yet,, make any numerical value must all contain certain error because all there is standard deviation in various detection methods.
Term " optical display " or " display panel " can refer to not illuminated and especially illuminated any conventional optical display, it comprises that (but not being subject to) multiword (for example accords with multi-thread indicating meter, liquid-crystal display (" LCD "), plasma display, preceding throwing and rear projection display, cathode tube (" CRT "), sign) and monocase or binary displays (for example, photodiode (" LED "), signal lamp and switch).The exposed surface of this display panel can be called " lens ".The present invention is specially adapted to its indicating meter of watching the surface to be run into or touch by pen, marking pen and other mark equipment, rag, paper product etc. easily.
The information that protective coating of the present invention can be used for multiple movable type and non-moving type shows goods.These goods comprise PDA, mobile phone (array configuration that comprises the PDA/ mobile phone), LCD TV (direct lighting mode and edge light mode), touch-screen, wrist-watch, auto-navigation system, global positioning system (GPS), depthometer, counter, e-book, CD Player and DVD player, projection TV screen, computer monitor, laptop computer displays, instrument, dashboard Abdeckteil, sign (for example, graphic presentation), or the like.The surface of watching of these goods can have any stock size and shape, and can be plane or on-plane surface, but flat-panel monitor is preferred.Also can or film and be used for multiple other goods coating composition of the present invention, for example, the head lamp and taillight, show case, glasses, pavement marker (for example, Tu Chu pavement marker) and pavement marker band, captions projector, stereophonic sound system cabinet door (stereo cabinet door), stereophonic sound system Abdeckteil, Biao Meng and CD and the magneto-optical recording etc. that are used for camera gun, glasses lens, binocular eyeglass, speculum, retrodirective reflection sheet material, automobile window, building window, train window, ship window, aircraft windows, vehicle.
Coating for these display unit it is desirable to, and this coating keeps optical transparence simultaneously with low surface energy (for example, bearing dirty property, pollution resistance, hate oil and/or hydrophobic nature) and weather resistance (for example, resistance to abrasion).The effect of described hard coat is to reduce to dazzle light loss, improves weather resistance and optical transparence simultaneously.
Can adopt several different methods to characterize surface energy, for example, adopt as contact angle and ink repellent and characterize surface energy according to the described determination of test method of example part.Preferably, the static contact angle of top layer as herein described and goods and water is at least 70 °.More preferably, the static contact angle of itself and water is at least 80 °, and more preferably, the static contact angle of itself and water is at least 90 °.Can be that the advancing contact angle of top layer as herein described and goods and n-Hexadecane is at least 50 °, more preferably at least 60 ° for other character or the character except that above-mentioned selected for use.Low surface energy can make exposed surface have the property of bearing dirty and easy to clean.
Another feature of low surface energy relates to: the one-tenth pearl degree of ink when fountain pen ink or mark pen ink are applied to exposed surface.When (for example with paper handkerchief or towel paper, can derive from the paper handkerchief of the commodity by name " SURPASS FACIAL TISSUE " of the Kimberly Clark company that is positioned at State of Georgia, US Roswell city) when the wiping exposed surface can easily be wiped fountain pen ink and mark pen ink, this top layer and goods show " ink repellent ".
Referring now to Fig. 1, Fig. 1 is the stereographic map with the goods (being computer monitor 10 at this) that are assemblied in the optical display 12 in the shell 14.Optical display 12 is the material of the substantially transparent that has light and strengthen the property, and the user can watch text, picture or other demonstration information by this display unit.Optical display 12 has the hard coat 18 that is coated on the optical element 16.
Can with various permanent be coated in the opposite side (being the dorsal part mutually of hard coat 18) of base material 16 with removable binder composition 25, thereby can easily these goods be installed on the display unit surface.Usually, tackiness agent 25, base material 16 and hard coat 18 are packed film forming 27 in advance, and this film has the peel ply (not shown) that sticks on the tackiness agent 25.Then, peel ply is removed, other zone of binder layer and shell 14 or goods 10 is bonding, to form optical display 12.
Under the situation of display panel, base material is a printing opacity, and promptly light can see through base material 16, thereby makes people can watch display unit.Display panel 10 can adopt transparent (for example glossiness) transmitting substrate 16, also can use lacklustre transmitting substrate 16.Lacklustre base material 16 has lower transmission value and the haze value of Geng Gao than glossiness film commonly used usually.But lacklustre film shows this character normally owing to the mineral filler (for example silicon-dioxide) that wherein exists with the scattered beam of micron order size dispersion.Exemplary lacklustre film can be the product available from the commodity " N4D2A " by name of the U.S.A.Kimoto Tech company that is positioned at State of Georgia, US Cedartown city.At the transparent substrate of transparent substrate, hard applying coating and have under the situation of display unit goods of transparent substrate, haze value is preferably less than 5%, more preferably less than 2% even more preferably less than 1%.The alternate manner that can Gong select for use or mode in addition are that transmissivity is preferably more than about 90%.
The blooming of various printing opacities is known, these films comprise (but not being subject to): multi-layer optical film, microstructure film (for example retrodirective reflection sheet material and brightness enhancement film), (for example reflectivity or absorptivity) polarizing coating, diffusion barrier and (for example twin shaft) phase shift films and compensate film (for example, described in U.S. Patent Application Publication No.2004/0184150 (its applying date is on January 29th, 2004)).
As described in U.S. Patent application 2003/0217806, multi-layer optical film is a kind of like this film, and this film obtains required transmission performance and/or reflecting properties by the arrangement of the different microbedding of specific refractory power at least in part.Each microbedding has different refractive index characteristics, thereby makes some light being reflected at the interface between adjacent microlayers.The thickness of microbedding is enough thin, between the light that makes place, a plurality of interface reflect constructive interference or destructive interference takes place, thereby makes film body have required reflecting properties or transmission performance.For the blooming of the light that is designed to be used for to reflect ultraviolet, visible or near-infrared wavelength place, the optical thickness of each microbedding (being that physical thickness multiply by specific refractory power) is generally less than about 1 μ m.Yet, wherein can also comprise thicker layer, for example, be positioned at the top layer of film outer surface, perhaps a plurality of microbedding assemblies are separated and be disposed in film with interior protective frictional belt.Multilayer optical film body can also contain one or more thick bonding coats, so that two in the lamination or multi-disc multi-layer optical film are glued together.
The reflecting properties of multilayer optical film body and transmission performance are the functions of the specific refractory power of each microbedding.Each microbedding localized positions in film at least can be by refractive index n in the face
x, n
yAnd the refractive index n relevant with the thickness axis of film
zCharacterized.These specific refractory poweres represent that separately measured material is to the specific refractory power along mutually orthogonal x axle, y axle and z axle polarising light.In force, control specific refractory power by rational selection of material and treatment condition.Can make film like this: will be generally two kinds of alternative polymer A, the coextrusion of B layer tens of or hundreds of layers, subsequently, can randomly make the multilayer extrudate by one or more multiplications mould (multiplicationdie), then extrudate is stretched or (otherwise) extrudate is orientated, to form final film.The film of gained is made up of tens of or hundreds of independent microbeddings usually, adjusts the thickness and the specific refractory power of microbedding, thereby forms one or more reflection bands of a spectrum in required SPECTRAL REGION (for example, visible region or near-infrared region).For the layer with proper amt obtains high reflectivity, preferably, adjacent microlayers is to poor (the δ n along the specific refractory power of x axle polarising light
x) be at least 0.05.If desired two kinds of orthogonal polarized light are shown high reflectivity, then further preferably, adjacent microlayers is to poor (the δ n along the specific refractory power of y axle polarising light
y) be at least 0.05.In addition, the difference of specific refractory power can be less than 0.05, and be preferably about 0, so multi-stacked to form, the vertical incidence light of a certain polarization state of this multi-stacked reflection and the vertical incidence light of transmission orthogonal polarization state.If desired, can also adjust adjacent microlayers to poor (δ n along the specific refractory power of z axle polarising light
z), thereby obtain required reflecting properties at the p polarized component of oblique incident ray.
Can in the open WO99/36248 of PCT people such as () Neavin, find the exemplary materials that can be used to make the polymer multi-layer blooming.What suit the requirements is that at least a material is the very big polymkeric substance of absolute value of stress optical coefficient.In other words, when this polymkeric substance is stretched, its tend to produce stronger double refraction (at least about 0.05, more preferably at least about 0.1 or even be 0.2).According to the application of multilayer film, can two orthogonal directionss in membrane plane between, produce double refraction in one or more interior directions and between perpendicular to the direction of membrane plane or between the direction of its array mode.In particular cases widely different between each isotropic specific refractory power that the tensile polymer layer is not had, can weaken the back that stretches and at least a polymkeric substance, produce strong birefringent trend, but double refraction is still desirable usually.When selective polymer is used for mirror coating and be used for polarizing coating (this film adopts twin shaft technology to make, and this technology stretches to film on two orthogonal interior directions), can produce this Special Circumstances.In addition, the ideal polymkeric substance can keep double refraction after stretching, thereby gives finished film with required optical property.Can select second polymkeric substance to be used for other layer of multilayer film, make that in finished film second polymkeric substance is obviously different with the specific refractory power of first polymkeric substance on this equidirectional in the specific refractory power at least one direction.For convenience, can make film like this: adopt only two kinds different polymer materials, and in extrusion, these materials are alternately placed, to form alternative layer A, layer B, layer A, layer B etc.Yet, only alternately place two kinds different polymer materialss not necessarily.The substitute is, each in the multi-layer optical film can be made of the unique material of not using in other layer of this film or mixture layer respectively.Preferably, all had identical or similar melt temperature by the polymkeric substance of coextrusion.
The combination that had not only had suitable refractive index difference but also had two kinds of exemplary polymkeric substance of suitable interlayer adhesion comprises: (1) for employing was mainly the polarization multi-layer optical film that the method for uniaxial extension makes, this was combined as PEN/coPEN, PET/coPET, PEN/sPS, PET/sPS, PEN/Easter
TMAnd PET/Easter
TMWherein " PEN " refers to PEN, " coPEN " refers to based on the multipolymer of naphthalic acid or blend, " PET " refers to polyethylene terephthalate, " coPET " refers to based on the multipolymer of terephthalic acid or blend, " sPS " refers to syndiotactic polystyrene and derivative thereof, Easter
TMBe can be available from the polyester or the copolyester (it is believed that it contains cyclohexanedimethanol unit and terephthalate unit) of Eastman Chemical company; (2) for the polarization multi-layer optical film that makes by the processing condition of controlling biaxial stretch-formed method, this is combined as PEN/coPEN, PEN/PET, PEN/PBT, PEN/PETG and PEN/PETcoPBT, wherein " PBT " refers to polybutylene terephthalate, " PETG " referred to adopt the PET multipolymer of second kind of dibasic alcohol (being generally cyclohexanedimethanol), " PETcoPBT " refers to terephthalic acid or its ester and ethylene glycol and 1, the copolyester that the mixture of 4-butyleneglycol forms; (3) for mirror coating (comprising colored mirror coating), this is combined as PEN/PMMA, coPEN/PMMA, PET/PMMA, PEN/Ecdel
TM, PET/Ecdel
TM, PEN/sPS, PET/sPS, PEN/coPET, PEN/PETG and PEN/THV
TM, wherein " PMMA " refers to polymethylmethacrylate, Ecdel
TMBe can be available from the thermoplastic polyester or the copolyester (it is believed that it contains cyclohexanedicarboxyester ester unit, polytetramethylene ether diol unit and cyclohexanedimethanol unit) of Eastman Chemical company, THV
TMBe can be available from the fluoropolymer of 3M company.
Can in people's such as open WO95/17303 of people's such as people's such as Jonza U.S. Patent No. 5,882,774, Ouderkirk PCT and Ouderkirk the open WO99/39224 of PCT, find the further details of suitable multi-layer optical film and dependency structure thereof.Polymer multi-layer blooming and film body can contain extra play and the coating of selecting for use in order to satisfy its optics, machinery and/or chemical property.U.S. Patent No. 6,368,699 referring to people such as Gilbert.Polymeric film and film body can also contain inorganic layer, for example metal or coating of metal oxides or layer.
In a preferred embodiment; hard coat 18 is formed by the solidified coating composition; in this coating composition; have at least one univalent poly-(oxidation hexafluoro propylidene) (HFPO) monobasic of part or polynary (methyl) acryl compound and compatilizer be (for example a spot of; acrylate or many acrylate that fluoroalkyl or fluorine alkylidene group replace) be added in the hydro carbons hard coating composition, this hydro carbons hard coating composition can randomly contain inorganic particle (the hard coating of ceramic polymer).
Compatilizer of the present invention has alleviated conventional hydro carbons hard coating composition or ceramic polymer and the inconsistent problem of HFPO derivative.As the visual inspection finding, the result obtains general comparatively smooth hard coat outside surface.The add-on of compatilizer is about 2 weight %-15 weight % of the dry state solid amount of composition in the layer 18, more preferably about 2 weight %-10 weight %.The amount of compatilizer is necessary at least 3 times of amount of the monobasic of HFPO or polynary (methyl) acryl compound, is preferably at least 5 times.
The chemical formula that contains the free radical reaction compatilizer of fluoroalkyl or fluorine alkylidene group is respectively done for oneself: (R
f) Q (X)
n(X)
nQ (R
F2) Q (X)
n, R wherein
fIt is fluoroalkyl; R
F2It is the fluorine alkylidene group; Q is a linking group, and it comprises alkylidene group, arylidene, arylidene-alkylidene group or alkylidene group-arylidene, and can comprise the linking group of straight or branched, and the linking group of this straight or branched can contain heteroatoms (for example O, N and S); X be selected from (methyl) acryl ,-free radical reaction group in SH, allyl group or the vinyl; N is 1-3.Typical Q group comprises :-SO
2N (R) CH
2CH
2-,-SO
2N (CH
2CH
2)
2-,-(CH
2)
m-,-CH
2O (CH
2)
3-and-C (O) N (R) CH
2CH
2-, wherein R is H or the low alkyl group that contains 1-4 carbon atom, m is 1-6.Preferably, fluoroalkyl or fluorine alkylidene group are perfluoroalkyl or perfluorinated alkylidene.
In a preferred embodiment, compatilizer is the compatilizer that perfluoroalkyl or perfluorinated alkylidene replace, and this compatilizer contains and is connected in acrylate carbochain part, that have at least five carbon atoms, and this compatilizer contains the fluorine of at least 30 weight %.
The compatilizer requirement when satisfying the above-mentioned composition that is used for hard coat 18, that the preferred fluoroalkyl of a class or fluorine alkylidene group replace is the acrylate compatilizer that perfluoro butyl replaces.Satisfy above-mentioned requirements and can be used for acrylate compatilizer that the exemplary and nonrestrictive perfluoro butyl among the present invention replaces and comprise in the following compounds one or more, described compound is:
C
4F
9SO
2N(CH
3)CH
2CH
2OC(O)CH＝CH
2、
C
4F
9SO
2N (CH
2CH
2OC (O) CH=CH
2)
2, or
C
4F
9SO
2N(CH
3)CH
2CH
2OC(O)C(CH
3)＝CH
2。
Other the nonrestrictive example that can be used for the compatilizer that the preferred fluoroalkyl in the composition of hard coat 18 replaces comprises: vinylformic acid 1H, 1H, 2H, 2H-perfluor ester in the last of the ten Heavenly stems can derive from the Lancaster Synthesis company that is positioned at Windham city, New Hampshire.People's such as Hulme-Lowe U.S. Patent No. 4; 968; 116 and people's such as Babirad U.S. Patent No. 5; mention multiple other (methyl) acryl compound that has perfluoroalkyl moieties of the composition that also can be used for hard coat 18 239,026 (comprising methacrylic acid perfluor cyclohexyl methyl esters).Other fluorochemicals (methyl) acrylate that satisfies above-mentioned requirements and can be used comprises (for example): diacrylate 2,2,3,3,4,4,5,5-octafluorohexane diol ester and vinylformic acid ω-hydrogen 2,2,3,3,4,4,5,5-octafluoro pentyl ester (H-C
4F
8-CH
2O-C (O)-CH=CH
2).People's such as Kang U.S. Patent No. 6,238,798 has been described other fluorochemicals (methyl) acrylate that can use separately or use as mixture.
In another preferred embodiment; in coating composition of the present invention; (HFPO) one or more monobasics of part or polynary (methyl) acryl compound and compatilizer (for example, fluoroalkyl or fluorine alkylidene group replace mercaptan or multi-thiol) are added in the ceramic polymer hard coating composition will to have at least one univalent poly-(oxidation hexafluoro propylidene).The nonrestrictive example of this compatilizer comprises one or more in the following compounds, and described compound is: C
4F
9SO
2N (CH
3) CH
2CH
2OC (O) CH
2SH, C
4F
9SO
2N (CH
3) CH
2CH
2OC (O) CH
2CH
2SH, C
4F
9SO
2N (CH
3) CH
2CH
2SH and C
4F
9SO
2N (CH
3) CH (OC (O) CH
2SH) CH
2OC (O) CH
2SH.
As used in the example part, except as otherwise noted, otherwise " HFPO-" all is meant methyl esters F (CF (CF
3) CF
2O)
aCF (CF
3) C (O) OCH
3End group F (CF (CF
3) CF
2O)
aCF (CF
3)-, wherein " a " average out to is about 6.8, and the molecular-weight average of this methyl esters is 1, the 211g/ mole, and can be prepared and adopt fractionating process to purify according to 3,250,808 reported method of U.S. Patent No. of people such as Moore.
Have at least one univalent poly-(oxidation hexafluoro propylidene) (HFPO) monobasic or the form that polynary (methyl) acryl compound is preferably the monobasic acrylate, the more preferably form of multicomponent methacrylate of part.The chemical formula of these materials is: R
FpeQ (X)
n, R wherein
FpeIt is the residue of univalent HFPO part; Q is a linking group, comprises alkylidene group, arylidene, arylidene-alkylidene group or alkylidene group-arylidene, and can comprise the linking group of straight or branched, and the linking group of this straight or branched can contain heteroatoms (for example O, N and S); X be selected from (methyl) acryl ,-free radical reaction group in SH, allyl group or the vinyl; N is 1-3.During n=1, typical Q group comprises :-(CH
2)
m-;-CH
2O (CH
2)
3-;-C (O) N (R) CH
2CH
2-; Wherein R is H or the low alkyl group that contains 1-4 carbon atom, and m is 1-6.
Have at least one univalent poly-(oxidation hexafluoro propylidene) (HFPO) class polynary (methyl) acryl compound of part comprise: U.S. Provisional Application No.60/569; 351 (file number 59795US002; the name be called " Fluoropolyether Polyacryl Compounds ", the applying date is on May 7th, 2004) described in compound.
Have at least one univalent poly-(oxidation hexafluoro propylidene) (HFPO) other monobasic or polynary (methyl) acryl compound of part comprise: U. S. application No.10/841; 792 (file numbers 59644; name is called " Polymerizable Copositions; Methods Of Making TheSame; And Composite Articles Therefrom "; the applying date is on May 7th, 2004) described in compound, this compound is the Michael addition adducts of HFPO amino derivative and many acrylate.
The many acrylate of HFPO-can be multiple different form.Following Table I comprises three kinds of many acrylate of HFPO-that preferably can be used among the present invention.In another preferred embodiment, the HFPO derivative has following structure: F-(CF (CF
3) CF
2O)
aCFC (=O) NHCH
2CH
2OAcr, wherein Acr represents (methyl) acryl group.
The add-on of HFPO derivative is about 0.01 weight %-1.0 weight % of the dry state total weight of solids of composition in the layer 18.More preferably, the add-on of HFPO derivative is about 0.06 weight %-0.75 weight % of the dry state total weight of solids of composition in the layer 18, most preferably, the add-on of HFPO derivative is about 0.10 weight %-0.24 weight % of the dry state total weight of solids of composition in the layer 18.
In any one preferred embodiment, the hydro carbons hard coating composition that is used for the composition of layer 18 is the known hydrocarbon materials of those of ordinary skill in the optical field.Most preferably, this hydrocarbon materials is the hard coating of esters of acrylic acid.A kind of preferred hard coating that is used for the present invention is based on the hard coating of PETA (tetramethylolmethane three/tetraacrylate).
The linking agent that can be used for hard coating composition can also comprise (for example) polynary (methyl) acryl monomer, wherein said polynary (methyl) acryl monomer is selected from: the compound that (a) contains two (methyl) acryl, for example, diacrylate 1, the 3-butanediol ester, diacrylate 1, the 4-butanediol ester, diacrylate 1,6-hexylene glycol ester, single vinylformic acid monomethyl vinylformic acid 1,6-hexylene glycol ester, ethylene glycol diacrylate, the alkoxy fatty alcohols diacrylate, the alkoxylate cyclohexane dimethanol diacrylate, the alkoxylate hexanediyl ester, the alkoxylate neopentylglycol diacrylate, caprolactone modification neopentyl glycol hydroxyl trimethylacetic acid ester diacrylate (caprolactone modified neopentylglycol hydroxypivalatediacrylate), caprolactone modification neopentyl glycol hydroxyl trimethylacetic acid ester diacrylate, cyclohexane dimethanol diacrylate, the diacrylate binaryglycol ester, dipropylene glycol diacrylate, ethoxylation (10) bisphenol a diacrylate, ethoxylation (3) bisphenol a diacrylate, ethoxylation (30) bisphenol a diacrylate, ethoxylation (4) bisphenol a diacrylate, hydroxy pivalin aldehyde modification trimethylolpropane diacrylate, diacrylic acid pentyl diol ester, polyoxyethylene glycol (200) diacrylate, polyoxyethylene glycol (400) diacrylate, polyoxyethylene glycol (600) diacrylate, ethoxylated neopentylglycol diacrylate, diacrylate Tetraglycol 99 ester, diacrylate tristane diformazan alcohol ester, Triethylene glycol diacrylate and tri (propylene glycol) diacrylate; (b) contain the compound of three (methyl) acryl, for example, three vinylformic acid glyceryl ester, Viscoat 295, the ethoxylation triacrylate (for example, ethoxylation (3) Viscoat 295, ethoxylation (6) Viscoat 295, ethoxylation (9) Viscoat 295, ethoxylation (20) Viscoat 295), pentaerythritol triacrylate, propoxylation triacrylate (for example, propoxylation (3) glycerol tri-acrylate, propoxylation (5.5) glycerol tri-acrylate, propoxylation (3) Viscoat 295, propoxylation (6) Viscoat 295), Viscoat 295 and ethoxylation cyamelide triacrylate (tris (2-hydroxyethyl) isocyanurate triacrylate); (c) contain the compound of higher functionality (methyl) acryl, for example, two (TriMethylolPropane(TMP)) tetraacrylate, Dipentaerythritol five acrylate, ethoxylation (4) tetramethylol methane tetraacrylate, tetramethylol methane tetraacrylate and caprolactone modification dipentaerythritol acrylate; (d) compound of oligomeric (methyl) acryl, such as for example, urethane acrylate, polyester acrylate and epoxy acrylate; The similar thing of polynary acrylamide of above-claimed cpd; And combination.This compounds can derive from supplier widely, such as for example, be positioned at the Sartomer company in Pennsylvania, America Exton city, be positioned at the UCB Chemicals company in State of Georgia, US Smyrna city, and the Aldrich Chemical company that is positioned at Wisconsin, USA Milwaukee city.Other available (methyl) esters of acrylic acid material comprises polynary (methyl) acrylate of containing glycolylurea part (for example, as United States Patent (USP) 4,262, described in 072 people such as () Wendling).
In another embodiment, granular matting agent is introduced in the composition of layer 18, to give layer the 18 anti-photosensitiveness of dazzling.Granular matting agent can also prevent the reflectivity that is caused by the interference between the hard coat that adjoins to be reduced and the uneven phenomenon of color and luster.Granular matting agent should be preferably transparent and its transmittance values for greater than about 90% granular matting agent.Can for select for use be or in addition be, its haze value be preferably less than about 5%, more preferably less than about 2%, most preferably be less than about 1%.
For example, U.S. Patent No. 6,693, but 746 described and matting agent is introduced in the hard coat it have the exemplary system that different hard coating is formed.In addition, exemplary matt film can be available from the Kimoto Tech company that is positioned at State of Georgia, US Cedartown city, and its commodity are called " N4D2A ".
According to the difference of the thickness of layer 18, the add-on of granular matting agent can be about 0.5%-10% of the solid amount in the composition, preferred add-on be in the composition solid amount about 2%.Anti-thickness of dazzling the layer 18 of light is preferably the 0.5-10 micron, 0.8-7 micron more preferably, and its thickness range is identical with the thickness range of glossiness hard coat usually.
The median size of granular matting agent has the minimum value of predesignating and the maximum value of the thickness that depends in part on layer.Yet generally speaking, median size can not reach competent less than 1.0 microns and anti-dazzle the light path degree and be left out; Median size is greater than 10.0 microns sharpness that then can reduce transmission image.Therefore, its median size (the number average bead diameter value of being measured according to the Coulter method) is preferably about 1.0-10.0 micron, 1.7-3.5 micron more preferably.
Inorganic particle or resin particle as granular matting agent comprise (for example): amorphous silica particles, TiO
2Particle, Al
2O
3Particle, cross-linked acrylic acid base polymer particle (for example particle that makes by crosslinked polymethylmethacrylaparticles), crosslinked polystyrene particle, melamine resin particle, benzoguanamine resin particle and cross linking polysiloxane particle.In process of production, consider that particle is at anti-dispersion stabilization and sedimentation stability of dazzling in the coating compound that photosphere and/or hard coat use, so more preferably resin particle (especially preferably using crosslinked polystyrene particle), this is because resin particle has strong affinity to binder material, and its proportion is little.
About the shape of granular matting agent, can use spheroidal particle and unbodied particle.Yet in order to obtain the anti-photosensitiveness of dazzling of homogeneous, spheroidal particle is preferred.Two or more particulate materials can also be used in combination.
The hydro carbons hard coating composition of layer 18 comprises the inorganic particle through surface modification, and this particle has strengthened the physical strength of gained coating, therefore is more prone to this hard coating composition is called ceramic polymer composition.The colloid silica of example of this particulate for reacting with following material: the silane coupling agent that methacryloyl replaces (A-174 for example; can derive from Natrochem company), other dispersing auxiliary (for example N,N-DMAA) and multiple other additive (stablizer, initiator etc.).
People's such as Kang U.S. Patent No. 6,238,798 has also been described the object lesson that can be used for the ceramic polymer composition of the preferred embodiments of the invention.According to United States Patent (USP) 5,677,050 the 10th hurdle 25-39 is capable and embodiment 1 is described, makes a kind of so hard coating of ceramic polymer.
Gained coating 18 in any one preferred embodiment all can make the performance of goods 10 be improved.Compare with not coated Optical devices or with the Optical devices of conventional hard applying coating, these performances that are improved comprise: the optical property that is improved (comprise and reduce the light transmission of dazzling light and being improved), the bearing dirty property that is improved, the ink repellent that is improved and pollution resistance.
In order to promote to solidify, can also contain at least a free radical thermal initiator and/or light trigger according to polymerisable compound of the present invention.Usually, if having this initiator and/or light trigger, then its content is the about 10 weight % less than the polymerisable compound gross weight, is more typically the about 5 weight % less than the polymerisable compound gross weight.The radically curing technology is well-known in the art, and it comprises (for example): thermal curing methods and the radiation-curing method such as electron beam or ultraviolet radiation.Can be at for example U.S. Patent No. 4,654,233 (people such as Grant), No.4,855,184 (people such as Klun) and No.6 among 224,949 (people such as Wright), find the further details about free radical thermopolymerization and light polymerization technique.
Available free radical thermal initiator comprises (for example): azo, superoxide, persulphate and redox initiator, and combination.
The available free radical photo-initiation comprises (for example): those in the known ultraviolet curing that can be used for acrylic polymer.This class initiator comprises: benzophenone and derivative thereof; Bitter almond oil camphor, Alpha-Methyl bitter almond oil camphor, α-phenyl bitter almond oil camphor, α-allyl group bitter almond oil camphor and α-benzyl bitter almond oil camphor; Benzoin ether, for example, benzoin dimethylether dimethyl ketal (can be available from the Ciba SpecialtyChemicals company that is positioned at New York, United States Tarrytown city, commodity are called " IRGACURE 651 "), benzoin methyl ether, Benzoin ethyl ether and st-yrax n-butyl ether; Methyl phenyl ketone and derivative thereof, for example, 2-hydroxy-2-methyl-1-phenyl-1-acetone (can be available from Ciba Specialty Chemicals company, commodity are called " DAROCUR 1173 ") and 1-hydroxycyclohexylphenylketone (also can be available from CibaSpecialty Chemicals company, commodity are called " IRGACURE 184 "); 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-(4-morpholinyl)-1-acetone (also can be, commodity are called " IRGACURE 907 ") available from Ciba SpecialtyChemicals company; 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl) phenyl]-1-butanone (also can be, commodity are called " IRGACURE 369 ") available from Ciba Specialty Chemicals company; The aromatic series ketone, for example, benzophenone and derivative thereof, anthraquinone and derivative thereof; Salt, for example, diazonium salt, salt compounded of iodine, sulfonium salt; Titanium complex for example, also can be called the titanium complex of " CGI 784DC " available from the commodity of Ciba Specialty Chemicals company; Halogenated methyl oil of mirbane; And monoacyl phosphine and two acylphosphanes; for example, the compound of by name " IRGACURE 1700 ", " IRGACURE 1800 " of commodity, " IRGACURE 1850 ", " IRGACURE 819 ", " IRGACURE 2005 ", " IRGACURE 2010 ", " IRGACURE 2020 " and " DAROCUR 4265 " (all can available from Ciba Specialty Chemicals company).Can use the combination of two or more light triggers.Furthermore, one or more light triggers (for example, " IRGACURE 369 ") and sensitizer (for example, the 2-isopropyl thioxanthone can be available from the First Chemical company that is positioned at Mississippi, America Pascagoula city) can be used together.
Can adopt comprise dip coating, forward rolling method and inverse roller coating method, the whole bag of tricks that the excellent coating method that winds the line (wire wcund rod coating) and mould are coated with method, coating 18 is coated on the base material 16.Mould is coated with machine and comprises: knife coater, gap coating machine, sliding type coating machine, fluid bearing coating machine (fluid bearing coater), slip heavy curtain coating machine, following stamping die heavy curtain coating machine (drop die curtain coater) and extrusion coated machine etc.Document (for example) Modern Coating and Drying Technology (Edward Cohen and Edgar Gutoff work, publish in 1992 by the VCH press that is positioned at the USA New York, ISBN3-527-28246-7) and Coating and Drying Defects:TroubleshootingOperating Problems (Gutoff and Cohen work, publish ISBN 0-471-59810-0 by the WileyInterscience that is positioned at the USA New York) in described polytype mould and be coated with machine.
Mould is coated with machine and typically refers to the equipment that adopts first module and second module to form manifold cavity (manifold die) and die slot.Flow through under pressure manifold cavity and flow out die slot of coating liquid forms and is coated with strip.Applying coating can be become individual layer or be applied as two or more laminations.Although base material is that the form of continuous tablet is comparatively convenient usually, base material also can be a series of single sheet.Other method that can Gong select for use that forms hard coat on the major surfaces of base material (for example, blooming) comprises: the tackiness agent (for example pressure sensitive adhesive, radiation-curable tackiness agent) of filming and be bonded on described the filming is carried out heat lamination.In a kind of concrete grammar, the film that in the following manner back side is had the thermoplastic adhesive layer is thermally bonded on the base material (for example, lens): the inner chamber that this film is placed on molding die; Close die; The injection melt polymer material makes it be full of dies cavity (thus optical element is carried out molded, by means of tackiness agent it with protective film is engaged simultaneously) substantially; Cool off described melt polymer material; Optical element is taken out from molding die.
Effect for the above-mentioned resulting hard coating formulation of each preferred embodiment of the present invention of identity basis, be mixed with hard coating sample with given composition, and it is coated on the PET base material, with this sample with do not possess the hard coating formulation that all must composition and compare.Visual inspection coating, and the ink repellent of testing coating, weather resistance and surface irregularity.Experimental technique and the experimental result of listing in the form are as described below:
I. experimental technique
A: composition
Except as otherwise noted, otherwise in each example, abbreviation " HFPO-" all is meant the wherein end group F (CF (CF of a average out to about 6.8
3) CF
2O)
aCF (CF
3)-.
F (CF (CF
3) CF
2O)
aCF (CF
3) COOCH
3(HFPO-C (O) OCH
3), wherein a average out to is about 6.8, and molecular-weight average is 1, the 211g/ mole, this compound can be according to U.S. Patent No. 3,250, and 808 (people such as Moore) reported method is prepared and adopts fractionating process to purify.
Viscoat 295 (" TMPTA ") derives from the Sartomer company that is positioned at Pennsylvania, America Exton city, and commodity " SR351 " by name (AC-1).
Tetramethylol methane tetraacrylate (" PETA ") derives from Sartomer company, and commodity are called " SR295 ".
Amine: triethylamine, diisopropylethylamine, N-methyl isophthalic acid, 3-propylene diamine, 2-amino-2-ethyl-1, ammediol, 2-amino-2-methyl-1, ammediol, 2-amino-1, ammediol, 2-monoethanolamine, 2-(2-aminoethyl amino) ethanol and 3-amino-1, the 2-propylene glycol all derives from the Sigma-Aldrich company that is positioned at Wisconsin, USA Milwaukee city.
Acrylate chloride derives from the Sigma-Aldrich company that is positioned at Wisconsin, USA Milwaukee city.
Ultraviolet initiator 1-hydroxycyclohexylphenylketone derives from the Ciba Specialty Products company that is positioned at New York, United States Tarrytown city, and commodity are called " Irgacure 184 ".
Employed light trigger 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholine third-1-ketone derives from the Ciba Specialty Products company that is positioned at New York, United States Tarrytown city, and commodity are called " Irgacure 907 ".
B: preparation experiment material
1. prepare simple function perfluoropolyether acrylate (MP-1)
HFPO-C(O)N(H)CH
2CH
2OC(O)CH＝CH
2(HFPO-AEA)
A. prepare starting raw material HFPO-C (O)-NH-CH
2CH
2-OH (being HFPO-AE-OH)
HFPO-C (O) OCH with 50.0 grams
3(that is MW=1211g/ mole) is placed in the round-bottomed flask of 200ml.Use the nitrogen purging flask, and flask is placed in the water-bath, make its temperature remain 50 ℃ or lower.In this flask, add 3.0 gram (0.045 mole) 2-monoethanolamines.With reaction mixture stir about 1 hour, after this, the infrared spectra of reaction mixture showed: 1790cm
-1The methyl esters bands of a spectrum at place thoroughly disappear and at 1710cm
-1There is the strong flexible peak of the carbonyl of acid amides in the place.(MTBE) is added in the reaction mixture with the 200ml methyl tertiary butyl ether, and water/HCl (about 5%) is with organic extractant phase twice, to remove unreacted amine and methyl alcohol.Use MgSO
4Dry MTBE layer.Under reduced pressure, remove MTBE, obtain transparent viscous liquid.Proton (
1H) nuclear magnetic resonance spectrum (NMR) and infrared spectra (IR) confirm to have formed title compound.
B. by starting raw material preparation (MP-1)
In three mouthfuls of round-bottomed flasks (this flask is equipped with mechanical stirrer, reflux exchanger, feed hopper and hose nipple, and this hose nipple links to each other with the nitrogen source of the gas), HFPO-AE-OH (600g) is mixed with ethyl acetate (600g) and triethylamine (57.9g).Under nitrogen atmosphere, stir the mixture, and be heated to 40 ℃.In about 30 minutes, acrylate chloride (51.75g derives from Aldrich Chemical company) is added drop-wise to the flask from feed hopper.Mixture is spent the night 40 ℃ of stirrings.Then, make mixture be cooled to room temperature, dilute this mixture with the 2N HCl aqueous solution of 300ml, and it is moved to separating funnel.Remove the waterbearing stratum, use the 2N hcl as extraction agent ethyl acetate layer of another part 300ml again.Then, with the sodium bicarbonate aqueous solution extracted organic phase of 5 weight % once, organic phase is separated, use dried over mgso, and with its filtration.Remove volatile component with rotary evaporator, obtain 596g product (93% productive rate).Proton (
1H) NMR and IR spectrum confirm to have formed title compound.
2. prepare simple function PFPE methacrylic ester (MP-2)
By being similar to U.S. Patent Application Publication No.2004-0077775 (file number 57823, its name is called " Fluorochemical Composition Comprising aFluorinated Polymer and Treatment of a Fibrous Substrate Therewith ", and the applying date is on May 24th, 2002) describedly be used to synthesize (HFPO)
kThe method of-methacrylic ester is with F (CF (CF
3) CF
2O)
aCF (CF
3) C (O) NHCH
2CH
2OH (a=6.8, molecular weight are 1344) replaces F (CF (CF
3) CF
2O)
aCF (CF
3) C (O) NHCH
2CH
2OH (a=10.5) makes HFPO-C (O) N (H) CH
2CH
2OC (O) C (CH
3)=CH
2(HFPO-AEMA) (MP-2).
3. prepare simple function perfluoropolyether acrylate (MP-3)
HFPO-C(O)N(H)(CH
2CH
2O)
3C(O)CH＝CH
2
A. prepare starting raw material HFPO-C (O) N (H) (CH
2CH
2O)
3H
With HFPO-C (O) N (H) C (CH described in the preparation that is similar to FC-1 below
2OH)
2CH
2CH
3The preparation method, with 100g (0.0826 mole) HFPO-C (O) CH
3With the pure H of 12.30g (0.0825 mole)
2N (CH
2CH
2O)
3H reacts, and obtains required product.
B. by starting raw material preparation (MP-3)
To be similar to HFPO-C (O) N (H) C (CH
2OC (O) CH=CH
2)
2CH
2CH
3The preparation method, with 25g (0.01822 mole) starting raw material HFPO-C (O) N (H) (CH
2CH
2O)
3H and 1.98g (0.02187 mole) acrylate chloride and 2.83g (0.02187 mole) diisopropylethylamine react in the 50g methyl tertiary butyl ether, after reaction is finished and passed through chromatographic separation, obtain required product, and this product is transparent liquid.
4. prepare the multifunctional perfluoro-polyether acrylate
HFPO-C(O)N(H)C(CH
2OC(O)CH＝CH
2)
2CH
2CH
3(FC-1)
A. prepare starting raw material HFPO-C (O) N (H) C (CH
2OH)
2CH
2CH
3
In the there-necked flask (this flask is equipped with stirring rod and reflux exchanger) of 500ml, add the H of 11.91g (0.1 mole)
2NC (CH
2OH)
2CH
2CH
3THF with 60g.Then, bathing under the about 85 ℃ condition of temperature, in about 80 minutes, add 121.1g (0.1 mole) HFPO-C (O) OCH through dropping funnel
3At first, reactant is muddy, but after about 1 hour of reaction, the reactant bleach.After reinforced the finishing, shut heating bath, and make reaction cooling 3 days.Under 55 ℃, under the vacuum condition that produces by suction unit, concentrate above-mentioned materials, obtain the slurry of 130.03g light colour.NMR analysis revealed, this product are to show that structure I: structure I I is 87: 13 a mixture down.
B. by starting raw material preparation (FC-1)
In three mouthfuls of round-bottomed flasks (this flask is equipped with top formula agitator) of 250ml, add 65g (0.05 mole) HFPO-C (O) N (H) C (CH
2OH)
2CH
2CH
3(product mixtures of above generation), 12.65g (0.125 mole) triethylamine and 65g ethyl acetate.Under the room temperature,, in 12 minutes 11.31g (0.125 mole) acrylate chloride is added in the flask with the pressure equilibrium dropping funnel, temperature of reaction rises to 40 ℃ of top temperatures from 25 ℃.Use this dropping funnel of 5g ethyl acetate rinse again, and it is joined in the reaction flask, flask is inserted reacted again in 40 ℃ of baths 2 hours 10 minutes then.Subsequently, use 65g 2% aqueous sulfuric acid, 65g 2% sodium bicarbonate aqueous solution and 65g water washing organic layer successively; Then, use anhydrous magnesium sulfate drying, filter, handle this organic layer with 16mg methoxyl group quinhydrones (MEHQ); Then, concentrate down at 45 ℃, obtain the 62.8g crude product with rotary evaporator.Then, use ethyl acetate: heptane be 25: 75 mixture as elutriant, go up this material of 35g carried out chromatographic separation at 600ml silica gel (SX0143U-3, Grade 62, the 60-200 order, EM Science company produces).The volume of two initial fractions is 250ml, and the volume of all the other fractions is 125ml.4-10 mixes with fraction, and 8mg MEHQ is added in this fraction mixture, removes down at 55 ℃ with rotary evaporator then and desolvates, and obtains the 25.36g product, and NMR analysis revealed, products therefrom are structure III: structure I V is 88: 12 a mixture.
5. prepare the multifunctional perfluoro-polyether acrylate
HFPO-C(O)N(H)C(CH
2OC(O)CH＝CH
2)
2H(FC-2)
A. prepare starting raw material HFPO-C (O) N (H) C (CH
2OH)
2H
Employing is similar to HFPO-C (O) N (H) C (CH
2OH)
2CH
2CH
3The preparation method, make 106.74g (0.088 mole) HFPO-C (O) CH
3And 8.03g (0.088 mole) 2-amino-1, ammediol reacts in 51g THF, obtains amide diol: the ester amino alcohol is 93: 7 a product.
B. by starting raw material preparation (FC-2)
Employing is similar to HFPO-C (O) N (H) C (CH
2OC (O) CH=CH
2)
2CH
2CH
3The preparation method, make 50g (0.3936 mole) starting raw material HFPO-C (O) N (H) C (CH
2OH)
2H and 8.55g (0.0945 mole) acrylate chloride and 9.56g (0.946 mole) triethylamine react in the 100g ethyl acetate, and after reaction was finished and passed through chromatographic separation, obtain diacrylate: the acrylamide-acrylicacid ester was 93: 7 a mixture.
6. prepare multifunctional perfluoro-polyether acrylate (FC-3)
HFPO-C(O)N(H)CH
2CH(OC(O)CH＝CH
2)CH
2OC(O)CH＝CH
2
A. prepare starting raw material HFPO-C (O) N (H) CH
2CH (OH) CH
2OH
Employing is similar to HFPO-C (O) N (H) C (CH
2OH)
2CH
2CH
3The preparation method, make 121.1g (0.100 mole) HFPO-C (O) CH
3And 9.11g (0.100 mole) 1-amino-2, ammediol reacts in 55.7g THF, obtains amide diol: the ester amino alcohol is 86: 14 a product.
B. by starting raw material preparation (FC-3)
Employing is similar to HFPO-C (O) N (H) C (CH
2OC (O) CH=CH
2)
2CH
2CH
3The preparation method, make 63.5g (0.050 mole) HFPO-C (O) N (H) CH
2CH (OH) CH
2OH and 11.26g (0.0945 mole) acrylate chloride and 9.56g (0.946 mole) triethylamine react in the 100g ethyl acetate, and after reaction was finished and passed through chromatographic separation, obtain diacrylate: the acrylamide-acrylicacid ester was 86: 14 a mixture.
7. preparation perfluoropolyether acrylate
HFPO-C(O)N(H)CH
2CH
2CH
2N(CH
2CH
2OC(O)CH＝CH
2)
2(FC-4)
A. prepare the multifunctional HFPO-C of starting raw material (O) N (H) CH
2CH
2CH
2N (CH
2CH
2OH)
2
To be similar to HFPO-C (O) N (H) C (CH
2OH)
2CH
2CH
3The preparation method, make 100g (0.0826 mole) HFPO-C (O) CH
3And the pure H of 13.40g (0.0826 mole)
2NCH
2CH
2CH
2N (CH
2CH
2OH)
2130 ℃ of reactions down, obtain required product, this product is dense yellow liquid.
B. by starting raw material preparation (FC-4)
To be similar to HFPO-C (O) N (H) C (CH
2OC (O) CH=CH
2)
2CH
2CH
3The preparation method, make 50g (0.03728 mole) starting raw material HFPO-C (O) N (H) CH
2CH
2CH
2N (CH
2CH
2OH)
2React in 68g methyl-tertbutyl ether with 7.42g (0.08202 mole) acrylate chloride and 10.60g (0.08202 mole) diisopropylethylamine, after reaction is finished and passed through chromatographic separation, obtain required product, this product is transparent liquid.
8. prepare multifunctional perfluoro-polyether acrylate (FC-5)
HFPO-C(O)N(H)CH
2CHN(C(O)CH＝CH
2)CH
2CH
2OC(O)CH＝CH
2
A. prepare starting raw material HFPO-C (O) N (H) CH
2CHNHCH
2CH
2OH
With 50.0g (0.413 mole) HFPO-C (O) OCH
3Join in the round-bottomed flask of 100ml, and in oil bath, be heated to 40 ℃.From oil bath, take out flask, and 4.30g (0.413 mole) 2-(2-aminoethyl amino) ethanol is joined in the flask.Material in the flask is rotated together, and in 65 ℃ oil bath, heat 3 hours while stirring, under the pressure condition that produces by suction unit, obtain product 65 ℃ of following concentrating then with rotary evaporator.
B. by starting raw material preparation (FC-5)
To be similar to HFPO-C (O) N (H) C (CH
2OC (O) CH=CH
2)
2CH
2CH
3The preparation method, with 64.15g (0.050 mole) HFPO-C (O) N (H) CH
2CHNHCH
2CH
2OH and 11.26g (0.125 mole) acrylate chloride and 12.65g (0.125 mole) triethylamine react in the 65g ethyl acetate, after reaction is finished and passed through chromatographic separation, obtain required product.
9. the preparation mol ratio is about 1: 1 starting raw material HFPO-C (=O) NHCH
2CH
2CH
2NHCH
3Affixture with TMPTA.(FC-6)
A. prepare starting raw material HFPO-C (=O) NHCH
2CH
2CH
2NHCH
3
At room temperature in 1 liter round-bottomed flask, add 291.24g (0.2405 mole) HFPOC (O) OCH
3And 21.2g (0.2405 mole) N-methyl isophthalic acid, the 3-propylene diamine obtains muddy solution.Rotate flask, the temperature of mixture is elevated to 45 ℃, obtains water white liquid, with it 55 ℃ of following heated overnight.Then this product is placed on the rotary evaporator, under 75 ℃, the condition of 28 inch of mercury vacuum, remove methyl alcohol, obtain the light yellow liquid of 301.88g viscosity, nominal molecular weight=1267.15g/ mole.
B. be about 1: 1 HFPO-C (=O) NHCH from mol ratio
2CH
2CH
2NHCH
3Affixture preparation (FC-6) with TMPTA.(FC-6)
In the round-bottomed flask of 250mL, add 4.48g (15.13 mmole) TMPTA, 4.45g tetrahydrofuran (THF) (THF) and 1.6mg thiodiphenylamine, and place 55 ℃ oil bath to heat in flask.Then, in the bottle of 100mL, with 20g (15.78 mmole) HFPO-C (=(O) NHCH
2CH
2CH
2NHCH
3Be dissolved among the 32g THF.This solution is placed in the dropping funnel of 60mL, this dropping funnel has pressure balanced side arm.Clean this bottle with about 3ml THF, and this THF is also added in the dropping funnel, under air atmosphere, the material in the funnel was joined in the mixture of TMPTA/THF/ thiodiphenylamine in 38 minutes.Reactant is muddy at first, but becomes transparent after about 30 minutes.During after dropwise operation is finished 20 minutes, with reaction flask be placed under 45-55 ℃, vacuum tightness is on the rotary evaporator of 28 inches of mercury, obtains the transparent viscosity yellow liquid of 24.38g, use
1H NMR and
13C NMR and HPLC/ mass spectrum characterize this liquid.Measure as the HPLC/ mass spectrum, the products distribution of representing with approximate molecular fraction of gained material is: 20% TMPTA, 40% it is believed that monoadduct with following chemical formula (5) and 40% diadduct.
10. fluoroalkyl acrylate and fluorine alkylidene group acrylate
Following material can derive from specified supplier, and described material is: methacrylic acid 2,2,2-trifluoro ethyl ester, diacrylate 2,2,3,3,4,4,5,5-octafluorohexane diol ester and vinylformic acid 1H, 1H-2,2,3,3,4,4,4-seven fluorine butyl esters all can derive from the Sigma-Aldrich company that is positioned at Wisconsin, USA Milwaukee city; Vinylformic acid ω-hydrogen 2,2,3,3,4,4,5,5-octafluoro pentyl ester can derive from the OakwoodProducts company that is positioned at South Carolina, United States West Columbia city.Can be of embodiment 1 in people's such as Savu the U.S. Patent No. 5,148,511, make methacrylic acid perfluor cyclohexyl methyl esters.
The method of embodiment 2A and 2B makes FBSEA (C among the employing WO01/30873A
4F
9SO
2N (CH
3) CH
2CH
2OC (O) CH=CH
2).
The method of embodiment 2A and 2B among the employing WO01/30873A, difference is: with methacrylic acid substitution vinylformic acid, make FBSEMA (C
4F
9SO
2N (CH
3) CH
2CH
2OC (O) C (CH
3)=CH
2).
Can be as U.S. Patent No. 3,734, the 5th hurdle the 31st row and Fig. 9 in 962 (1973) are described, make FBSEE (C
4F
9SO
2N (C
2H
4OH)
2), this compound is a kind of fluorochemicals dibasic alcohol.
The capable described method of the 25th hurdle 49-63 in people's such as employing Kang the U.S. Patent No. 6,238,798 makes FBSAA (C
4F
9SO
2N (CH
2CH
2OC (O) CH=CH
2)
2).
11. preparation C
4F
9SO
2N (CH
3) C
2H
4OC (O) CH
2SH:(FC-SH)
In three mouthfuls of round-bottomed flasks of 500ml, add 16.86gC
4F
9SO
2N (CH
3) CH
2CH
2OH (MW=357; 47.22 mmole; Be the A of embodiment 2 among the WO01/30873), 4.35g HSCH
2CO
2H (MW=92.12,47.22 mmoles; Derive from Sigma Aldrich company), two catalyzer CF
3SO
3H and 120ml toluene.Under the stirring action of mechanical stirrer, with this mixture reflux 8 hours under 115-120 ℃, nitrogen atmosphere.Remove moisture by component distillation.Fourier transform infrared spectroscopy (FTIR) analysis revealed has formed ester.Adopt rotary evaporator to remove toluene, obtain the 21.35g solid.
C. experiment
Capable and embodiment 1 is described as the 10th hurdle 25-39 of people's such as Bilkaldi U.S. Patent No. 5,677,050, make the hard coating of ceramic polymer (" HC-1 ") that uses in the example of the present invention.
The coating solution in the example shown in the Table I of the about 40 solid % of preparation and the Table II in Virahol, adopt the coiling rod No. 9, this solution is coated on Melinex 618 polyethylene terephthalates (PET) film (deriving from the E.I.DuPont de Nemours and Company company that is positioned at Delaware, USA Wilmington city) of 5 mils with about 6 microns dry state thickness.Use the ceramic polymer hard coating resin of HC-1 as routine.With coating in 80 ℃ baking oven dry about 2 minutes, place it in subsequently on the conveying belt, with the H type bulb of 500 watts of Fusion under nitrogen atmosphere, this coating is implemented ultraviolet radiation with the speed of 35 feet per minute clocks, thereby with coating curing on the PET base material.Numerical value in all forms and the example all refers to the solid % of every kind of composition in the dry coating.
In Table I and II, adopt King
TMMarking pen, the material in the his-and-hers watches carries out the ink repellent evaluation, wherein, with razor blade the top of marking pen is cut and to have a certain degree, and obtaining the mark width of broad, and streaks the upper surface of hard coat with the speed of about 6 inch per seconds with marking pen.Make ink dry on coatingsurface, by 1 (ink repellent is the strongest) to the standard of 5 (ink repellent is the most weak) with the ink repellent grading.This operation repeats 3 times, writes down its average.
Contact angle: before the contact angle of testing coating and water, in IPA, stir coating cleaning 1 minute earlier with hand.(this deionized water passes through filtration system filters to adopt deionized water, wherein said filtering system derives from the Millipore company that is positioned at Massachusetts, United States Billerica city), on video contact angle analyser, test, this video contact angle analyser can be available from the AST Products company that is positioned at Massachusetts, United States Billerica city, and production number is VCA-2500XE.The numerical value of record is the mean value of test data that at least three samples are measured in its left and right sides separately, and this value is shown among Table IV and the V.During the tested static contact angle, the volume of every sample is 5 μ L; When test advancing contact angle and receding angle, the volume of every sample is 1-3 μ L.
Planarization: in some listed hereinafter forms, the planarization of coated dry state film is carried out visual inspection.Although the measuring method of visual inspection planarization is a kind of subjective judgement, but according to purpose of the present invention, flatted membrane is considered to such top layer: when with multiple possible this coatingsurface of angle visual observations, this top layer is continuous substantially, and can't see defective in its reflected light.Usually, visual observations is to realize by the following method: watch the light of light source from the coatingsurface reflection to become about 60 ° angle with vertical direction.Can observed visible defects include, but is not limited to: known other the visual feature of the those of ordinary skill in pit, white dirt, orange peel, caking or ripple substantially or optics and the paint field.Therefore, " coarse " surface hereinafter described has one or more above-mentioned features, and it may show that in coating one or more compositions in the composition are incompatible each other.Opposite is, according to purpose of the present invention, the smooth substantially coating that hereinafter is characterized by " smooth " surface is considered to contain following such coating composition: in this coating composition, the various compositions that are in the reaction final state form coating, in this coating, various compositions are compatible with each other, perhaps through adjustment and compatible with each other; Furthermore, if this coating has any " coarse " surface feature, then only have seldom " coarse " surface feature.
In Table I,, estimate the influence of the consumption increase of HFPO-mono acrylic ester (HFPO-A) and the many acrylate of HFPO-(HFPO-MA) to the surface quality and the ink repellent of coating by visual inspection.
Table I: the HFPO acrylate is for the Effect on Performance of hating the hard coating of mark pen ink
| HC-1％ | MP-1％ | FC-2％ | FC-4％ | FC-5％ | Ink repellent |
| 99.5 | 0.5 | 1 | |||
| 99.8 | 0.2 | 2-3 | |||
| 99.9 | 0.1 | 2-3 | |||
| 99.0 | 1.0 | 1 | |||
| 98.0 | 2.0 | 1 | |||
| 99.0 | 1.0 | 1 | |||
| 98.0 | 2.0 | 1 | |||
| 99.0 | 1.0 | 1 | |||
| 98.0 | 2.0 | 1 |
As shown in Table I, add the many acrylate of small amount of H FPO-(HFPO-MA) and just can show outstanding ink repellent.Also can find out in addition: in the hard coating of HC-1, add 0.5 weight % or more HFPO-mono acrylic ester, can obtain similar best ink repellent.
Yet, the surface quality of these samples of visual inspection, the result shows: these surface irregularities.Think in theory: this surface imperfection is caused by the inconsistent problem between the hard coating of HC-1 and HFPO-mono acrylic ester or the many acrylate of HFPO-.
Below, as shown in Table II, multiple fluoropolymer chemical compatilizer is added separately or add, to estimate the surface characteristic and the ink repellent of coating with HFPO-mono acrylic ester or the many acrylate of HFPO-.
Table II: the FC compatilizer is to hating the Effect on Performance of the hard coating of mark pen ink
| HC-1％ | MP-1％ | FC-2％ | FBSEA％ | FC-SH％ | Coatingsurface | Ink repellent |
| 99.8 | 0.2 | Coarse | 2-3 | |||
| 89.9 | 0.1 | 10 | Smooth | 1-2 | ||
| 95 | 0.2 | 4.8 | Smooth | 1 | ||
| 90 | 10 | Smooth | 3 | |||
| 90 | 10 | Smooth | 3 |
Test-results in the Table II shows: (at this is FBSEA to the acrylate that perfluoro butyl replaces, add-on is 10 weight %) and the mode that adds together of HFPO-mono acrylic ester MP-1, compare with the mode (" benchmark mode ") that separately the HFPO-acrylate is added among the HC-1, the former shows the surface characteristic that is improved.Although do not want to be bound by theory, the result shows: the acrylate that perfluoro butyl replaces has improved the consistency between hard coating of HC-1 and the HFPO-mono acrylic ester, and the result has improved profile pattern.
This test-results also shows: (at this is FBSEA to the acrylate that perfluoro butyl is replaced separately, add-on is 10 weight %) add the mode among the people HC-1, compare with the benchmark mode, the former shows the profile pattern that is improved, but does not obtain required ink repellent.
Table II also shows: the mode that mercaptan (at this is FC-SH, and add-on is 4.8 weight %) that perfluoro butyl replaces and HFPO-mono acrylic ester or FC-2 add together, compare with the benchmark mode, and the former shows surface characteristic and the profile pattern that is improved.Yet, add FC-SH (add-on is 10%) and do not add the mode of HFPO-mono acrylic ester, though can obtain required profile pattern, required ink repellent do not obtained.
The solution of following Table III institute general description is at Virahol: ethyl acetate is the solution of the 30 solid % that prepare in 1: 1 the solvent mixture, adopts the coiling rod No. 9, and this solution is coated on Melinex 618 films of 5 mils with about 4 microns dry state thickness.With this coating in 80 ℃ baking oven dry 1 minute, place it in subsequently on the conveying belt that links to each other with ultraviolet (UV) light curring unit, and under nitrogen atmosphere, with the speed of 20 feet per minute clocks, make it carry out ultraviolet light polymerization with the H type bulb of 500 watts of Fusion.
The vibration sand method (Oscillating Sand Method) of employing through adjusting (ASTMF735-94), the weather resistance of testing coating.In the method, base material after coating cuts out the disk that diameter is 85mm, place it in (bottle W216922 in the bottle cap of 16 ounces of bottles, derive from the Wheaton company that is positioned at N.J. Millville city), use 50g20-30 purpose Ottawa sand (deriving from the VWR company that is positioned at Bristol city, U.S. Kang Naitige state) with its covering then.This bottle cap is placed on the bottle, and the bottle that assembles is placed on orbital shaker (VWR DE-5000E derives from the VWR company that is arranged in Bristol city, U.S. Kang Naitige state), this vibrator is set to 275 rev/mins.After vibrating about 10 minutes, take out coated base material, the visual inspection surfaceness.In addition, with marking pen (this marking pen is Sanford Sharpie, Fine Point permanent marker, No.30001) ink streaks the diameter of coated disk surfaces with form of straight lines, and the viewing test phenomenon.Measure the wetting base material of ink and do not show dehumidification or become the length of that part of line of ink marker of pearl property, with this length records in Table III.Length numerical value is that the coating of 85mm is considered to lose fully ink repellent, is considered to have the ideal weather resistance and test number is the coating of 0mm.
Table III
| HC-1％ | MP-2％ | Fluorochemicals acrylate % | Carbon chain lengths is fluoridized % | Whether the surface is coarse | Ink repellent (mm) |
| 90.9 | 0.10 | 9.0 methacrylic acid 2,2, the 2-trifluoro ethyl ester | 2， 34％ | Be | 69 |
| 90.9 | 0.10 | 9.0 vinylformic acid ω-hydrogen 2,2,3,3,4,4,5,5-octafluoro pentyl ester | 5， 50％ | Not | 66 |
| 90.9 | 0.10 | 9.0 methacrylic acid perfluor cyclohexyl methyl esters | 7， 51％ | Not | 59 |
| 90.9 | 0.10 | 9.0 vinylformic acid 1H, 1H ,-2,2,3,3,4,4,4-seven fluorine butyl esters | 4， 51％ | Be | 62 |
| 90.9 | 0.10 | 9.0 diacrylate 2,2,3,3,4,4,5,5-octafluorohexane diol ester | 6， 36％ | Not | 50 |
| 90.9 | 0.10 | 9.0 FBSAA | 8， 34％ | Not | 52 |
| 90.9 | 0.10 | 9.0 FBSEMA | 7， 40％ | Not | 52 |
| 90.9 | 0.10 | 9.0 FBSEA | 7， 41.5％ | Not | 54 |
| 99.9 | 0.10 | Do not have | Inapplicable | Be | 59 |
As shown in Table III, wherein added carbon chain lengths and be at least 5 carbon atoms and fluorine content sample greater than 30% fluorochemicals acrylate, compare with control sample (the HFPO derivative that only contains hard coating of HC-1 and 0.1 weight %), the former shows the surface irregularity feature that is improved, and the two shows similar ink repellent feature.
In addition, wherein added the sample that carbon chain lengths is at least the fluorochemicals acrylate of 5 carbon atoms, with added carbon chain lengths the sample of short fluorochemicals acrylate compare, the former shows the surface irregularity feature that is improved.
At Virahol: ethyl acetate is that the solids concn that makes 93.62%HC-1/6.3%FBSEA/0.08%FC-6 is the sample of 30 solid % in 1: 1 the solvent mixture.Adopt the method identical, apply and solidify this solution with example shown in the Table III.After 10 minutes sand test (270rpm), the ink repellent of smooth coating is 57.
At Virahol: ethyl acetate is that the solids concn that makes 98.42%HC-1/5%FBSEA/0.18%FC-1 is the sample of 30 solid % in 1: 1 the solvent mixture.Adopt the method identical, apply and solidify this solution with example shown in the Table III.After 10 minutes sand test (270rpm), the ink repellent of coating is 40.
Below, the experiment of being carried out in Table IV is: acrylate (is FBSEA at this) and HFPO-mono acrylic ester that the perfluoro butyl of different amounts is replaced are added in the HC-1 resin.Estimate the ink repellent and the receding angle (water is as test(ing) liquid) of gained coating.For these experiments, the sand test was carried out under the condition of 300rpm 15 minutes.
Table IV
| HC-1％ | FB SEA％ | MP-2％ | Hate fountain pen ink (mm) | Receding angle (degree) |
| 85.26 | 14.5 | 0.24 | 15 | 103.6 |
| 88.76 | 11 | 0.24 | 30 | 103.9 |
| 92.26 | 7.5 | 0.24 | 26 | 99.7 |
| 95.76 | 4 | 0.24 | 42 | 100.6 |
| 85.32 | 14.5 | 0.18 | 25 | 103.1 |
| 88.82 | 11 | 0.18 | 15 | 103.9 |
| 92.32 | 7.5 | 0.18 | 35 | 97.4 |
| 95.82 | 4 | 0.18 | 38 | 101.1 |
| 85.38 | 14.5 | 0.12 | 40 | 98.4 |
| 88.88 | 11 | 0.12 | 32 | 100 |
| 92.38 | 7.5 | 0.12 | 30 | 99 |
| 95.88 | 4 | 0.12 | 65 | 84.2 |
| 85.44 | 14.5 | 0.06 | 76 | 67.8 |
| 88.94 | 11 | 0.06 | 75 | 69.7 |
| 92.44 | 7.5 | 0.06 | 62 | 93.5 |
| 95.94 | 4 | 0.06 | 62 | 98.4 |
As can be seen, for each consumption of HFPO mono acrylic ester derivative, all exist best FBSEA consumption.The consumption of HFPO mono acrylic ester derivative is high more, and the amount that then obtains the required FBSEA of optimum contact angle is also high more.The HFPO mono acrylic ester of low consumption uses with the FBSEA of too high consumption, can cause ink repellent reduction and contact angle to reduce.
In Table V, the experiment of being carried out is: acrylate (is FBSEA at this) and the many acrylate of HFPO-that the perfluoro butyl of different amounts is replaced are added among the HC-1.Through 15 minutes sand tests (300rpm) afterwards, estimate the ink repellent and the contact angle (water is as test(ing) liquid) of gained coating.
Table V
| HC-1％ | FBSEA％ | The HFPO derivative, % | Ink repellent (mm) | Receding angle (degree) with water |
| 91.67 | 8.25 | FC-3，0.08 | 30 | 93.2 |
| 93.92 | 6.00 | FC-3，0.08 | 0 | 92.3 |
| 95.82 | 4.10 | FC-3，0.08 | 0 | 99.4 |
| 91.67 | 8.25 | MP-3，0.08 | 85 | 48.9 |
| 93.92 | 6.00 | MP-3，0.08 | 0 | 88.2 |
| 95.82 | 4.10 | MP-3，0.08 | 0 | 95.6 |
| 91.67 | 8.25 | FC-2，0.08 | 45 | 86.1 |
| 93.92 | 6.00 | FC-2，0.08 | 25 | 93.3 |
| 95.82 | 4.10 | FC-2，0.08 | 12 | 93.1 |
As shown in Table V, the many acrylate of HFPO many acrylate with the sample that uses of the less FBSEA of amount than HFPO and have obtained better ink repellent with the sample that the more FBSEA of amount uses, confirm thus: the FBSEA that can be added in the hard coating of HC-1 (wherein having used the many acrylate derivatives of HFPO) exists best maximum consumption, and continuing to increase its consumption then can influence ink repellent unfriendly.
Another experiment of being carried out is: adopt gageable accurate mould coating method, HC-1 is coated onto on Melinex 618 films of 5 mils.Should in Virahol, be diluted to 30 solid weight % by hard coating, and it was coated on the PET backing of 5 mils, obtain 5 microns dry state thickness.Monitor and set from the flow velocity of the material of pressurized vessel discharge with under meter.By changing the air pressure in the sealed vessel, adjust flow velocity, wherein said air pressure drives the liquid discharge and by pipeline, strainer, under meter, passes through mould then.With drying and the film after solidifying on wind up roll.
Under 100 ℃, this coating is dry in 10 feet baking oven, and with 100%, 75%, 50% and 25% power it is solidified respectively with 300 watts Fusion Systems H type bulb.In preparation 1, FBSEA (as the acrylate of perfluoro butyl replacement) as the hard coating of ceramic polymer, is formed ceramic polymer as HFPO derivative, HC-1 as compatilizer, MP-2.In preparation 2, FBSEA (as the acrylate of perfluoro butyl replacement) as the hard coating of ceramic polymer, is formed ceramic polymer as HFPO derivative, HC-1 as compatilizer, FC-3.Under the condition of 300rpm, carry out 15 minutes sand test.Test-results is summarized in the Table VI:
Table VI
| HC-1 weight % | FBSEA weight % | HPFO compound weight % | UV dosage, power % | Ink repellent (mm) | |
| MP-2 | |||||
| Preparation 1 | 89.83 | 10.00 | 0.17 | 100 | 0 |
| Preparation 1 | 89.83 | 10.00 | 0.17 | 75 | 38.5 |
| Preparation 1 | 89.83 | 10.00 | 0.17 | 50 | 38.5 |
| Preparation 1 | 89.83 | 10.00 | 0.17 | 25 | 64.1 |
| FC-3 | |||||
| Preparation 2 | 97.87 | 2.00 | 0.13 | 100 | 0 |
| Preparation 2 | 97.87 | 2.00 | 0.13 | 75 | 0 |
| Preparation 2 | 97.87 | 2.00 | 0.13 | 50 | 0 |
| Preparation 2 | 97.87 | 2.00 | 0.13 | 25 | 51.3 |
Can be confirmed that by the result shown in the Table VI the ceramic polymer coating of preparation 1 and preparation 2 last gained has experienced crosslinking reaction really in the ultraviolet lighting process, this point can be confirmed from the result that ink repellent under the higher UV radiation dose improves.In addition, many acrylate of HFPO-FC-3 has higher acrylate functionalities, makes it take place to solidify more completely than HFPO-monofunctional acrylate MP-2, and is especially all the more so under lower radiation dose.
Make the sample of 93.62%HC-1/6.3%FBSEA/0.08%FC-6.Apply this sample with the method identical with other example.After 10 minutes sands tests (270rpm), it is 57 smooth coating that the result obtains ink repellent.
With with the identical mode of example in the Table III, the example in the preparation Table VII, and with its coating and curing, difference is: the sample of coating is the solution of the sample that contains PETA of the 30 solid % that prepare in ethyl acetate.All coatings that obtain at last all are smooth.The sand test was carried out under the condition of 300rpm 20 minutes.
Table VII
| HC-1％ | PETA％ | MP-2％ | FC-3％ | FBSEA ％ | Irgacure 907 ％ | Ink repellent (mm) |
| 89.8 | 0.2 | 10 | 52 | |||
| 89.8 | 0.2 | 10 | 2 | 46 | ||
| 97.85 | 0.15 | 2 | 2 | 0 |
Data in the Table VII show: do not contain nanoparticle but contain the HFPO acrylate and the hard coating of many acrylate and compatilizer as hard coating, it is functional.
Therefore, the invention provides be used to obtain smooth, have a multiple novel method of the hard coat of anti-mark and pollution resistance and low surface energy, described hard coat on Optical devices as independent layer.This hard coating is easy to produce and coating.
Although invention has been described according to preferred embodiment,, it should be understood that certainly the present invention is not limited, because those skilled in the art can make various changes, especially can make various changes according to above-mentioned instruction.
Claims (27)
1. film that is used to form the stain repellent optical display unit, this display unit has smooth substantially outside surface on goods, and this film comprises:
Optical element;
Be arranged in the hard coating composition layer on the major surfaces of described optical element, described hard coating composition contains the hard coating of ceramic polymer, has the monobasic or polynary (methyl) acryl compound of at least one univalent poly-(oxidation hexafluoro propylidene) part and is selected from the compatilizer that contains fluoroalkyl and contain the free radical reaction compatilizer in the compatilizer of fluorine alkylidene group;
Optional adhesive material, described adhesive material is applied in the another side of described optical element, makes described optical element between described hard coating composition layer and described adhesive material; And optional removable peel ply, described peel ply is applied on the described adhesive material.
2. the described film of claim 1, the hard coating of wherein said ceramic polymer is based on the hard coating formulation of multifunctional acrylic acid ceramic polymer.
3. the described film of claim 1, wherein said monobasic or polynary (methyl) acryl compound that has at least one univalent poly-(oxidation hexafluoro propylidene) part is selected from: HFPO-C (=O) NHCH
2CH
2OC (O) CH=CH
2, HFPO-C (=O) NHCH
2CH
2OC (O) C (CH
3)=CH
2With poly-(oxidation hexafluoro propylidene) multicomponent methacrylate.
4. the described film of claim 1 wherein saidly has the monobasic of at least one univalent poly-(oxidation hexafluoro propylidene) part or the chemical formula of polynary (methyl) acryl compound is:
R
fpeQ(X)
n，
R wherein
FpeIt is the residue of univalent HFPO part;
Wherein Q is the linking group that is selected from alkylidene group, arylene group, arylidene-alkylidene group and the alkylidene group-arylene group;
Wherein X be selected from (methyl) acryl reactive group ,-free radical reaction group in SH reactive group, allyl reaction group and the vinyl reactive group; With
Wherein n is 1-3.
5. the described film of claim 4, wherein Q is selected from :-SO
2N (R) CH
2CH
2-,-(CH
2)
m-,-CH
2O (CH
2)
3-and-C (O) N (R) CH
2CH
2-, wherein R is H or the low alkyl group that contains 1-4 carbon atom, m is 1-6.
6. the described film of claim 5, wherein Q is-SO
2N (CH
2CH
2)
2-.
7. the described film of claim 4, wherein Q is the linking group of straight or branched, the linking group of this straight or branched contains the heteroatoms that is selected among O, N and the S.
8. the described film of claim 1 describedly has the monobasic of at least one univalent poly-(oxidation hexafluoro propylidene) part or the chemical formula of polynary (methyl) acryl compound is selected from: HFPO-C (O) N (H) C (CH
2OC (O) CH=CH
2)
2CH
2CH
3HFPO-C (O)-N (H) CH (CH
2OC (O)-CH=CH
2)
2HFPO-C (O) N (H) CH
2CH (OC (O) CH=CH
2) CH
2OC (O) CH=CH
2HFPO-C (O)-N (H) (CH
2)
3N (CH
2CH
2OC (O) CH=CH
2)
2HFPO-C (O)-NHCH
2CH
2N (CO-CH=CH
2) (CH
2CH
2OCOCH=CH
2); And mol ratio is 1: 1 HFPO-C (=O) NHCH
2CH
2CH
2NHCH
3Adduct with Viscoat 295.
9. the described film of claim 1, wherein said free radical reaction compatilizer are the acrylate compatilizer that perfluoro butyl replaces.
10. the described film of claim 9, the acrylate compatilizer that wherein said perfluoro butyl replaces is selected from: C
4F
9SO
2N (CH
3) CH
2CH
2OC (O) CH=CH
2, C
4F
9SO
2N (CH
2CH
2OC (O) CH=CH
2)
2, C
4F
9SO
2N (CH
3) CH
2CH
2OC (O) C (CH
3)=CH
2And composition thereof.
11. the described film of claim 1, the wherein said chemical formula that contains the compatilizer of fluoroalkyl is (R
f) Q (X)
n:
R wherein
fIt is fluoroalkyl;
Wherein Q is the linking group that is selected from alkylidene group, arylene group, arylidene-alkylidene group and the alkylidene group-arylene group;
Wherein X be selected from (methyl) acryl reactive group ,-free radical reaction group in SH reactive group, allyl reaction group and the vinyl reactive group; With
Wherein n is 1-3.
12. the described film of claim 11, wherein Q is the linking group of straight or branched, and the linking group of this straight or branched contains the heteroatoms that is selected among O, N and the S.
13. the described film of claim 11, wherein Q is selected from:
-SO
2N (R) CH
2CH
2-group ,-(CH
2)
m-group ,-CH
2O (CH
2)
3-group and-C (O) N (R) CH
2CH
2-group, wherein m is 1-6, wherein R is H or the low alkyl group that contains 1-4 carbon atom.
14. the described film of claim 13, wherein Q is-SO
2N (CH
2CH
2)
2-group.
15. the described film of claim 13, wherein R is the low alkyl group that contains 1-4 carbon atom.
16. the described film of claim 1, the wherein said chemical formula that contains the compatilizer of fluorine alkylidene group is: ((X)
nQR
F2Q (X)
n),
R wherein
F2It is the fluorine alkylidene group;
Wherein Q is the linking group that is selected from alkylidene group, arylene group, arylidene-alkylidene group and the alkylidene group-arylene group;
Wherein X be selected from (methyl) acryl group ,-free radical reaction group in SH group, allyl group and the vinyl groups; With
Wherein n is 1-3.
17. the described film of claim 16, wherein Q is the linking group of straight or branched, and the linking group of this straight or branched contains the heteroatoms that is selected among O, N and the S.
18. the described film of claim 16, wherein Q is selected from:
-SO
2N (R) CH
2CH
2-group ,-(CH
2)
m-group ,-CH
2O (CH
2)
3-group and-C (O) N (R) CH
2CH
2-group, wherein m is 1-6, wherein R is H or the low alkyl group that contains 1-4 carbon atom.
19. the described film of claim 18, wherein Q is-SO
2N (CH
2CH
2)
2-group.
20. the described film of claim 18, wherein R is the low alkyl group that contains 1-4 carbon atom.
21. the described film of claim 11, wherein X is selected from thiol group and multi-thiol group.
22. the described film of claim 1; the wherein said compatilizer that contains fluoroalkyl is the acrylate compatilizer that contains the replacement of perfluoroalkyl; this acrylate compatilizer has the carbochain that contains five carbon atoms at least that links to each other with (methyl) acryl end group, and the fluorine content of this compatilizer is also greater than 30 weight % of the gross weight of the acrylate compatilizer of the described replacement that contains perfluoroalkyl.
23. the described film of claim 22, the wherein said acrylate compatilizer that contains the replacement of perfluoroalkyl is selected from: vinylformic acid (perfluor cyclohexyl) methyl esters, diacrylate 2,2,3,3,4,4,5,5-octafluorohexane diol ester, methacrylic acid perfluor cyclohexyl methyl esters, vinylformic acid ω-hydrogen 2,2,3,3,4,4,5,5-octafluoro pentyl ester, C
4F
9SO
2N (CH
3) CH
2CH
2OC (O) CH=CH
2, C
4F
9SO
2N (CH
2CH
2OC (O) CH=CH
2)
2, C
4F
9SO
2N (CH
3) CH
2CH
2OC (O) C (CH
3)=CH
2And composition thereof.
24. the described film of claim 1, the consumption of wherein said free radical reaction compatilizer are the 2%-15% of the gross weight of described hard coating composition.
25. the described film of claim 1, the consumption of wherein said free radical reaction compatilizer are at least 3 times of amount that have the monobasic of at least one univalent poly-(oxidation hexafluoro propylidene) part or polynary (methyl) acryl compound described in the described hard coating composition.
26. the optical display with film according to claim 1, described film is applied in and is cured on the optical element.
27. a composition that is used as smooth substantially hard coat in optical display, said composition contains:
The hard coating of pottery polymer;
Monobasic or polynary (methyl) acryl compound of having at least one univalent poly-(oxidation hexafluoro propylidene) part; With
Be selected from the free radical reaction compatilizer in compatilizer that contains fluoroalkyl and the compatilizer that contains the fluorine alkylidene group.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US56935104P | 2004-05-07 | 2004-05-07 | |
| US10/841,159 | 2004-05-07 | ||
| US10/841,159 US7101618B2 (en) | 2004-05-07 | 2004-05-07 | Article comprising fluorochemical surface layer |
| US60/569,351 | 2004-05-07 | ||
| US11/026,700 | 2004-12-30 | ||
| US11/026,700 US20050249956A1 (en) | 2004-05-07 | 2004-12-30 | Stain repellent optical hard coating |
| PCT/US2005/015573 WO2005111157A1 (en) | 2004-05-07 | 2005-05-04 | Stain repellent optical hard coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1965037A CN1965037A (en) | 2007-05-16 |
| CN100594222C true CN100594222C (en) | 2010-03-17 |
Family
ID=38083481
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800144613A Pending CN1980980A (en) | 2004-05-07 | 2005-05-04 | Fluoropolyether poly(meth)acryl compounds |
| CN200580018583A Active CN100594222C (en) | 2004-05-07 | 2005-05-04 | Stain repellent optical hard coating |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800144613A Pending CN1980980A (en) | 2004-05-07 | 2005-05-04 | Fluoropolyether poly(meth)acryl compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1980980A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040619A (en) * | 2019-12-31 | 2020-04-21 | 凯鑫森(上海)功能性薄膜产业有限公司 | Water-resistant UV (ultraviolet) curing resin composition as well as preparation method and application thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101384110B1 (en) * | 2010-10-29 | 2014-04-10 | 박준영 | Method of preparing pad for touch panel and pad for touch panel prepared thereby |
| CN103429664B (en) * | 2011-02-15 | 2016-05-11 | 日产化学工业株式会社 | Light-cured type film forms the manufacture method by composition and cured film |
| JP5612003B2 (en) * | 2012-03-03 | 2014-10-22 | 株式会社ホンダロック | Electrochromic mirror |
| JP6006443B1 (en) * | 2016-01-29 | 2016-10-12 | ダイアモールディング株式会社 | Front panel manufacturing method |
-
2005
- 2005-05-04 CN CNA2005800144613A patent/CN1980980A/en active Pending
- 2005-05-04 CN CN200580018583A patent/CN100594222C/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040619A (en) * | 2019-12-31 | 2020-04-21 | 凯鑫森(上海)功能性薄膜产业有限公司 | Water-resistant UV (ultraviolet) curing resin composition as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1980980A (en) | 2007-06-13 |
| CN1965037A (en) | 2007-05-16 |
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