CN101627064A - The microstructured optical films that comprises biphenyl difunctional monomers - Google Patents

The microstructured optical films that comprises biphenyl difunctional monomers Download PDF

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CN101627064A
CN101627064A CN200880007639A CN200880007639A CN101627064A CN 101627064 A CN101627064 A CN 101627064A CN 200880007639 A CN200880007639 A CN 200880007639A CN 200880007639 A CN200880007639 A CN 200880007639A CN 101627064 A CN101627064 A CN 101627064A
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朱迪思·M·因维埃
布赖恩·V·亨特
凯尔·J·林德斯特伦
戴维·B·奥尔森
安东尼·M·伦斯特伦
克林顿·L·琼斯
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3M Innovative Properties Co
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Abstract

The invention describes optical thin film with polymeric microstructure surface.Described polymeric microstructure surface comprises the reaction product of polymerizable resin composition, and described polymerizable resin composition comprises at least a two (methyl) biphenyl acrylate monomer of 10% to 100 weight %.Described two (methyl) acrylate monomer comprises the core biphenyl structural, and described core biphenyl structural has two aromatic rings that link to each other by the C-C key.Described two (methyl) biphenyl acrylate monomer contains adjacent and/or (methyl) acrylate substituting group of sufficient amount, makes described monomer be liquid down at 25 ℃.

Description

The microstructured optical films that comprises biphenyl difunctional monomers
CROSS-REFERENCE TO RELATED PATENT
The application requires the right of priority of the U.S. Provisional Application No.60/893593 of submission on March 9th, 2007.
Background technology
Some microstructured optical product (for example in U.S. Patent No. 5,175,030 and 5,183, described in 597) is commonly called " brightness enhancement film ".Brightness enhancement film is used for increasing the brightness of the flat-panel monitor backlight such as liquid-crystal display (LCD) in many electronic products, this liquid-crystal display comprises those that are used for electroluminescent panel, laptop computer, word processor, both desktop monitors, televisor, pick up camera, and the indicating meter of automobile and aircraft.
Brightness enhancement film advantageously shows specific optics and physical property, comprises and the relevant brightness enhancement film specific refractory power of generation luminance gain (i.e. " gain ").The improvement of brightness makes by using less energy illuminated displays that electronic product is more effectively operated, thereby reduces energy expenditure, lower to the thermal load of element, and prolongs the work-ing life of product.
Brightness enhancement film is made by curing with high refractive index or polymerization single polymerization monomer.Usually adopt halogenation (for example, bromination) monomer or oligopolymer, for example to obtain 1.56 or bigger specific refractory power.The another kind of mode that obtains the high refractive index composition is to adopt to comprise high refractive index nano particulate polymerizable organic composite, for example U.S. Patent Publication No.2006/0204745,2006/0210726,2006/0204676 and US 2006/0128853 described in.
Summary of the invention
The invention describes optical thin film with polymeric microstructure surface.The polymeric microstructure surface comprises the reaction product of polymerizable resin composition, and this polymerizable resin composition comprises at least a two (methyl) biphenyl acrylate monomer of 10% to 100 weight %.Two (methyl) acrylate monomer comprises the core biphenyl structural, and this structure has two aromatic rings that link to each other by the C-C key.In one embodiment, two (methyl) biphenyl acrylate monomer is liquid down at 25 ℃.In another embodiment, the monomeric aromatic ring of two (methyl) biphenyl acrylate at the ortho position or a position have at least one (methyl) acrylate substituting group.
Two (methyl) biphenyl acrylate monomer has following formula: H 2C=(R1) C (O)---Ar-Ar---(O) C (R1)=CH 2Wherein each Ar group is phenyl or naphthyl independently, and R1 is H or methyl.
One class preferred two (methyl) biphenyl acrylate monomer has following formula:
Figure G2008800076395D00021
Wherein each R1 is H or methyl independently;
Each R2 is Br independently;
M is in 0 to 4 scope;
Each Q is O or S independently;
N is in 0 to 10 scope;
C2 to the C12 alkyl of L for can randomly being replaced by one or more hydroxyls;
Z is an aromatic ring;
T is 0 or 1 independently;
And-Q[L-O] n C (O) C (R1)=CH 2In the group at least one is substituted in an ortho position or a position.
Embodiment
The invention describes the optical thin film with polymeric microstructure surface, this polymeric microstructure surface comprises the reaction product of polymerizable resin composition, and this polymerizable resin composition contains the unsaturated biphenyl monomer of some polymerizable ethylene linkage formula.
Polymeric microstructure can be optical element or the optical articles that is made of basic unit and polymeric microstructure optical layers.Basic unit and optical layers can be formed by identical or different polymer materials.A kind of preferred optical thin film with polymeric microstructure surface is a brightness enhancement film.
Usually, brightness enhancement film can strengthen the axial brightness (this paper is called " brightness ") of light-emitting device.Brightness enhancement film can be the micro-structural film of printing opacity.The shape characteristic of micro-structural can be the lip-deep a plurality of prisms of film, makes that this film can be used for changing direction of light by reflection and refraction.Prismatical height usually about 1 micron to about 75 microns scope.When (for example being used for optical display, be present in the optical display in laptop computer, the wrist-watch etc.) time, microstructured optical films can strengthen the brightness of optical display in the following way: will be limited in from the light that indicating meter is overflowed and see through this optical display in the pair of planar that becomes required angle with its normal axis.Therefore, the light outside this tolerable limit that penetrates from indicating meter is reflected back toward the indicating meter, and the part in these light can be by " recycle ", and so that the angle of luminous energy effusion indicating meter turns back to the micro-structural film.This circulation is useful, makes displaying appliance that the required energy expenditure of required gray scale be arranged because it can reduce.
Brightness enhancement film of the present invention generally includes basic unit's (for example, preformed polymeric membrane) and optical layers.Optical layers comprises linearly aligned regular rectangular prism.Each prism has first and second.Prism is formed in the substrate, this substrate have on it prismatical first surface of formation and smooth basically or be planar and with the opposing second surface of first surface.So-called rectangular prism is meant that drift angle is generally about 90 °.Yet this angle can be in 70 ° to 120 ° scope, and can be in 80 ° to 100 ° scope.These tops can be sharp, circle or that flatten or cut flat.For example, can make ridge become circle, make its radius in 4 to 7 to 15 microns scope.Prismatic peak-to-peak spacing (or pitch) can be 5 to 300 microns.For brightness enhancement film, pitch is preferably 10 to 36 microns, and more preferably is 18 to 24 microns.Corresponding with it prism heights is preferably about 5 to 18 microns, and more preferably is about 9 to 12 microns.Prismatical face needn't be identical, and prism also can be tilted in relation to each other.Relation between optical goods total thickness and the prism heights can change.Yet, wish to use relatively thin optical layers usually with clear and definite faceted pebble.Near for the brightness enhancement film of 1 mil (20-35 micron), the typical ratios of prism heights and total thickness is usually between 0.2 and 0.4 for thickness in the substrate.
As U.S. Patent No. 5,183, described in 597 (Lu) and the U.S. Patent No. 5,175,030 people such as () Lu, the goods (as brightness enhancement film) with microstructure can be by the method preparation that may further comprise the steps: (a) preparation polymerisable compound; (b) polymerisable compound is deposited on the apparent surface on micro-structural die casting surface of motherboard with the amount that only is enough to fill the motherboard cavity; (c) by making the polymerisable compound globule between preformed substrate and motherboard (at least one among both is flexible), move filled chamber; (d) solidify said composition.This motherboard can be a metal, and for example nickel, nickel-clad copper or nickel-plated brass perhaps can be stable under polymerizing condition, and preferably has the thermoplastic material of the surface energy that makes that polymeric material can remove from the motherboard neatly.Can choose wantonly the one or more surperficial upper base of basement membrane or handle to improve the sticking power of optical layers to substrate.
In certain embodiments, polymerizable resin composition comprises the inorganic nanoparticles of surface modification.In this type of embodiment, " polymerisable compound " is meant total composition, i.e. the inorganic nanoparticles of organic constituent and surface modification." organic constituent " is meant all components except the inorganic nanoparticles of surface modification in the composition.Because surface treatment agent is adsorbed or is connected to the surface of inorganic nanoparticles usually, so think that surface treatment agent is not the part of organic constituent.When composition did not contain the inorganic materials of inorganic nanoparticles and so on of surface modification for example, polymerisable compound and organic constituent were equal to.
Preferably, organic constituent and polymerisable compound are substantially free of solvent." be substantially free of solvent " and be meant that polymerisable compound contains the non-polymerizable solvent (as organic solvent) less than 5 weight %, 4 weight %, 3 weight %, 2 weight %, 1 weight % and 0.5 weight %.The concentration of solvent can be measured by currently known methods, for example vapor-phase chromatography (described in ASTM D5403).Preferred solvent concentration is less than 0.5 weight %.
The preferred component of organic constituent of selecting makes this organic constituent have low viscosity.The viscosity of organic constituent is lower than 1000cps, and is usually less than 900cps.The viscosity of organic constituent can be lower than 800cps, is lower than 700cps, is lower than 600cps or is lower than 500cps under coating temperature.As used herein, on the parallel plate of 25mm, measure (shearing rate is up to 1000sec-1) viscosity with the dynamic stress rheometer.In addition, the viscosity of organic constituent is generally 10cps at least under coating temperature, be more typically 50cps at least.
Coating temperature usually in 77 of envrionment temperatures (25 ℃) to the scope of 180 (82 ℃).Coating temperature can be lower than 170 °F (77 ℃), is lower than 160 °F (71 ℃), is lower than 150 °F (66 ℃), is lower than 140 °F (60 ℃), is lower than 130 °F (54 ℃) or is lower than 120 °F (49 ℃).Organic constituent can or comprise solid ingredient for solid, and precondition is that the fusing point of polymerisable compound is lower than coating temperature.Organic constituent is preferably liquid at ambient temperature.
The specific refractory power of two (methyl) biphenyl acrylate monomer and/or organic constituent is at least 1.55,1.56,1.57,1.58,1.59 or 1.60.The specific refractory power that comprises high refractive index nano particulate polymerisable compound can be up to 1.70.(for example, at least 1.61,1.62,1.63,1.64,1.65,1.66,1.67,1.68 or 1.69).Usually also preferably in visible light, has high transmittance.
The time scale of the energy-curable of polymerisable compound preferably is less than five minutes (for example, for the brightness enhancement film of 75 micron thickness).Polymerisable compound is preferred full cross-linked so that the second-order transition temperature greater than 45 ℃ to be provided usually.Second-order transition temperature can be measured by methods known in the art, for example dsc (DSC), modulation DSC or dynamic mechanical analysis method.Polymerisable compound can pass through the polymerization of conventional radical polymerization method.
The optical thin film that the present invention describes is prepared from by polymerizable resin composition, and this polymerizable resin composition comprises at least a substituent difunctionality biphenyl of polymerizable (methyl) the acrylate monomer that contains.This type of monomer comprises the biphenyl core texture, and wherein two phenyl groups are not condensed, but links to each other by the C-C singly-bound.This type of biphenyl monomer of being paid close attention to does not contain any connection base between phenyl group.Each phenyl group has the substituting group of the polymerizable of comprising (methyl) acrylate or sulfo-(methyl) acrylate (for example, end) group.
In the aromatic ring at least one at the ortho position or a position comprise (methyl) acrylate substituting group.Two (methyl) biphenyl acrylate monomer contains adjacent and/or (methyl) acrylate substituting group of sufficient amount, makes this monomer be liquid down at 25 ℃.In certain embodiments, each comprises the substituting group of (methyl) acrylate group and aromatic ring group at the ortho position or a position bonding.Preferably, two (methyl) biphenyl acrylate monomer contains neighbour's (methyl) acrylate substituting group (promptly replacing fiduciary point two (methyl) biphenyl acrylate monomeric at least 50%, 60%, 70%, 80%, 90% or 95%) of volume.In certain embodiments, each comprises the substituting group of (methyl) acrylate group and aromatic ring group at the ortho position or a position bonding.Along with the particularly increase of para-orienting group quantity of a position, the viscosity of organic constituent also increases together.In addition, at room temperature be solid to two (methyl) biphenyl acrylate monomer, solubleness very little (promptly less than 10%), even in vinylformic acid phenoxy group ethyl ester and vinylformic acid tetrahydro furfuryl ester, also be like this.
Two (methyl) biphenyl acrylate monomer has following formula usually:
H 2C＝(R1)C(O)---Ar-Ar---(O)C(R1)＝CH 2??(I)
Wherein each Ar group is phenyl or naphthyl independently, and R1 is H or methyl.
C (R1)=CH preferably ,-(O) 2In the group at least one and Ar group are at the ortho position or a position bonding.Usually, each-(O) C (R1)=CH 2Group and Ar group are at the ortho position or a position bonding.Most preferably, each-(O) C (R1)=CH 2Group and Ar group are at the ortho position bonding.In some respects, direct and each (methyl) acrylate or sulfo-(methyl) acrylate group bonding of biphenyl group.In other embodiments, connecting base can provide between phenyl group and (methyl) acrylate group.For example, alcoxyl connects base (wherein carbon atom can randomly be replaced by hydroxyl) can provide between phenyl group and (methyl) acrylate group.The molecule of connection base (as, atom) measure usually less than 1200 gram/moles.Preferably, connect the C2-C3 alkoxyl group of base for can randomly being replaced by one or more hydroxyls.
In certain embodiments, monomer has formula (II)
Wherein each R1 is H or methyl independently;
Each R2 is Br independently;
M is in 0 to 4 scope;
Each Q is O or S independently;
N is in 0 to 10 scope;
C2 to the C12 alkyl of L for can randomly being replaced by one or more hydroxyls;
Z is an aromatic ring;
T is 0 or 1 independently;
And-Q[L-O] nC (O) C (R1)=CH 2In the group at least one is substituted in an ortho position or a position.In certain embodiments, each-Q[L-O] nC (O) C (R1)=CH 2Group is substituted in an ortho position or a position.In other embodiments, each-Q[L-O] nC (O) C (R1)=CH 2Group is substituted at the ortho position.
In some respects, Q is preferably O.In addition, n is generally 0,1 or 2.L is generally C 2Or C 3Alternatively, L is generally the C that hydroxyl replaces 2Or C 3In certain embodiments, z preferably condenses with phenyl group, thereby forms the dinaphthalene core texture.
In certain embodiments, preferably, polymeric microstructure surface, polymerizable resin composition and biphenyl monomer are substantially free of (promptly containing less than 1 weight %) bromine.In other embodiments, the total content of bromine and chlorine is less than 1 weight %.In some respects, polymeric microstructure surface or optical thin film, polymerizable resin composition and three benzene monomers right and wrong halogenated (promptly comprising altogether bromine, chlorine, fluorine and iodine) basically less than 1 weight %.
Some concrete monomers have formula as follows:
Figure G2008800076395D00071
Figure G2008800076395D00081
Figure G2008800076395D00091
Describe to some extent in the suitable synthetic method example below of above-mentioned molecule according to structure III and IV.Two (methyl) biphenyl acrylate monomer according to structure V can prepare by the following method: with 2,2 '-dihydroxybiphenyl and epichlorohydrin reaction generate the diether epoxide, existing under the situation of catalyzer, obtain final monomer then with this intermediate and vinylformic acid reaction.Each dinaphthalene molecule (for example, structure VI-VIII) can use 2 by similar synthetic method preparation, 2 '-dihydroxyl-1, and 1 '-dinaphthalene is as raw material rather than 2,2 '-dihydroxybiphenyl.Those of ordinary skill in the art also can adopt other synthetic methods.
Organic constituent comprises two (methyl) biphenyl acrylate monomer of one or more content at least 10 weight %, 15 weight %, 20 weight %, 25 weight %, 30 weight %, 35 weight % or 40 weight %.Although organic constituent can only be made up of one or more two (methyl) biphenyl acrylate monomers, but usually preferably, with at least a two (methyl) biphenyl acrylate monomer and second (being different) difunctionality (methyl) acrylate monomer or oligopolymer combination.In this embodiment, organic constituent comprises two (methyl) biphenyl acrylate monomer that is not more than 75 weight % usually.
Organic constituent preferably comprises at least 5 weight %, 10 weight %, 15 weight %, 20 weight %, and preferably second (being different) difunctionality (methyl) acrylate monomer or the oligopolymer of 25 weight %.The total amount of other difunctionalitys (methyl) acrylate monomer is no more than 75 weight % usually.Organic constituent preferably comprises one or more and does not contain biphenyl group aromatics difunctionality (methyl) acrylate monomer of (wherein aromatic ring links to each other by the C-C key).
In one embodiment, polymerisable compound comprises aromatics difunctionality (methyl) acrylate monomer, and this monomer comprises the major portion with following formula:
Wherein each R1 is hydrogen or methyl independently.Each R2 is hydrogen or bromine independently.Z is-C (CH 3) 2-,-CH 2-,-C (O)-,-S-,-S (O)-or-S (O) 2-, and each Q is O or S independently.Usually, the R1 group is identical.Usually, the R2 group is also mutually the same.L-O is for connecting base.L can comprise C side chain or straight chain independently 2-C 12Alkyl (is C 2, C 3, C 4, C 5, C 6, C 7, C 8, C 9, C 10, C 11Or C 12).In addition, the carbon atom of alkyl can be chosen wantonly by one or more hydroxyls and replace.For example L can be-CH 2CH (OH) CH 2-.Usually, it is identical connecting base.Preferably alkyl comprises and is no more than 8 carbon atom, and more preferably is no more than 6 carbon atom.Each n can be in the scope of 0-10.Each n is preferably at least 1.The molecular weight that connects base is usually less than 1200 gram/moles.Preferably, connect the C2-C3 alkoxyl group of base for can randomly being replaced by one or more hydroxyls.
Two (methyl) acrylate monomer can synthesize or buy.As used herein, major portion is meant the monomer that contains above-mentioned concrete structure of 60-70 weight % at least.It has been generally acknowledged that other reaction product also exist with this type of monomeric synthesising by-product form usually.Two (methyl) acrylate monomer can be tetrabromo-bisphenol diglycidylether and acrylic acid reaction product.This type of monomer can trade(brand)name " RDX-51027 " derive from UCB. S.A. (BE) Bruxelles Belgium, Smyrna, GA.This material is included as the major portion of 2-vinylformic acid, (1-methyl ethylidene) two [(2,6-two bromo-4,1-phenylene) oxo (2-hydroxyl-3,1-glyceryl)] ester.
Alternatively or in addition, organic constituent also can comprise the aromatic epoxy resin oligopolymer of one or more (methyl) acroleic acid esterifications.For example, the aromatic epoxy resin of (methyl) acroleic acid esterification (being described as the epoxy acrylate of modification) can trade(brand)name " CN104 ", " CN120 ", " CN118 ", " CN115 " and " CN112C60 " derive from Sartomer, Exton, PA.The aromatics epoxy oligomer (being described as epoxy acrylate oligomer) of (methyl) acroleic acid esterification can trade(brand)name " CN2204 " derive from Sartomer.In addition, the aromatics epoxy oligomer of (methyl) acroleic acid esterification (being described as the epoxy novolac acrylate with 40% Viscoat 295 blend) can trade(brand)name " CN112C60 " derive from Sartomer.
In certain embodiments, aromatic ring oxypropylene acid ester derivative for example has those of previously described structure from dihydroxyphenyl propane.In other embodiments, aromatic ring oxypropylene acid ester derivative is from the monomer that is different from dihydroxyphenyl propane.
A kind of bisphenol a diacrylate monomer of exemplary ethoxylation is can trade(brand)name " SR602 " (it is reported that the viscosity under 20 ℃ is that 610cps and Tg are 2 ℃) commercially available from Sartomer.Another kind of exemplary bisphenol A ethoxy diacrylate monomer is can trade(brand)name " SR601 " (it is reported that the viscosity under 20 ℃ is that 1080cps and Tg are 60 ℃) commercially available from Sartomer.
In one embodiment, polymerizable resin composition comprises: one or more of 25 weight % to 75 weight % at the ortho position or a position have (methyl) acrylate substituent two (methyl) biphenyl acrylate monomer; And one or more dihydroxyphenyl propane two (methyl) acrylate monomers of 25 weight % to 75 weight %.
Organic constituent can randomly comprise the monofunctional diluent of one or more content up to about 40 weight % of total organic constituent.
The specific refractory power of preferable absorbent can be greater than 1.50 (as greater than 1.55).This type of reactive diluent can be halogenated or non-halogenated (as non-bromo).
Suitable reactive diluent for example comprises (methyl) phenoxyethyl acrylate; Phenoxy group-2-methylethyl (methyl) acrylate; Phenoxy group ethoxyethyl group (methyl) acrylate, 3-hydroxyl-2-hydroxypropyl (methyl) acrylate; (methyl) benzyl acrylate; The thiophenyl ethyl propenoate; 2-naphthalene sulfenyl ethyl propenoate; 1-naphthalene sulfenyl ethyl propenoate; 2,4,6-tribromophenoxy ethyl propenoate; 2,4-dibromo-phenoxy base ethyl propenoate; 2-bromine phenoxy group ethyl propenoate; 1-naphthyloxy ethyl propenoate; 2-naphthyloxy ethyl propenoate; Phenoxy group 2-methylethyl acrylate; Phenoxy group ethoxyethyl group acrylate; 3-phenoxy group-2-hydroxyl acrylic propyl ester; 2,4-two bromo-6-secondary butyl phenenyl acrylate; 2,4-two bromo-6-isopropyl phenyl acrylate; Benzyl acrylate; Phenyl acrylate; 2,4,6-tribromo phenyl acrylate.Also can use other high refractive index monomers, for example pentabromobenzyl acrylate and penta-bromophenyl acrylate.
A kind of preferable absorbent is (methyl) phenoxyethyl acrylate, particularly phenoxyethyl acrylate (PEA).Phenoxyethyl acrylate can be commercially available from a more than source, comprises with trade(brand)name " SR339 " commercially available from Sartomer; Commercially available with trade(brand)name " Etermer 210 " from EternalChemical Co.Ltd.; And it is commercially available from Toagosei Co.Ltd with trade(brand)name " TO-1166 ".Another kind of preferable absorbent is thiophenyl ethyl propenoate (PTEA), also can be commercially available from Cognis.
Another kind of high refractive index thinner comprises the simple function biphenyl monomer that contains terminal biphenyl group, and wherein two phenyl groups are not condensed, but links to each other by key or end group, and this end group comprises by connecting two aromatic groups that base (as Q) connects.For example, when the connection base was methane, end group was the biphenyl methyl.Alternatively, wherein connecting base is-(C (CH 3) 2-, end group is a 4-cumyl phenyl.Simple function biphenyl monomer also comprises single ethylenic unsaturated group, and this group preferably can be by being exposed to radiation (as UV) polymerization.It is acrylate-based that simple function biphenyl monomer preferably comprises single (methyl) acrylate-based or single sulfo-(methyl).Common preferred acrylate functional group.
In some respects, xenyl directly is attached on ethylenic unsaturated (as (methyl) acrylate) group.Such exemplary monomer is vinylformic acid 2-phenyl-phenyl ester.Single (methyl) biphenyl acrylate or sulfo-(methyl) biphenyl acrylate monomer also can comprise the optional alkyl (as the alkyl of 1 to 5 carbon atom) that is replaced by one or more hydroxyls.Such exemplary material is vinylformic acid 2-phenyl-2-ethyl phenoxy.
In one embodiment, adopt simple function (methyl) the biphenyl acrylate monomer of representing by following general formula:
Figure G2008800076395D00121
Wherein R1 is H or CH 3
X is O or S;
N is (is 1,2,3,4,5,6,7,8,9 or 10 as n) in 0 to 10 scope;
And
L is the alkyl (being methyl, ethyl, propyl group, butyl or amyl group) with 1 to 5 carbon atom, and this alkyl can be chosen wantonly by hydroxyl and replace.
In another embodiment, simple function (methyl) biphenyl acrylate is represented by following general formula:
Figure G2008800076395D00131
Wherein R1 is H or CH 3
X is O or S;
Q is selected from-(C (CH 3) 2-,-CH 2,-C (O)-,-S (O)-and-S (O) 2-;
N is (is 1,2,3,4,5,6,7,8,9 or 10 as n) in 0 to 10 scope;
And
L is the alkyl (being methyl, ethyl, butyl or amyl group) with 1 to 5 carbon atom, and this alkyl can be chosen wantonly by hydroxyl and replace.
Can for example comprise vinylformic acid 2-phenyl-phenyl ester of obtaining with trade(brand)name " TO-2344 " from some commercially available concrete monomers of the Toagosei Co.Ltd. of Japan, 4-(2-phenyl-2-propyl group) phenyl acrylate that obtains with trade(brand)name " TO-2345 " and the vinylformic acid 2-phenyl-2-ethyl phenoxy that obtains with trade(brand)name " TO-1463 ".
Can adopt the various combinations of aromatics simple function (methyl) acrylate monomer.For example, (methyl) acrylate monomer that comprises phenyl group can be used in combination with one or more (methyl) acrylate monomers that comprises biphenyl group.In addition, also can adopt two kinds of different biphenyl (methyl) acrylate monofunctional monomer.
Polymerizing resin can randomly comprise various other the non-halogenated ethylenically unsaturated monomers up to 35 weight %.For example, when being cast into a fixed structure (as prism structure) and on the preformed polymeric membrane of polycarbonate during photocuring, polymerizable resin composition can comprise one or more N, N-two replaces (methyl) acrylamide monomers.These acrylamide monomers comprise N-alkyl acrylamide and N, N-dialkyl group acrylamide, and especially those contain C 1-4Alkyl.Example is N-N-isopropylacrylamide, N tert butyl acrylamide, N,N-DMAA, N, N-diethyl acrylamide, N-vinyl pyrrolidone and N-caprolactam.
Polymerizable resin composition also can randomly comprise the non-aromatics linking agent that contains at least three (methyl) acrylate groups up to 20 weight %.Suitable crosslinking agent comprises for example tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, two pentaerythrityl five (methyl) acrylate, two pentaerythrityl six (methyl) acrylate, TriMethylolPropane(TMP) oxyethyl group three (methyl) acrylate, three (methyl) vinylformic acid glyceryl ester, tetramethylolmethane propoxy-three (methyl) acrylate and two (trishydroxymethyl) propane four (methyl) acrylate.Can adopt the combination of any linking agent or linking agent.Because the reactivity of methacrylate based group often is lower than acrylate group, so linking agent does not preferably contain methacrylate functional.
Organic constituent can randomly comprise at least a contain at least three (methyl) acrylate groups (as, non-halogenated) linking agent.Suitable crosslinking agent comprises for example tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, two pentaerythrityl five (methyl) acrylate, two pentaerythrityl six (methyl) acrylate, TriMethylolPropane(TMP) oxyethyl group three (methyl) acrylate, three (methyl) vinylformic acid glyceryl ester, tetramethylolmethane propoxy-three (methyl) acrylate and two (trishydroxymethyl) propane four (methyl) acrylate.Can adopt the combination of any linking agent or linking agent.Because the reactivity of methacrylate based group often is lower than acrylate group, so linking agent does not preferably contain methacrylate functional.
The multiple linking agent of commercially available acquisition.For example, pentaerythritol triacrylate (PETA) can trade(brand)name " SR444 " from Sartomer Company, Exton, PA is commercially available; With trade(brand)name " Viscoat #300 " from Osaka Organic Chemical Industry, Ltd.Osaka, Japan is commercially available; With trade(brand)name " Aronix M-305 " from Toagosei Co.Ltd., Tokyo, Japan is commercially available; And with trade(brand)name " Etermer 235 " from EternalChemical Co., Ltd., Kaohsiung, Taiwan is commercially available.Viscoat 295 (TMPTA) is can trade(brand)name " SR351 " commercially available from Sartomer company.TMPTA can also trade(brand)name " Aronix M-309 " derive from Toagosei Co.Ltd..In addition, ethoxylated trimethylolpropane triacrylate and ethoxylation pentaerythritol triacrylate also can be commercially available from Sartomer with trade(brand)name " SR454 " and " SR494 " respectively.
Linking agent can be present in the polymerisable compound at least about the amount of 2 weight %.Usually, the amount of linking agent is not more than about 25 weight %.Linking agent can the extremely interior any amount existence of about 15 weight % scopes of about 5 weight %.
The polymerisable compound of UV-curable comprises at least a light trigger.Can in brightness enhancement film of the present invention, use single light trigger or its blend.In general, light trigger is partly soluble at least (for example, solvable under the processing temperature of resin), and colourless basically after the polymerization.Light trigger can be colored (for example yellow), and precondition is that light trigger becomes after being exposed to the UV light source colourless basically.
Suitable light trigger comprises monoacyl phosphine oxide and two acylphosphine oxide.The monoacyl phosphine oxide of commercially available acquisition or two acylphosphine oxide light trigger comprise 2,4, and the oxidation of 6-trimethylbenzoyl biphenyl is seen (can trade(brand)name " Lucirin TPO " from BASF (Charlotte, NC) commercially available); Ethyl-2,4, the oxidation of 6-trimethylbenzoyl phenyl see (also can trade(brand)name " Lucirin TPO-L " commercially available) from BASF; (can trade(brand)name " Irgacure 819 " commercially available from Ciba Specialty Chemicals) sees with two (2,4, the 6-trimethylbenzoyl)-phenyl oxidations.Other suitable light triggers comprise 2-hydroxy-2-methyl-1-phenyl third-1-ketone (can trade(brand)name " Darocur 1173 " commercially available from Ciba Specialty Chemicals) and other light triggers (can trade(brand)name " Darocur 4265 ", " Irgacure 651 ", " Irgacure 1800 ", " Irgacure 369 ", " Irgacure 1700 " and " Irgacure 907 " commercially available from Ciba Specialty Chemicals).
Can working concentration be about 0.1 light trigger to about 10 weight %.More preferably, working concentration is about 0.5 light trigger to about 5 weight %.In view of the trend that the yellowing that causes brightness enhancement film is arranged, normally disadvantageous greater than 5 weight %.One or more light triggers that can suitably adopt other to determine also by those of ordinary skills.
Can choose wantonly tensio-active agent (for example fluorochemical surfactant and based on organosilyl tensio-active agent) is included in the polymerisable compound, to reduce surface tension, improve wettability, to make coating more smooth and the defective of coating is still less waited.
Described before two (methyl) biphenyl acrylate monomer is particularly useful for making non-halogenated high refractive index polymerizable organic composite.In certain embodiments, composition does not contain inorganic nanoparticles.
In other embodiments, polymerisable compound also comprises inorganic nanoparticles.
(for example, colloidal state) nano particle of surface modification can effectively strengthen the wearing quality of goods or optical element and/or the amount of specific refractory power is present in the paradigmatic structure.The total amount that is present in the inorganic nanoparticles of the surface modification in polymerizing resin or the optical goods is at least 10 weight %, 20 weight %, 30 weight % or 40 weight %.Concentration is usually less than 70 weight %, and more generally is lower than 60 weight %, thereby makes polymerizable resin composition have suitable viscosity for use in casting and the curing process of making microstructured film.
Select this class particulate size to avoid significant visible light scattering.The mixture that maybe advantageously adopts the inorganic oxide particles type is to optimize optical property or material behavior and to reduce the total composition cost.The colloid nano particle of surface modification can be to have (non-association) primary particle sizes or the association granularity oxide particle greater than 1nm, 5nm or 10nm.Primary or association granularity is usually less than 100nm, 75nm or 50nm.Usually, primary or association granularity is less than 40nm, 30nm or 20nm.Preferably unassociated nano particle.These particulate are measured can be based on transmission electron microscope (TEM).Nano particle can comprise metal oxide, for example aluminum oxide, zirconium white, titanium dioxide and their mixtures, or their mixed oxide.The colloid nano particle of surface modification can condense basically fully.
The degree of crystallinity of Ning Ju nano particle (except that silicon-dioxide) (measuring as isolating metal oxide particle) usually greater than 55%, is preferably greater than 60%, more preferably greater than 70% fully.For example, the scope of degree of crystallinity can be about 86% or higher at most.Degree of crystallinity can be measured by x-ray diffraction technique.Crystal (as the zirconium white) nano particle of cohesion has high refractive index, and amorphous nano particle has lower specific refractory power usually.
The granularity of zirconium white and titania nanoparticles can be 5 to 50nm, or 5 to 15nm, or 8 to 12nm.Zirconium oxide nano grain can 10 to 70 weight %, or the amount of 30 to 60 weight % is present in durable goods or the optical element.The zirconium white that is used for composition of the present invention and goods can trade(brand)name " Nalco OOSSOO8 " obtain from Nalco Chemical Co., all right trade(brand)name " Buhler zirconia Z-WO sol " (Buhler zirconia Z-WO sol) is from BuhlerAG Uzwil, and Switzerland obtains.
Zirconia particles can use the hydrothermal technique preparation described in the U.S. Patent application No.2006/0148950 that announces.Nano particle is a surface modification.Surface modification relates to surface-modifying agent is connected to inorganic oxide (for example zirconium white) particle to change surface property.The overall goal that inorganic particle is carried out surface modification provides has uniform component and preferred low viscous resin, and this resin can be made the film that (for example making by casting and curing process) has high brightness.
Often nano particle is carried out surface modification with the consistency of raising with the organic substrate material.The nano particle of the surface modification in the organic substrate material usually is non-associated, non-cohesion or their combination.The light control film of the nano particle that contains these surface modifications of gained often has high optical clarity and low haze.Compare the gain that the adding of the nano particle of the surface modification of high refractive index (for example zirconium white) can improve brightness enhancement film with the film that only comprises the polymerization organic materials.
The monocarboxylic acid surface treatment agent preferably comprises the consistency group.Monocarboxylic acid can represent that wherein the A group is the group (as monocarboxylic acid) that can be connected to nano particle (as zirconium white or titanium dioxide) surface with chemical formula A-B, and B is the consistency group that contains multiple different functional groups.Hydroxy-acid group can and/or form ionic linkage by absorption and be connected to the surface.General select the consistency group B so that the polymerizing resin of it and optical goods (as the blast optical goods) is compatible.The consistency group B can be reactive or non-reacted, and can be polar or nonpolar.
The consistency group B that can give the nonpolar character of zirconia particles comprises (for example) aromatic hydrocarbons straight chain or side chain or aliphatic hydrocrbon.That representative example with nonpolar properties-correcting agent of carboxylic acid functional comprises is sad, dodecylic acid, stearic acid, oleic acid and their combination.
Can be randomly, the consistency group B can be reactive, make its can with the organic substrate copolymerization of optical goods (as the blast optical goods).For example, the free redical polymerization group such as (methyl) vinylformic acid consistency group can with the copolymerization of (methyl) acrylate-functional organic monomer, to generate the good brightness enhancement article of homogeneity.
Suitable surface modification is described in the U.S. Patent No. 60/891812 of U.S. Patent Publication No.2007/0112097 and submission on February 27th, 2007 to some extent.
Surface modified granules can be passed to the whole bag of tricks mixes in curable (that is, polymerisable) resin combination.One preferred aspect, utilize solvent exchange step, by this resin is joined in the colloidal sol of surface modification, remove by evaporation subsequently and anhydrate and solubility promoter (if you are using), thereby allow particles dispersed in polymerisable resin.Evaporation step can be finished by (for example) distillation, rotary evaporation or oven drying.On the other hand, surface modified granules can be extracted into can not with the miscible solvent of water in, carry out exchange of solvent (if necessary) then.Alternatively, another method that the nano particle of surface modification is mixed in the polymerizing resin relates to the particle drying powdered through modification, adds resin material subsequently, and particles dispersed is in this resin material.Drying step in this method can be finished by the ordinary method (for example oven drying or spraying drying) that is fit to this system.
Optical layers can directly contact with basic unit or with basic unit's optical alignment, and can have size, shape and the thickness of the bootable or concentrated light stream of the optical layers of making.Optical layers can have the surface of structurizing or micro-structural, and this surface can have for example U.S. Patent No. 7,074, any described in 463 and in a plurality of available figure that illustrates.Microstructured surface can be a plurality of parallel longitudinal direction ridges along the length of film or width extension.These ridges can be formed by a plurality of prism tips.These tops can be sharp, circle or that flatten or cut flat.For example, can make ridge become circle, make its radius in 4 to 7 to 15 microns scope.
These comprise rule or irregular prismatic figure, and it can be annular prismatic figure, solid angle figure or any other lenticular microstructure.A kind of available microstructure is to serve as the regular prism figure of complete internal reflection film when being used as brightness enhancement film.Another kind of available microstructure is to serve as the prismatic figure of three rigging-angle cones of reflex reflection film or element when being used as reflectance coating.Another kind of available microstructure is to serve as the prismatic figure of optical element when being used for optical display.Another kind of available microstructure is to serve as the prismatic figure of optical inversion film when being used for optical display.
Basic unit can be natural goods and the composition that is applicable to optical articles (promptly being designed for the product of control light stream).As long as optically enough transparent and structurally firm as to be enough to be assembled into or be applied in the concrete optical articles, almost any material all can be used as base material.Can select to have the base material of enough heatproofs and ageing resistance, thereby make the performance of optical articles can not descend as time passes.
Be used for the concrete chemical constitution of base material of any optical articles and thickness and can be depending on requirement the concrete optical articles that will construct.That is to say, between intensity, transparency, temperature tolerance, surface energy, requirements such as adhesivity, carry out balance optical layers.
The available base material comprises (for example) styrene-acrylonitrile, cellulose acetate butyrate, cellulose acetate propionate, cellulose triacetate, polyethersulfone, polymethylmethacrylate, urethane, polyester, polycarbonate, polyvinyl chloride, polystyrene, PEN, based on the multipolymer of naphthalic acid or blend, poly-cycloolefin, polyimide and glass.Optional is that described base material can contain these mixtures of material or composition.In one embodiment, substrate can be a multi-layer type, perhaps can contain to suspend or be dispersed in dispersed component in the external phase.
For example with for the product (for example brightness enhancement film) of microstructure, the example of preferred substrate comprises polyethylene terephthalate (PET) and polycarbonate for some optical articles.The example of available polyethylene terephthalate film comprises other polyethylene terephthalate of optical grade and derives from DuPont Films (Wilmington, MELINEX Del) TMPET.
Some base materials can be optically active, and can be used as polarized material.Known multiple substrate (being also referred to as film or substrate in this article) can be used as polarized material in the optical articles field.For example, optionally absorb the light that passes through by in thin-film material, introducing the dichroic polarizing sheet, thereby can make light generation polarization by film.Also can be by introducing inorganic materials (for example Ding Xiang mica wafer) or realizing light polarization by the discontinuous phase (for example being dispersed in the optical modulation liquid crystal of the one-tenth microballon in the continuous film) that is dispersed in the continuous film.As a kind of selection, can prepare film with the superthin layer of differing materials.For example, can be by adopting such as oriented film, applying electric field or methods such as magnetic field and paint-on technique and make polarized material in the described film along the polarization direction orientation.
The example of polarization film comprises as U.S. Patent No. 5,825,543 and 5,783, and those described in 120.U.S. Patent No. 6,111 has been described the purposes of these polarization films and brightness enhancement film combination in 696.
Second example that can be used as the polarization film of substrate is U.S. Patent No. 5,882, those films described in 774.Commercially available film is the multilayer film that 3M sells with trade(brand)name DBEF (reflecting type polarizing brightness enhancement film).The purposes of this type of multilayer polarization optical film in brightness enhancement film be in U.S. Patent No. 5,828, describes to some extent in 488.
The universal method of measuring the validity of this type of light recycle is the gain of measuring optical thin film.As used herein, " relative gain " is defined as: as measuring by the testing method described in the example, and the ratio of the axial brightness the when axial brightness of optical thin film (or optical thin film assembly) when being arranged at the light box top and light box top do not have the optics film and exist.This definition can be summarized by the following relationship formula:
Relative gain=(brightness of measuring when having optical thin film)/
(brightness of measuring during no optics film)
In one embodiment, the optical thin film with microstructured surface that comprises light transmission (as, solidified) polymer materials has been described.This optical thin film is unpolarized film basically, and its monolithic relative gain is at least 1.60.Monolithic gain is not more than 2.05 usually relatively.Therefore, the monolithic relative gain can also be comprise 1.65,1.70,1.75,1.80,1.85 and 1.90 or a series of relative gain value scopes of bigger value in any numerical value.
In other embodiments, the present invention relates to comprise two or more films or the multiple assembly of forming by two or more films.That each assembly comprises is contiguous second (as, micro-structural or non-structure) first microstructured optical films of optical thin film.
So-called vicinity is meant fully approaching." vicinity " can comprise that first microstructured optical films contacts with second optical thin film, for example by film only being stacked or can connecting film by variety of way.Film can be mechanically, chemical mode, hot mode or their combination connect.Chemical mode comprises various pressure-sensitive, solvent-borne types and hotmelt and two portions curing adhesive composition (be exposed to heat, moisture or radiation after crosslinked).Hot mode comprises and for example heats welding of roller platen, radio frequency (RF) and ultra-sonic welded.Optical thin film also can be in the whole plane of film, only selected point or only edge (as, connect continuously).Alternatively, Lin Jin optical thin film also can be separated mutually by air interface.Air interface can form by the thickness that increases one or two optical thin film periphery, for example by using tackiness agent.When film is to pile up rather than when being laminated together, the air interface between the optical thin film may only have several microns.
In certain embodiments, contiguous second microstructured optical films of first microstructured optical films.In this class component, the microstructured surface of bottom thin film preferably is arranged on the non-structure surface of adjacent top film.For the embodiment that adopts prismatic microstructured film, the prism of film is arranged in parallel on a main direction usually, and prism is separated by groove.General preferred with the align prism (or groove) of second (as the bottom) microstructured optical films of the mode of stacking, make that the prism of this prism and first (as the top) film is vertical substantially.Yet, also can adopt other arrangement modes.For example, the prism of second optical thin film can be with respect to the prism setting of second optical thin film so that groove or prismatic intersect the angle that forms about 70 ° to about 120 ° scope.
In a concrete assembly, the contiguous second unpolarized basically microstructured optical films of the first unpolarized basically microstructured optical films.The gain of this assembly is at least 2.50.First optical thin film can be identical with second optical thin film also can be different.For example, second film can have different substrate combination, different microstructured surface composition, and/or can have different surface micro-structures.The relative gain of this class component is usually less than 3.32.Therefore, the relative gain of this class component can also be comprise 2.55,2.60,2.65,2.70,2.75,2.80,2.85,2.90,2.95 and 3.00 or a series of relative gain value scopes of bigger value in any value.
For with undefined term, be as the criterion with these definition, unless provided different definition in addition in the claims or in other parts of this specification sheets.
Term used herein " microstructure " is as U.S. Patent No. 4,576, in 850 define and explain.Therefore, it is meant the structure on the surface of the predetermined ideal purposes of describing or characterize the goods with microstructure or function.Discontinuous thing on the described product surface such as projection and depression will depart from the average centerline of passing microstructure in shape, make the above area summation that surface profile surrounded of medullary ray equal the following area summation of this line, described line is substantially parallel with the nominal surface (band microstructure) of goods.The described height that departs from will be generally approximately+/-0.005 to+/-750 microns, this characteristic features length (for example 1-30cm) by optics or electron microscope surface measurements gets.Described average centerline can be piano shape, depression, convex, aspheric surface or their combination.Described depart from be the low order of magnitude (for example from+/-0.005 to+/-0.1 or preferred+/-0.05 micron) and the goods of the low or few generation of described offset frequency (promptly the surface is without any significant discontinuous thing) be that surfaces of those band microstructures are the goods on the surface of " smooth " or " smoothly " substantially, this based article can be used as (for example) precison optical component or has the element at precision optics interface, for example ophthalmic lens.The described low and goods frequent generation of the order of magnitude that depart from comprise that those have the goods of anti-reflection microstructure.Described depart from be the high order of magnitude (for example from+/-0.1 to+/-750 microns) and be attributable to comprise a plurality of effective discontinuums (identical or different, and with random or orderly mode spatially separate or in abutting connection with) the goods of microstructure be goods such as reflex reflection cube comer sheetings, linear Fresnel lens, video disc and brightness enhancement film.The surface of band microstructure can comprise effective discontinuum of the described low order of magnitude and the high order of magnitude simultaneously.The surface of band microstructure can comprise outside or non-effective discontinuum, as long as the predetermined ideal function of described goods is not significantly disturbed or influence unfriendly to their amount or type.
" specific refractory power " or " refractive index " is meant the absolute refractive index of material (for example monomer), and absolute refractive index is understood that the ratio of electromagnetic radiation speed in a vacuum and the radiation velocity in this material.Specific refractory power can use currently known methods to measure, and use Abbe refractometer or Bauschand Lomb refractometer (Bausch and Lomb Refractometer usually, article No. 33.46.10) (commercially available acquisition, for example, measure at visible region from Fisher Instruments (Pittsburgh, PA)).Common sense be that according to used instrument, the specific refractory power that records generally has variation to a certain degree.
" (methyl) acrylate " is meant acrylic compound and methacrylate compound.
Term " nano particle " defines in this article and is meant the particle (primary particle or associating primary particle) of diameter less than about 100nm.
" the colloid nano particle of surface modification " refers to that each all has the nano particle of modified surface, and this makes nano particle can form stable dispersion.
Not agglomerative dispersion after " stabilising dispersions " is defined as wherein in this article, and the colloid nano particle leaves standstill for some time under envrionment conditions (for example about 24 hours), described envrionment conditions is for example room temperature (about 20-22 ℃), barometric point and do not have extreme electromagnetic force.
" gathering " is meant the potent association between the primary particle, and particle may mutually combine by chemical bond.Be difficult to realize aggregate is resolved into smaller particles.
" cohesion " is meant the weak association between the primary particle, and they may be to be together with each other by electric charge or polarity, and can be broken down into small individuals.
" primary particle sizes " refers to the mean diameter of individual particle (non-gathering, non-cohesion).
Numerical range by the end points statement comprises all numerical value (for example, 1 to 5 comprises 1,1.5,2,2.75,3,3.80,4 and 5) that are included in this scope.
As used in this specification and attached claims, unless in have in addition clearly statement, the word of singulative " ", " a kind of " and " described " comprise a plurality of things that refer to.Therefore, this phraseology of composition that for example, comprises " a kind of compound " comprises the mixture of two or more compounds.As used in this specification and attached claims, term " or " generally with comprise " and/or " the meaning use, unless in have in addition clearly statement.
Except as otherwise noted, otherwise should understand, all expression component contents, character all numerals such as are measured and are all modified with term " about " in all cases in this specification sheets and the claim.
The present invention should not be considered as being subject to specific examples as herein described, contains all aspects of the present invention of clearly setting forth in the appended claims and be construed as.For those skilled in the art in the invention of indication of the present invention, read this specification sheets after, the multiple structure that multiple modification, equivalent processes and the present invention are suitable for will be conspicuous.
Example:
Two (methyl) biphenyl acrylate is monomeric synthetic
1. 2, the preparation of 2 '-dihydroxyl oxyethyl group-biphenyl
Figure G2008800076395D00221
In the 2000mL three neck round-bottomed bottles of being furnished with overhead stirrer, temperature probe and heating unit, add 2,2 '-dihydroxyl-biphenyl (500g, 2.68 mole, 1.0eq), ethylene carbonate (520.2g, 5.9 moles, 2.2eq.), potassiumiodide (5g, 0.03 mole, 0.01eq.), N, dinethylformamide (DMF) (47g, 50mL), and be heated to 150 ℃.By GC monitoring reaction, afterreaction finished in 4 hours.Reaction is cooled to 40 ℃, adds the 1000mL ethyl acetate, and with 500mL sodium chloride salt water washing 3 times.With ethyl acetate MgSO 4Drying is filtered and is concentrated in a vacuum, obtains Vandyke brown product (736g, 99%).
2. 2, the preparation of 2 '-diethoxy-biphenyl diacrylate (" BPDA-1 ")
Figure G2008800076395D00231
In the 2000mL three neck round-bottomed bottles of being furnished with overhead stirrer, Dean Stark water trap and temperature probe, add 2,2 '-dihydroxyl oxyethyl group-biphenyl (368g, 1.34 mole, 1.0eq.), toluene (700g), Prostab 5198 (0.023g), N-nitrosophenyl hydroxylamine aluminium (NPAL) (0.059g), manganous acetate (0.023g), vinylformic acid (212.7g, 2.95 moles, 2.2eq), tosic acid (pTSA, 23.1g, 0.13 mole, 0.1eq.), and reflux.2.5 after hour, reaction stops, and has about 45/45 product/intermediate and 10% raw material.With vinylformic acid (26g) and pTSA (5g) processing reaction thing and continuation backflow.Not observing other product generates.Add vinylformic acid (50g) and methylsulfonic acid (5g).Dean Stark water trap continues to collect moisture.After reaction is spent the night, obtain about 75% product and 7% mono acrylic ester.Reactant with sodium chloride brine (200mL) washing 3 times, with salt solution (200mL) washing that contains some 1N NaOH 3 times, with saturated sodium carbonate solution (200mL) washing 3 times, is used MgSO 4(5g) drying is filtered and is concentrated in a vacuum, reclaims product.This product (500g) with 50% hexane/chloroform by the elution of 3 posts series to carry out purifying, being recovered to purity is 220g product and 3 kinds of other cuts that purity is lower of 92% (GC).The detecting refractive index of monomer (being uncured) is 1.559.
3. 2, the preparation of 2 '-biphenyl diacrylate (" BPDA-2 ")
Figure G2008800076395D00241
In the 1000mL three neck round-bottomed bottles of being furnished with overhead stirrer and temperature probe, add 2,2 '-dihydroxyl-biphenyl (50g), Prostab 5198 (0.02g), DMF (150mL) and triethylamine (59.8g).Reaction is cooled to＜0C with methyl alcohol/the dry ice bath, and adds acrylate chloride (51g) at leisure.GC shows that reacting major part finishes, and obtains about 15% mono acrylic ester.Add triethylamine (10g), add acrylate chloride (9g) then.GC shows that reaction finishes.With (300mL) methyl tertiary butyl ether and (300mL) deionized water processing reaction product.Separate organic moiety and with 200mL sodium chloride salt water washing 5 times.Handle organic moiety with the 50g flocculating aids, mixing is also passed through the skim filtered through silica gel.Concentrated filtrate under vacuum reclaims yellow oil.Should be dissolved in the 300mL chloroform by oil (69g), and filter by short silicagel column (5.5 inches of diameters, thick 4 inches), and with chloroform/heptane elution.Under vacuum, concentrate eluant to reclaim product (52g).GC shows that the purity of product is greater than 98%.The detecting refractive index of monomer (promptly uncured) is 1.571.
Polymerizable resin composition
Polymerizable resin composition 1: in amber wide-necked bottle, with 50 parts of BPDA-2,25 parts of CN120 (epoxy acrylates, can derive from Sartomer Company, Exton, PA, the viscosity of Sartomer report is 2150cps (25 ℃), specific refractory power is 1.5556, second-order transition temperature is 60 ℃), (ethoxylated bisphenol a diacrylate can derive from SartomerCompany to 25 parts of SR601, and the viscosity of report is 1080cps (25 ℃), specific refractory power is 1.5340, second-order transition temperature is 60 ℃) and 0.6 part of Darocur 4265 (can derive from Ciba SpecialtyChemicals, Tarrytown, NY) thorough mixing is together.The detecting refractive index of this resin combination is 1.560.
Polymerizable resin composition 2: in amber wide-necked bottle, 50 parts of BPDA-1,25 parts of CN120,25 parts of SR601 are in the same place with 0.6 part of Darocur 4265 thorough mixing.The detecting refractive index of this resin combination is 1.553.
Polymerizable resin composition 3: in amber wide-necked bottle, 50 parts of BPDA-1,50 parts of CN120 are in the same place with 0.6 part of Darocur 4265 thorough mixing.The detecting refractive index of this resin combination is 1.558.
Be used for the optical thin film specimen preparation of polymerizable resin composition 1-3:
Use polymerizable resin composition 1-3 to prepare the brightness enhancement film sample.About 3 grams are warm resin-coated on the pre-prepd polyethylene terephthalate of 2 mils (polyester) film, this pet film can trade(brand)name " Melinex 623 " derive from DuPont, and is close to the microstructured tool that has with commercially available similar 90/24 figure of Vikuiti TBEF-90/24 and places.Make polyethylene terephthalate, resin and mould by being set to about 150 heating laminator, to form the uniform sample of thickness.The instrument that makes the resin sample that comprises film and coating with 30fpm by in D type fluorescent tube, comprising the Fusion UV treater of two 600W/10, to solidify this film.Polyethylene terephthalate and solidified resin are removed and cut into sample from mould.It is as follows to estimate the employed testing method of this film:
ZrO 2 Colloidal sol
The ZrO that is used for this example 2Colloidal sol has following characteristic (measuring according to the U.S. Patent application No.2006/0204745 that announces and the photon correlation spectroscopy (PCS) described in the U.S. Patent application No.11/078468, X-ray diffraction and gravitational thermal analysis method):
Figure G2008800076395D00251
Figure G2008800076395D00252
The %C/T=primary particle sizes
ZrO 2The preparation of colloidal sol is described in the U.S. Patent application No.11/078468 of U.S. Patent application No.2006/0204745 that announces and submission on March 11st, 2005 to some extent.
Polymerizable resin composition 4
With ZrO2 colloidal sol (500g, 40.87% solid), mono succinate-[2-(2-methoxy ethoxy)-ethyl] ester (43.2g, in 1-methoxyl group-2-propyl alcohol, be 50% solid), 1-methoxyl group-2-propyl alcohol (345g), mono succinate-(2-acryloxy-ethyl) ester (62.6g is 50% solid in 1-methoxyl group-2-propyl alcohol), vinylformic acid 2-phenyl-phenyl ester/diethoxy biphenyl diacrylate (BPDA-1) blend and ProStab 5198 (.08g) (128.3g) of 50/50 add in the three neck round-bottomed flasks of 2L.Remove water and alcohol by vacuum distilling, make the dispersions obtained about 53.0%ZrO2 in acrylic resin that is.Using the specific refractory power of the final blend of Bausch and Lomb refractometer (article No. 33.46.10) mensuration is 1.657.The 28.4g resin blend is added in the amber wide-necked bottle.In amber wide-necked bottle, add 0.71g SR 238 (HDODA derives from SartomerCo.) and 0.14g Darocure 1173 again, and thorough mixing.The detecting refractive index of blending resin is 1.647.
Be used for the optical thin film specimen preparation of polymerizable resin composition 4:
Place one 8 " * 11 " metal motherboard on the hot plate and be heated to 140 °F, this metal motherboard by nominal pitch be spaced apart 50 microns 90 the degree prismatic linear array form, this prism figure and VikuitiBEF II (can be from 3M Co., St.Paul, MN is commercially available) on prismatic geometricdrawing similar.Use disposable volumetric pipette, the polymerizing resin globule of the 4mL of example 1 or example 2 is coated on the master tool respectively.Then, MELINEX 623 polyethylene terephthalates (specification 500) that derive from Dupont Teijin Films are placed on resin globule and the master tool.
Adjust the direction of pet film, make the orientation of linear prism and the high gain axle approximate vertical of film (90 °+/-20 °).With master tool, resin and the polyethylene terephthalate heating nip rolls by 160, nip rolls imposes enough pressure and makes resin completely filled master tool, removes any air of carrying secretly simultaneously then.Use then and derive from Fusion UVSystems, Inc.Gaithersburg, the 600W/in. variable power supply of MD exposes the master tool of the filling linear velocity with 50fpm twice in the ultraviolet radiation from " D type fluorescent tube ".Manually pet film is removed from master tool then.The coat-thickness of the prismatic coating that forms on the pet film is about 25 microns.
The gain test method
With deriving from Photo Research, Inc, Chatsworth, the SpectraScan of CA with MS-75 lens TMThe PR-650 spectrocolorimeter is measured the optical property of film.Film is placed the top of the hollow light box of diffuse transmission.The diffuse transmission of light box and diffuse-reflectance can be depicted as lambertian pattern.Light box is the hexad hollow cube, is of a size of about 12.5cm * 12.5cm * 11.5cm (length * wide * height), and it is that the PTFE diffusing panel of about 6mm is made by thickness.The one side of selecting this light box is as sample surfaces.The specular reflectance excluded measured value at the sample surfaces place of hollow light box is about 0.83 (for example average out to is about 83% in the 400-700nm wavelength region, adopts following method to measure).In the gain test process, the circular hole of the about 1cm of this light box by being positioned at light box bottom throw light on internally (bottom of this light box is relative with sample surfaces, and light is internally according to sample surfaces).Provide this illumination with stable band incandescent light sources, wherein this light source is connected to fibre bundle (the Fostec DCR-II with fibre bundle extended line of the about 1cm of diameter that is used for conducting light, can derive from Schott-Fostec LLC, Marlborough MA and Auburn, NY).Between sales kit (SK) and photographic camera, place the linear absorption polaroid (as Melles Griot 03 FPG 007) of standard.Camera focus on the light box sample surfaces of camera lens apart from about 34cm, and is placed the about 2.5cm of camera distance camera lens place with absorptive polarizer.Do not have being placed with polaroid under the situation of sample thin film, record the brightness＞150cd/m of illuminated light box 2When sample thin film is parallel to the light box sample surfaces and places (sample thin film contacts with light box usually), incide the sample brightness on the sample surfaces plane of light box with the PR-650 measuring vertical.By being compared with the brightness of the independent light box that records in the same manner, sample brightness calculates relative gain.Whole mensuration process is all carried out in the darkroom, to eliminate source of stray light.
Be the integrating sphere that scribbles Spectralon of 15.25cm (6 inches), stable broadband halogen light source and measure the specular reflectance excluded of light box that with diameter (Sutton NH) provides by Labsphere for integrating sphere, light source and power supply for the power supply of light source power supply.Integrating sphere has three openings, an opening is light inlet (diameter is 2.5cm), one is the detector mouth (diameter is 2.5cm) that is 90 degree along second, and the 3rd opening is the sample port (diameter is 5cm) that is 90 degree along the 3rd (promptly with all vertical axle of preceding two axles).PR-650 spectrocolorimeter (the same) is focused on the detector mouth of its about 38cm.The reflection efficiency of integrating sphere adopts the calibration that is provided by Labsphere company to calculate with reflectance standard (SRT-99-050), and this standard film has about 99% specular reflectance excluded.This standard film is calibrated by Labsphere company, and can consult NIST standard (SRS-99-020-REFL-51).The reflection efficiency of integrating sphere is calculated as follows:
Spheroid luminance factor=1/ (1-R spheroid * R standard)
In this case, the spheroid luminance factor is the ratio that covers the brightness gained that the brightness that records at detector mouth place after the sample port records at detector mouth place when not covering sample port with reference sample.When the reflection efficiency (R standard film) of this luminance factor and calibration standard sheet is known, get final product the reflection efficiency R spheroid of calculated product bulb separation.And then this value is used for similar formula, with the reflectivity of measure sample (being the PTFE light box in this case):
Spheroid luminance factor=1/ (1-R spheroid * R sample)
At this moment, the measured spheroid luminance factor resulting ratio of brightness that to be the detector brightness of sample when being positioned at sample port record when not having sample.Owing to learnt the R spheroid from above experiment, therefore can calculate the R sample.Press these reflectivity of wavelength distance computation of 4nm, and write down the mean value of these reflectivity in the 400-700nm wavelength region.
In the vertical direction (or with respect to the front of diffusion light box used in the E.T. tester vertical orientated) is measured monolithic gain.In the constructed by lamellae of level or intersection, the base lamina of film stack is vertically oriented and the positive level of top laminate and diffusion light box or parallel.
Following table 1 shows the test result of optical thin film.When using monomer of the present invention and resin combination, the luminance gain that these films are realized is very high.
Table 1
Polymerizable resin composition Monolithic gain The cross-piece gain
??1 ??1.63 ??2.59
??2 ??1.63 ??2.56
??3 ??1.61 ??2.62
??4 ??1.80 ??2.97

Claims (25)

1. optical thin film with polymeric microstructure surface, described polymeric microstructure surface comprises the reaction product of polymerizable resin composition, described polymerizable resin composition comprises at least a two (methyl) biphenyl acrylate monomer that contains two aromatic rings that link to each other by the C-C key of 10% to 100 weight %, and wherein said two (methyl) biphenyl acrylate monomer is a liquid at 25 ℃.
2. optical thin film with polymeric microstructure surface, described polymeric microstructure surface comprises the reaction product of polymerizable resin composition, at least a two (methyl) biphenyl acrylate monomer that contains two aromatic rings that link to each other by the C-C key that described polymerizable resin composition comprises 10% to 100 weight %, and described aromatic ring at the ortho position or a position have at least one (methyl) acrylate substituting group.
3. according to each described optical thin film in claim 1 or 2, wherein said two (methyl) biphenyl acrylate monomer has following formula:
H 2C=(R1) C (O)---Ar-Ar---(O) C (R1)=CH 2Wherein each Ar group is phenyl or naphthyl independently, and R1 is H or methyl.
4. according to each described optical thin film among the claim 1-3, wherein each (methyl) acrylate group and aromatic ring group are at the ortho position or a position bonding.
5. according to each described optical thin film among the claim 1-3, wherein each (methyl) acrylate group and aromatic ring group are at the ortho position bonding.
6. according to each described optical thin film among the claim 1-3, wherein each (methyl) acrylate group by molecular weight less than the connection base of 1200 gram/moles independently with the aromatic ring bonding.
7. optical thin film according to claim 6, wherein said connection base is an alkoxyl group.
8. optical thin film according to claim 3, wherein said two (methyl) biphenyl acrylate monomer has following formula:
Wherein each R1 is H or methyl independently;
Each R2 is Br independently;
M is in 0 to 4 scope;
Each Q is O or S independently;
N is in 0 to 10 scope;
C2 to the C12 alkyl of L for can randomly being replaced by one or more hydroxyls;
Z is an aromatic ring;
T is 0 or 1 independently;
And-Q[L-O] n C (O) C (R1)=CH 2In the group at least one is substituted in an ortho position or a position.
9. optical thin film according to claim 8, wherein Q is O.
10. optical thin film according to claim 8, wherein n is 0,1 or 2.
11. optical thin film according to claim 8, wherein L is C2 or C3.
12. optical thin film according to claim 8, wherein L is C2 or the C3 that hydroxyl replaces.
13. optical thin film according to claim 8, wherein each-Q[L-O] nC (O) C (R1)=CH 2Be substituted in an ortho position or a position.
14. optical thin film according to claim 8, wherein each-Q[L-O] nC (O) C (R1)=CH 2Be substituted in the ortho position.
15. optical thin film according to claim 8, wherein z is a condensed.
16. optical thin film according to claim 8, wherein said two (methyl) biphenyl acrylate monomer is non-halogenated.
17. optical thin film according to claim 8, wherein said monomer has following formula:
Figure A2008800076390004C1
18. optical thin film according to claim 8, wherein said monomer has following formula:
Figure A2008800076390004C2
19. according to each described optical thin film among the claim 1-3, wherein said monomeric specific refractory power is at least 1.55.
20. the optical thin film with polymeric microstructure surface, described polymeric microstructure surface comprises the reaction product of polymerizable resin composition, and described polymerizable resin composition comprises:
One or more of 25 weight % to 75 weight % at the ortho position or a position have (methyl) acrylate substituent two (methyl) biphenyl acrylate monomer; And
One or more dihydroxyphenyl propane two (methyl) acrylate monomers of 25 weight % to 75 weight %.
21. according to each described optical thin film among the claim 1-20, wherein said polymerizable resin composition is non-halogenated.
22. according to each described optical thin film among the claim 1-20, wherein said polymerizing resin does not contain inorganic nanoparticles.
23. according to each described optical thin film among the claim 1-20, wherein said polymerizing resin comprises the inorganic nanoparticles of the surface modification of at least 10 weight %.
24. optical thin film according to claim 23, wherein said inorganic nanoparticles comprises zirconium white.
25. according to each described optical thin film among the claim 1-24, wherein said optical thin film is that monolithic gain is at least 1.59 brightness enhancement film.
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