WO1997023524A1 - Materiaux acryliques thermodurcissables a haute temperature de transition vitreuse - Google Patents

Materiaux acryliques thermodurcissables a haute temperature de transition vitreuse Download PDF

Info

Publication number
WO1997023524A1
WO1997023524A1 PCT/US1996/020310 US9620310W WO9723524A1 WO 1997023524 A1 WO1997023524 A1 WO 1997023524A1 US 9620310 W US9620310 W US 9620310W WO 9723524 A1 WO9723524 A1 WO 9723524A1
Authority
WO
WIPO (PCT)
Prior art keywords
mixture
acrylates
acrylate
polymerization initiator
meth
Prior art date
Application number
PCT/US1996/020310
Other languages
English (en)
Inventor
Chengzeng Xu
Terri R. Carvagno
James T. Yardley
Original Assignee
Alliedsignal Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Alliedsignal Inc. filed Critical Alliedsignal Inc.
Publication of WO1997023524A1 publication Critical patent/WO1997023524A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups

Definitions

  • the present invention relates to novel acrylic compositions, optical films produced from such compositions, a process for making such films, and articles of manufacture produced therefrom. More specifically, the invention is directed to an optical film useful as a substrate for visual flat panel displays (FPDs) such as liquid crystal displays (LCDs).
  • FPDs visual flat panel displays
  • LCDs liquid crystal displays
  • LCDs Due to product requirements as well as complex fabrication processes, the substrates for LCD cells must meet stringent prerequisites. Most flat panel visual displays, such as LCDs use an inorganic glass as its substrate.
  • glass suffers from a number of disadvantages.
  • the high price of the special grade of glass that meets stringent LCD requirements as well as the inability of glass to be used in a roll-to-roll assembly line contributes to the high cost of LCDs.
  • Glass is also less desirable for portable LCD devices because of its fragility and weight. The fragility of glass also causes many other problems for storage and transportation.
  • the shape of glass for LCDs is also limited due to its brittleness.
  • Plastic substrates offer many advantages 5 compared to glass substrates. It has thus been proposed and attempted to use transparent plastic substrates to replace glass as LCD substrates. This is desired not only because of the need for rugged display products but also because of the greater manufacturing yields it enables.
  • thermoplastic plastic substrates are limited since they cannot meet all the LCD display requirements. Most suffer from low heat distortion temperature (HDT), insufficient stability, high birefringence, low
  • thermosetting acrylic compositions which are useful for producing high optical quality films which are clear, transparent materials with HDT over 210 °C, surface hardness of 3H or higher, high chemical resistance, and low birefringence.
  • the materials are thermally stable enough to endure high temperature device fabrication processes such as coating of polyimide alignment layers and thermal cycles for final product applications in different environments.
  • the materials possess good optical properties including low birefringence for high contrast and color purity, low haze high transmission for minimal light loss to reduce power consumption and increase brightness.
  • the films produced with these thermoset acrylics also demonstrate high flatness, chemical resistance, scratch resistance and dimensional stability.
  • thermosetting (meth)acr late materials for applications in FPDs, especially LCDs, as substrates having excellent properties and performance that meet or exceed the key LCD industry material requirements.
  • Figure 1 is a schematic representation of a color liquid crystal display.
  • thermosetting acrylic composition which comprises: a) a mixture of polymerizable acrylates comprising: (i) at least one multifunctional acrylic monomer having the generalized formula PC ⁇ 7US96/20310
  • Ri is an aliphatic, aromatic or mixed aromatic and aliphatic moiety having a molecular weight of less than about 500; n ranges from 2 to about 6, and R is H or CH . ; (ii) at least one multifunctional acrylic oligomer having the generalized formula
  • R 3 is an aliphatic, aromatic or mixed aromatic and aliphatic moiety having a molecular weight of from about 500 to about 30,000; m ranges from 2 to about 10, and R_ is H or CH 3 ; b) a bimodal polymerization initiator composition comprising a mixture of (i) and (ii):
  • At least one polymerization initiator selected from the group consisting of at least one photopolymerization initiator capable of initiating polymerization of the mixture of acrylates (a) upon exposure to sufficient actinic radiation, and at least one low temperature thermal polymerization initiator capable of initiating polymerization of the mixture of acrylates (a) at a temperature of from about 40 °C to about 120 °C; (ii) at least one high temperature thermal polymerization initiator capable of initiating polymerization or crosslinking of the mixture of acrylates (a), and the product of the polymerization of the mixture of acrylates (a) with the at least one polymerization initiator (i), at a temperature of from about 180 °C or more.
  • the invention also provides a method of producing a thermoset acrylic film which comprises (I) forming the above thermosetting acrylic composition; (II) casting the thermosetting composition into a film having a substantially uniform thickness; (HE) polymerizing the mixture of polymerizable acrylates with the at least one polymerization initiator (I); and (IV) further o polymerizing or crosslinking the result from (IH) with the at least one thermal polymerization initiator (ii).
  • thermoset acrylic film which comprises a substantially uniform layer of a polymerized and crosslinked acrylic 5 composition, which acrylic composition, prior to being polymerized and crosslinked comprises the above thermosetting composition; said film having a thickness of from about 0.05 mm to about 1.0 mm, being substantially colorless on the Gardner Yellow Color Scale according to ASTM D1544, having a optical transparency in the visible region of the electromagnetic o spectrum as measured by a spectrophotometer of at least about 85%, excluding reflection loss; Tg of at least about 190°C; an optical birefringence of less than about 15 nm net retardation per 100 ⁇ m of film thickness; a surface hardness as measured by ASTM D3363 of at least about 3H; a coefficient of thermal expansion of less than about 60 ppm K; sufficient 5 chemical resistance to pass ASTM D543; sufficient flexibility to pass the 0.5 inch mandrel test of ASTM D1737; is capable of retaining optical transparency when heated at 200 °C for 1 hour, and having less than about
  • multifunctional means a compound which have more than one reaction site available for a polymerization or crosslinking reaction.
  • the multifunctional polymerizable acrylate monomer or monomers used in this invention have the generalized formula O
  • R t is an aliphatic, aromatic or mixed aromatic and aliphatic moiety having a molecular weight of less than about 500; n ranges from 2 to about
  • R_ comprises flexible aliphatic chains of about 10 carbon atoms or less and preferably 4 carbon atoms or less per acrylate functionality.
  • Suitable linkage structures include methylene, ethylene, propylene, hexylene, ethylene oxide, ethoxylated bisphenol A, phenylene, etc.
  • thermally stable molecular structures of Ri are preferred.
  • Suitable linkage structures include saturated aliphatic and aromatic hydrocarbons, ethers and esters. To ensure low birefringence, Ri linkages with low stress optic coefficient and optical polarizabiuty are preferred.
  • Suitable linkage structures include alkylene, alkylene oxide, etc.
  • R 2 isCH 3 .
  • suitable multifunctional acrylate monomers include, but are not limited to bifiinctional monomers such as 1 ,4-butanediol di(meth)acrylate; butylene glycol di(meth)acrylate; ethoxylated bisphenol A di(meth)acrylate; 1,6- hexanediol di(meth)acrylate; and neopentyl glycol di(meth)acrylate; tri unctional monomers such as ethoxylated trimethylolpropane tri(meth)acrylate; pentaerythritol tri(meth)acrylate; tris(2-hydroxyethyl) 5 isocyanurate tri(meth)acrylate; and trimethylolpropane tri(meth)acrylate; tetrafunctional monomers such as di-trimethylolpropane tetra(
  • the acrylate monomer is present in an amount 20 of from about 10% to about 98%, preferably from about 50% to about 95% and most preferably from about 75% to about 95% based on the weight of the overall thermosetting acrylic composition.
  • thermosetting acrylate polymers are very brittle 5 and not suitable to fabricate large-area, free-standing thin films. As such, thermosetting acrylate thin films that are larger than 4x4 inch and meet the aforementioned criteria are unknown in the prior art.
  • oligomers were incorporated into the composition. The oligomer also increases viscosity for better film formation. Since high optical clarity is required for optical substrate applications, oligomers that provide homogeneous films are preferred. Such oligomers are covalently bonded to the acrylate network during thermal curing to prevent phase separation during prolonged use which reduces the optical clarity due to light scattering.
  • the thermosetting acrylic composition of this invention contains at least one multifunctional acrylic oligomer having the generalized formula O
  • R 3 is an aliphatic, aromatic or mixed aromatic and aliphatic moiety having a molecular weight of from about 500 to about 30,000; m ranges from 2 to about 10, and R 2 is H or CH 3 .
  • the molecular weight of the oligomer preferably ranges from about 500 to about 10,000, and most preferably from about 1,000 to about 5,000.
  • thermally stable molecular structures of R 3 are preferred.
  • Suitable oligomer structures include aliphatic polyether and polyester urethanes, polyethers, polyesters, poly(styrene-maleimide), etc.
  • R 3 linkages with low stress optic coefficient and optical polarizabiuty are preferred.
  • Suitable linkage structures include alkylene, alkylene oxide, etc.
  • suitable oligomers include, but are not limited to polyether urethane (meth)acrylates; polyester urethane (meth)ac ⁇ ylates; epoxy (meth)acrylates; novolac epoxy(meth)ac_ylates; polybutadiene (meth)acrylates, and resins with ( eth)acrylate side groups such as (meth)ac ylated styrene-maleimide copolymers.
  • Preferred oligomers include those which are miscible with the acrylate monomers and include Craynor aliphatic urethane diacrylates available from Sartomer Company under the trade name of "CN964" and “CN981" and polybutadiene diacrylate also from Sartomer Company under the trade name of "CN300".
  • the acrylate oligomer is present in an amount of from about 2% to about 90%, preferably from about 5% to about 50 % 5 and most preferably from about 5% to about 25% based on the weight of the overall thermosetting acrylic composition.
  • the acrylate materials of this invention require a dual polymerization initiator system.
  • the first polymerization initiator comprises either a low temperature l o thermal polymerization initiator capable of initiating polymerization of the mixture of acrylates at a temperature of from about 40 °C to about 120 °C or a photopolymerization initiator capable of initiating polymerization of the mixture of acrylates upon exposure to sufficient actinic radiation.
  • the second polymerization initiator is a high temperature thermal polymerization
  • the "bimodal polymerization initiator composition” refers to the use of two or more initiators whereby the low temperature or photoini tiator facilitates film
  • low temperature thermal polymerization initiators are defined as those 5 with a one hour half-life time temperature (Tj) below about 120°C.
  • Tj from about 40 °C to about 120 °C is preferred and T; from about 80°C to about 100 °C is more preferred.
  • the "high temperature thermal polymerization initiators” are those with T; greater than or equal to about 120°C, Ti preferably from about 120°C to about 250 °C is preferred and T ; from about 180 °C to about 220 °C is more preferred.
  • T greater than or equal to about 120°C
  • Ti preferably from about 120°C to about 250 °C is preferred and T ; from about 180 °C to about 220 °C is more preferred.
  • the half life times can be determined through spectrophotometric techniques or chemical techniques known to practitioners of the art.
  • Suitable low temperature thermal polymerization initiators nonexclusively include peroxides such as benzoyl peroxide (BPO), di(sec- butyl)peroxydicarbonate, t-butyl per oxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, 1 , 1 -di-(amylperoxy)-cyclohexane, alpha-cumyl peroxyneodecanoate, t-amyi peroxyneodecanoate, laurolyl peroxide, dipropylperoxydicarbonate, decanoyi peroxide, and alkyl azo compounds wherein the alkyl group contains from about 1 to about 20 carbon atoms and preferably from about 2 to about 12 carbon atoms, such as 2,2-azobis-2- methylpropionitrile, and mixtures thereof.
  • BPO benzoyl peroxide
  • di(sec- butyl)peroxydicarbonate t
  • Suitable high temperature thermal polymerization initiators nonexclusively include cumene hydroperoxide, t-butyl cumyl peroxide, dicumyi peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, di-t-butyl diperoxy-phthalate, t- amyl perbenzoate, t-butyl perbenzoate, t-butyl peroxyacetate, 2,5-dimethyl- 2,5-dH_-butylperoxy)hexane, 2,5-dihydroperoxy-2,5-dimethylhexane, t-amyl hydroperoxide, ethyl-3,3-di-(t-butylperoxy)-butyrate, 2,2-di-(t-butylperoxy)- butane and 2,2-dt(t-amylperoxy)propane and mixtures thereof.
  • the low temperature thermal polymerization initiator may be substituted by a free radical generating photoinitiator which photolyticaily generates free radicals.
  • Free radical liberating photoinitiators include any compounds which liberate free radicals on stimulation by actinic radiation.
  • the photoinitiator is a free radical generating addition polymerization initiator activated by actinic light and is preferably thermally inactive near room temperature (e.g. from about 20 °C to about 60 °C.)
  • Preferred 5 photoinitiators nonexclusively include those described in U.S. Patent No. 4,942,112, quinoxaline compounds as described in U. S. Patent 3,765,898; the vicinal polyketaldonyl compounds in U. S.
  • Patent 2,367,660 the alpha-carbonyls in U.S. Patents 2,367,661 and 2,367,670; the acyioin ethers in U. S. Patent 2,448,828; the triarylimidazolyl dimers in U. S. Patent l o 3,479, 185; the alpha-hydrocarbon substituted aromatic acyloins in U. S. Patent 2,722,512; polynuclear quinones in U. S. Patents 2,951,758 and 3,046,127; and s-triazines in U. S. Patent 4,656,272 which are inco ⁇ orated herein by reference.
  • Suitable photoinitiators include aromatic ketones such as benzophenone, acrylated benzophenone, 2-ethylanthraquinone,
  • initiators are 1-hydroxy-cyclohexyl-phenyl ketone (Irgacure 184), benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, benzodimethyl ketal (Irgacure 651), ⁇ , ⁇ -diethyloxy acetophenone, ⁇ , ⁇ -dimethyloxy- ⁇ - hydroxy acetophenone (Darocur 1173), l-[4-(2-hydroxyethoxy)phenyl]-2- hydroxy-2-methyl-propan-l-one (Darocur 2959), 2-methyl- 1 -[4- 5 methylthio)phenyl]-2-mo ⁇ holino-propan- 1 -one (Irgacure 907), 2-benzyl-2- dimethylamino-l-(4-mo ⁇ holinophenyl)-butan-l-one (Irgacure 369), poly ⁇ l- [
  • the most preferred photoinitiators are those which tend not to yellow upon irradiation. Selection of a photoinitiator will depend upon the processing time and or the spectra of the ultraviolet (UV) light curing source employed.
  • the most preferred photoinitiators include benzodimethyl ketal (Irgacure 651), ⁇ , ⁇ -dimethyloxy-a-hydroxy acetophenone (Darocur 1173), l-hydroxy-cyclohexyl-phenyl ketone (Irgacure- 184), and l-[4-(2- hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propan-l-one (Darocur 2959); 2-hydroxy-2-methyl-l -phenyl- 1-propanone available from Ciba-Geigy under the tradename "Daracur 1178", benzophenone and mixtures thereof.
  • the low temperature thermal polymerization initiator or photoinitiator is present in an amount of from about .005 % to about 5%, preferably from about .02% to about 3 % and most preferably from about .05% to about .5% based on the weight of the overall thermosetting acrylic composition.
  • the high temperature thermal polymerization initiator is present in an amount of from about .005% to about 5%, preferably from about .02% to about 3 % and most preferably from about .05% to about .5% based on the weight of the overall thermosetting acrylic composition.
  • the thermosetting acrylic composition may optionally include one or more additives including but not limited to defoaming agents such as those available from BYK under the tradename "BYK-A500”; surfactants such as those available from BASF under the tradename "L-12”; antioxidants such as phenols and more particularly hindered phenols including Irganox 1010 from Ciba-Geigy; sulfides; organoboron compounds; organophosphorous compounds; N, N'-hexamethylenebis(3,5-_U-.er.-butyl-4- hydroxycinnamamide) available from Ciba-Geigy under the tradename "Irganox 1098”; photostabilizers and more particularly hindered amine light stabilizers including but not limited to poly[(6-mo ⁇ holino-s-triazine-2,4- diyl)[2,2,6,6,-tetramethyl-4-piperidyl)imino]-hexamethylene [2,2,6,6,-
  • composition of the present invention which is in the form of a viscous liquid solution, may be made by mixing the acrylate monomers), the acrylate oligomer(s), and any optional additives, preferably in the absence of solvent, under conditions of ambient pressure and a temperature of from about 25 °C to about 100 °C, and preferably from about 40 °C to about 80 °C using conventional mixing apparatus known in the art, i.e. mechanical stirrer or shakers, for about 10 minutes to about 4 hours, and preferably from about 10 minutes to about 1 hour or until the mixture is visually uniform.
  • the chosen initiators are added thereto, and the result is further mixed for about 10 minutes to about 10 hours, and preferably from about 10 minutes to about 2 hours or until the mixture is uniform.
  • all reagents including the initiators and any optional additives may be mixed together using conventional mixing devices for about 10 minutes to about 4 hours, and preferably from about 10 minutes to about 1 hour under conditions of ambient pressure and a temperature less than or equal to about 60 °C, and preferably less than or equal to about 40 °C if using either a dual thermal initiator or a low temperature thermal initiator, or a temperature of less than or equal to about 100 °C, and preferably less than or equal to about 80 °C if using a photoinitiator or a high temperature thermal initiator.
  • a solvent may be mixed in with the reagents and optional additives either before, during, or after the addition of the thermal initiator thereto.
  • Suitable solvents include, but are not limited to, esters, ketones, ethers, haloalkanes having from about 1 carbon atom to about 24 carbon atoms, aromatic solvents, and mixtures thereof.
  • the solvent may be added in an amount ranging, based upon the total weight of reagents and optional additives in the composition, of from about 0% to about 80 %, and preferably from about 0 % to about 20 %.
  • the resulting composition may be formed into various articl . _ such as films using methods well known in the art including but not limited to ca: ⁇ molding, injection molding, direct liquid casting, reactive injection molding (“RIM”), resin transfer molding (“RTM”), and slot coating.
  • Direct liquid casting and RIM are preferred.
  • Continuous direct liquid casting which is similar to polymer solution casting, is more preferred.
  • direct liquid casting a liquid composition is spread onto a web, then the coated web is exposed to a curing source.
  • the webs may be comprised of, for example, aluminum, stainless steel, chromium, and the like. Further details of direct liquid casting processing may be found in, for example, 15 Encyclopedia of Polymer Science and Engineering, 146 - 153 (2nd Ed. 1989), which is inco ⁇ orated herein by reference.
  • Curing which may involve one or more curing steps, may be performed via techniques known by one skilled in the ait at or above atmospheric pressure and at a temperature of from about 150 °C to about 250 °C and preferably from about 180°C to about 220°C for single step curing or from about 60 °C to about 120 °C and preferably from about 80°C to about 100 ⁇ C for the low temperature step(s) in multistep curing and from about 120 °C to about 250 °C and preferably from about 180°C to about 220°C for the high temperature step(s) in multistep curing.
  • the time per step for curing may range from about 1 minute to about 2 hours and preferably from about 5 minutes to about 60 minutes, depending upon the heat source selected.
  • Suitable curing heat sources include microwave, ultraviolet (“UV”) light, laser, light, infrared, or thermal, with the thermal method being preferred. More preferably, curing may occur in a nitrogen-purged, temperature controllable thermal oven. Curing with UV light is particularly preferred when a dual initiator, and more specifically when at least one photoinitiator is used.
  • the optional solvents may be removed from the composition either before curing such as by vacuum evaporation techniques known in the art or by evaporation during curing.
  • Various articles such as substrates having a thickness of from about 0.05 mm to about .5 cm and preferably from about 0.05 mm to about 1.0 mm, suitable for use in flat panel displays including LCDs, plasma displays, field emission displays, and light emitting diodes, may be formed from the composition of the present invention.
  • the making of such substrates is well known in the ait and is described in, for example, U.S. Patent 4,526,818 which is inco ⁇ orated herein by reference.
  • These visual displays basically comprise a substrate, the thermoset acrylic film of this invention attached to the substrate, and a visual display material between the substrate and the thermoset acrylic film.
  • Liquid crystal displays comprise a substrate, the 5 thermoset acrylic film of this invention attached to the substrate, and a layer of a liquid crystal composition constrained between the substrate and the thermoset acrylic film.
  • Other uses for articles comprised of the composition of the present invention include solar cells, optical waveguides and windows.
  • FIG. 1 shows a typical structure of a liquid crystal color display panel 10. It has a front transparent substrate 11 which may be produced according to this invention and a front
  • transparent electrode 13 on the inner surface thereof. It also has a back transparent substrate 12 which may also be produced according to this invention and a back transparent electrode 14 in the form of a mosaic array of dot electrodes on the inner surface thereof arranged in parallel with each other. A gasket 15 is sandwiched therebetween.
  • liquid crystal layer 16 is inte ⁇ osed between the substrates 11 and 12.
  • the outer surface of the front transparent substrate 11 is optionally provided with a front linear polarizer 17 and the outer surface of the back substrate 12 is provided with optional back linear polarizer 18 so that the polarization axes of the polarizers 17 and 18 are parallel with each other.
  • the back linear polarizer 18 is a mosaic color filter 19 with a mosaic array of red, green and blue filter elements observed from the front (top of the figure) which may be illuminated by a light source (not shown) located at the rear (bottom of the figure).
  • a light source not shown located at the rear (bottom of the figure).
  • Films formed from these resins have surface hardness of at least about 3H and preferably at least about 4H, which eliminates the need for a hardcoating layer, and excellent chemical resistance because of crosslinking of the materials.
  • these substrates may optionally be coated with one or more of the following coatings, for example, moisture barrier, gas and/or oxygen and/or nitrogen barrier, hard coat, adhesion promotion layer, alignment layer, indium tin oxide ("ITO") or other conductive coating, color filter, retardation layer, antireflection coating, and integral coatings.
  • the films produced according to the invention are substantially colorless on the Gardner Yellow Color Scale according to ASTM D1544, have a optical transparency in the visible region of the electromagnetic spectrum as measured by a spectrophotometer of at least about 85% and preferably at least about 90% excluding reflection loss; have a Tg of at least about 190°C, preferably at least about 210 °C and more preferably at least about 250 °C; an optical birefringence of less than about 15 nm, preferably less than about 10 nm net retardation per 100 ⁇ m of film thickness; a surface hardness as 5 measured by ASTM D3363 of at least about 3H, preferably at least about 6H; a coefficient of thermal expansion of less than about 60 ppm/K, preferably less than about 50 ppm K; sufficient chemical resistance to pass ASTM D543; sufficient flexibility to pass the 0.5 inch mandrel test of ASTM D 1737 so that the film can be rolled; and are capable retaining optical o transparency when heated at 200 °C for 1
  • ASTM D543 with modifications: a film sample is placed into a given chemical such as sodium hydroxide (NaOH); hydrochloric acid (HCl); N-methyl pyrrolidinone (l-methyl-2-pyrrolidinone or "NMP"), ethyl alcohol, ethanol amine, tetraethyl ammonium hydroxide, 5 acetone, isopropanol (IPA), acetone, and liquid crystals such as "ET available from EM Industries, Inc.
  • a given chemical such as sodium hydroxide (NaOH); hydrochloric acid (HCl); N-methyl pyrrolidinone (l-methyl-2-pyrrolidinone or "NMP"), ethyl alcohol, ethanol amine, tetraethyl ammonium hydroxide, 5 acetone, isopropanol (IPA), acetone, and liquid crystals such as "ET available from EM Industries, Inc.
  • Spectrometer 110 available from Seiko Instruments Inc., USA set in the Flexural Mode (3 point bending mode) with a frequency of 1 Hz; the samples are heated at a rate of 3 °C/minute from -20 °C to 300 ⁇ C.
  • Td Thermal Decomposition Temperature
  • CTE Coefficient of thermal expansion
  • TMA temperature is increased at a rate of 10 °C/min. from -50°C to 300 °C;
  • Example 1 A resin mixture was prepared by mixing, based upon the total weight of the resin, 40% (20.0 g) ethoxylated bisphenol A dimethacrylate (EBDMA) available from Sartomer under the tradename “SR 348", 40% (20.0 g) trimethylolpropane trimethacrylate (TMPTMA) available from Sartomer under the tradename "SR 350”, 20% (10.0 g) craynor aliphatic urethane acrylate oligomers available from Sartomer under the tradename "CN964", under ambient pressure and a temperature of 60 °C in a conventional mechanical mixer.
  • ESDMA ethoxylated bisphenol A dimethacrylate
  • TMPTMA trimethylolpropane trimethacrylate
  • Example 2 A resin mixture was prepared by mixing, based upon the total weight of the resin, 45% (20.0 g) ethoxylated bisphenol A dimethacrylate (EBDMA) available from Sartomer under the tradename “SR 348”, 45% (20.0 g) trimethylolpropane trimethacrylate (TMPTMA) available from Sartomer under the tradename "SR 350”, 10% (4.4 g) craynor aliphatic urethane acrylate oligomers available from Sartomer under the tradename "CN964", under ambient pressure and a temperature of 60 °C in a conventional mechanical mixer.
  • ESDMA ethoxylated bisphenol A dimethacrylate
  • TMPTMA trimethylolpropane trimethacrylate
  • Example 3 (Comparative): A resin mixture was prepared by mixing, based 5 upon the total weight of the resin, 33% (10.0 g) of an acrylate terminated aromatic urethane oligomer available from Biddle Sawyer Company under the tradename "T-1600" and 67% (20.0 g) 1,6-hexanediol diaciylate (HDD A) under ambient pressure and a temperature of 60 °C in a conventional mechanical mixer. After allowing the temperature of the l o mixture to drop to 25 °C, 0.5% (0.15 g) 2,2-azobis-2-methylpropionitrile (AH3N) based upon the total weight of the resin, were added thereto and mixed for 30 minutes under ambient conditions. The resulting resin mixture was spread onto glass substrates under ambient conditions, and subsequently thermally cured at 80°C for 2 h. The film was then annealed at 200°C for 1
  • Example 1 The thickness of the film is about 100 ⁇ m. Properties are listed in Table 1. Unlike the films obtained in Example 1 and 2, the color of the film obtained is yellow. This discoloration is attributed to the aromatic urethane unit from the oligomer used in Example 3, which is thermally unstable and discolors upon thermal aging. The thermal discoloration of aromatic
  • Example 4 A resin mixture was prepared by mixing, based upon the total weight of the resin, 50% (20.0 g) ethoxylated bisphenol A dimethacrylate (EBDMA) available from Sartomer under the tradename “SR 5 348” and 50% (20.0 g) trimethylolpropane trimethacrylate (TMPTMA) available from Sartomer under the tradename "SR 350” under ambient pressure and a temperature of 60 °C in a conventional mechanical mixer.
  • ELDMA ethoxylated bisphenol A dimethacrylate
  • TMPTMA trimethylolpropane trimethacrylate
  • Example 5 A resin mixture was prepared by mixing, based upon the total weight of the resin, 50% (20.0 g) hexakis(methac_yloxyethoxy triphosphazene) (PPZ) and 50% (20.0 g) trimethylolpropane trimethacrylate (TMPTMA) under ambient pressure and a temperature of 60 °C in a conventional mechanical mixer. After allowing the temperature of the 5 mixture to drop to 25 °C, 0.2% (0.08 g) benzoperoxide (BPO), and 0.3% (0.12 g) cumene hydroperoxide (CHP), based upon the total weight of the resin, were added thereto and mixed for 30 minutes under ambient conditions.
  • PPZ hexakis(methac_yloxyethoxy triphosphazene)
  • TMPTMA trimethylolpropane trimethacrylate
  • the resulting resin mixture was spread onto glass substrates under ambient conditions, then subsequently thermally cured at two o temperature stages, for 60 minutes at 90 °C and for 60 minutes at 200°C, respectively. Properties are given in Table 1. No integral large film was obtained. The color of the film is yellow, with a color index of 3. This color is caused by the thermal discoloration of the PPZ component.
  • Example 6 A resin mixture was prepared by mixing, based upon the total weight of the resin, 67% (20.0 g) ethoxylated bisphenol A dimethacrylate (EBDMA) available from Sartomer under the tradename “SR 348” and 33% (10.0 g) trifunctional methacrylate ester available from Sartomer under the tradename "SR 9011” under ambient pressure and a temperature of 60 °C in a conventional mechanical mixer. After allowing the temperature of the mixture to drop to 25 °C, 0.2% (0.06 g) benzoperoxide (BPO), and 0.3% (0.09 g) cumene hydroperoxide (CHP), based upon the total weight of the resin, were added thereto and mixed for 30 minutes under ambient conditions. The resulting resin mixture was spread onto glass substrates under ambient conditions, then subsequently thermally cured at two temperature stages, for 60 minutes at 90 °C and for 60 minutes at 200°C, respectively. Properties are given in Table 1.
  • ESDMA ethoxylated bisphenol A dimeth
  • Example 7 A resin mixture was prepared by mixing, based upon the total weight of the resin, 67% (20.0 g) ethoxylated bisphenol A dimethacrylate (EBDMA) available from Sartomer under the tradename "SR 348" and 33% (10.0 g) 1,6-hexanediol dimethacrylate (HDDMA) under ambient pressure and a temperature of 60 °C in a conventional mechanical mixer. After allowing the temperature of the mixture to drop to 25 °C, 0.2% (0.06 g) benzoperoxide (BPO), and 0.3% (0.09 g) cumene hydroperoxide (CHP), based upon the total weight of the resin, were added thereto and mixed for 30 minutes under ambient conditions.
  • ESDMA ethoxylated bisphenol A dimethacrylate
  • HDDMA 1,6-hexanediol dimethacrylate
  • BPO benzoperoxide
  • CHP cumene hydroperoxide
  • Example 8 A resin mixture was prepared by mixing, based upon the total weight of the resin, 50% (20.0 g) ethoxylated bisphenol A dimethacrylate (EBDMA) available from Sartomer under the tradename "SR 348", 25% (10.0 g) trimethylolpropane trimethacrylate (TMPTMA) available from Sartomer under the tradename "SR 350”, 25% (10.0 g) 1,6-hexanediol dimethacrylate (HDDMA) under ambient pressure and a temperature of 60 °C in a conventional mechanical mixer.
  • ESDMA ethoxylated bisphenol A dimethacrylate
  • TMPTMA trimethylolpropane trimethacrylate
  • HDDMA 1,6-hexanediol dimethacrylate
  • Example 9 A resin mixture was prepared by mixing, based upon the total weight of the resin, 57% (40.0 g) ethoxylated bisphenol A dimethacrylate (EBDMA) available from Sartomer under the tradename "SR 348", 14% (10.0 g) a polyether urethane acrylate oligomer available from Sartomer under the tradename "CN 981”, 29% (20.0 g) 1,6-hexanediol dimethacrylate (HDDMA) under ambient pressure and a temperature of 60 °C in a conventional mechanical mixer.
  • ESDMA ethoxylated bisphenol A dimethacrylate
  • Example 10 A resin mixture was prepared by mixing, based upon the total weight of the resin, 67% (20.0 g) ethoxylated bisphenol A dimethacrylate (EBDMA) available from Sartomer under the tradename "SR 348", 33% (10.0 g) isobornyl methacrylate (IMA) under ambient pressure and a temperature of 60 °C in a conventional mechanical mixer. After allowing the o temperature of the mixture to drop to 25 °C, 1.0% (0.30 g) di-t-butyl peroxide, based upon the total weight of the resin, were added thereto and mixed for 30 minutes under ambient conditions. The resulting resin mixture was spread onto glass substrates under ambient conditions, then subsequently thermally cured 200°C for 1 h. Properties are listed in Table 1. 5
  • Example 11 A resin mixture was prepared by mixing, based upon the total weight of the resin, 50% (20.0 g) highly ethoxylated bisphenol A diacrylate (EBDA-10) available from Sartomer under the trade name "SR 602" and o 50% (20.0 g) pentaerythritol tetraacrylate (PET A) under ambient pressure and a temperature of 60 °C in a conventional mechanical mixer. After allowing the temperature of the mixture to drop to 25 °C, 0.5% (0.2 g) 2,2- azobis-2-methylpropionitrile (AIBN) based upon the total weight of the resin, were added thereto and mixed for 30 minutes under ambient 5 conditions.
  • EBDA-10 highly ethoxylated bisphenol A diacrylate
  • PET A pentaerythritol tetraacrylate
  • AIBN 2,2- azobis-2-methylpropionitrile
  • the resulting resin mixture was spread onto glass substrates under ambient conditions, then subsequently thermally cured at two temperature stages, for 60 minutes at 60 °C and for 60 minutes at 120°C, respectively.
  • the thickness of the film obtained is about 100 ⁇ m.
  • Property data are listed in Table 1.
  • Example 12 A resin mixture was prepared by mixing, based upon the total weight of the resin, 50% (20.0 g) tripropyleneglycol diacrylate (TPGDA) and 50% (20.0 g) pentaerythritol tetraacrylate (PET A) under ambient pressure and a temperature of 60 °C in a conventional mechanical mixer. After allowing the temperature of the mixture to drop to 25 °C, 0.5% (0.2 g) 2,2-azobis-2-methylpropionitrile (AIBN) based upon the total weight of the resin, were added thereto and mixed for 30 minutes under ambient conditions.
  • TPGDA tripropyleneglycol diacrylate
  • PET A pentaerythritol tetraacrylate
  • AIBN 2,2-azobis-2-methylpropionitrile
  • the resulting resin mixture was spread onto glass substrates under ambient conditions, then subsequently thermally cured at two temperature stages, for 60 minutes at 60 °C and for 60 minutes at 120°C, respectively.
  • the thickness of the film obtained is about 100 ⁇ m.
  • Property data are given in Table 1.
  • Example 13 (Comparative): A resin mixture was prepared by mixing, based upon the total weight of the resin, 50% (20.0 g) trimethylolpropane triacrylate (TMPTA) and 50% (20.0 g) pentaerythritol tetraacrylate (PET A) under ambient pressure and a temperature of 60 °C in a conventional mechanical mixer. After allowing the temperature of the mixture to drop to 25 °C, 0.5% (0.2 g) 2,2-azobis-2-methylpropionitrile (AIBN) based upon the total weight of the resin, were added thereto and mixed for 30 minutes under ambient conditions.
  • TMPTA trimethylolpropane triacrylate
  • PET A pentaerythritol tetraacrylate
  • AIBN 2,2-azobis-2-methylpropionitrile
  • Example 14 (Comparative): A free standing thin film of poly(methyl methacrylate), available from Aldrich Chemical Company, was prepared by solution casting techniques known in the prior art. The film was annealed at 200°C for 1 h before being used as a reference for the thermosetting acrylate polymers provided in this invention. The measured properties are given in Table 1. Compared with the highly crosslinked thermosetting acrylate polymers, the linear poly(methyl methacrylate) suffers from low Tg, poor dimensional stability (large CTE), poor chemical resistance and low surface hardness, which are intrinsic problems for most thermoplastic polymers.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne de nouvelles compositions acryliques thermodurcissables, des films optiques, un procédé de fabrication de ces films, et des articles ainsi fabriqués. L'invention a plus particulièrement pour objet l'utilisation de ce type de films optiques comme substrat pour des dispositifs d'affichage à panneau plat, tels que des affichages à cristaux liquides. Ces matériaux présentent de bonnes propriétés optiques parmi lesquelles une faible biréfringence pour l'obtention de forts contrastes et une pureté des couleurs, une transmission élevée à faible voile pour assurer une perte de lumière minimale et réduire la consommation de puissance tout en augmentant la luminosité. Ces films présentent un degré de planéité, de bonnes propriétés de barrière gazeuse, une bonne résistance chimique, une résistance aux rayures élevée et une stabilité dimensionnelle appropriée. Cette composition acrylique thermodurcissable comprend un mélange d'acrylates polymérisables avec au moins un monomère acrylique multifonctionnel, au moins un oligomère acrylique multifonctionnel et une composition formant initiateur de polymérisation bimodal comprenant un mélange d'un initiateur de photopolymérisation ou un initiateur de polymérisation à faible température qui initie la polymérisation à une température comprise entre environ 40 et environ 120 °C, plus un initiateur de polymérisation thermique à haute température qui initie la polymérisation ou la réticulation des acrylates et des acrylates prépolymérisés à une température comprise entre 180 °C ou plus.
PCT/US1996/020310 1995-12-22 1996-12-20 Materiaux acryliques thermodurcissables a haute temperature de transition vitreuse WO1997023524A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US909995P 1995-12-22 1995-12-22
US60/009,099 1995-12-22
US76457996A 1996-12-13 1996-12-13
US08/764,579 1996-12-13

Publications (1)

Publication Number Publication Date
WO1997023524A1 true WO1997023524A1 (fr) 1997-07-03

Family

ID=26679048

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/020310 WO1997023524A1 (fr) 1995-12-22 1996-12-20 Materiaux acryliques thermodurcissables a haute temperature de transition vitreuse

Country Status (1)

Country Link
WO (1) WO1997023524A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7211368B2 (en) * 2003-01-07 2007-05-01 3 Birds, Inc. Stereolithography resins and methods
US8072562B2 (en) 2008-09-15 2011-12-06 Au Optronics Corporation Liquid crystal panel and liquid crystal mixture
US10968367B2 (en) 2016-11-08 2021-04-06 H.B. Fuller Company Low temperature curable adhesive composition and articles including the same
WO2021141927A1 (fr) * 2020-01-06 2021-07-15 Gentex Corporation Mise en correspondance de trouble dans un ensemble d'affichage masqué

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0027162A1 (fr) * 1979-08-01 1981-04-22 Matsushita Electric Industrial Co., Ltd. Composition de revêtement durcissable par radiation UV et/ou par la chaleur
GB2089819A (en) * 1980-12-22 1982-06-30 Grace W R & Co Conformal coating curable by combination of radiation and heat
JPS57207609A (en) * 1981-06-15 1982-12-20 Matsushita Electric Works Ltd Unsaturated polyester resin composition
US4629637A (en) * 1984-04-21 1986-12-16 Bayer Aktiengesellschaft Coated optically isotropic or monoaxially film of plastic
JPS62235310A (ja) * 1986-04-04 1987-10-15 Japan Synthetic Rubber Co Ltd 樹脂組成物の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0027162A1 (fr) * 1979-08-01 1981-04-22 Matsushita Electric Industrial Co., Ltd. Composition de revêtement durcissable par radiation UV et/ou par la chaleur
GB2089819A (en) * 1980-12-22 1982-06-30 Grace W R & Co Conformal coating curable by combination of radiation and heat
JPS57207609A (en) * 1981-06-15 1982-12-20 Matsushita Electric Works Ltd Unsaturated polyester resin composition
US4629637A (en) * 1984-04-21 1986-12-16 Bayer Aktiengesellschaft Coated optically isotropic or monoaxially film of plastic
JPS62235310A (ja) * 1986-04-04 1987-10-15 Japan Synthetic Rubber Co Ltd 樹脂組成物の製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 007, no. 061 (C - 156) 15 March 1983 (1983-03-15) *
PATENT ABSTRACTS OF JAPAN vol. 012, no. 110 (C - 486) 8 April 1988 (1988-04-08) *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7211368B2 (en) * 2003-01-07 2007-05-01 3 Birds, Inc. Stereolithography resins and methods
US8072562B2 (en) 2008-09-15 2011-12-06 Au Optronics Corporation Liquid crystal panel and liquid crystal mixture
US10968367B2 (en) 2016-11-08 2021-04-06 H.B. Fuller Company Low temperature curable adhesive composition and articles including the same
WO2021141927A1 (fr) * 2020-01-06 2021-07-15 Gentex Corporation Mise en correspondance de trouble dans un ensemble d'affichage masqué
US11719868B2 (en) 2020-01-06 2023-08-08 Gentex Corporation Haze matching in a masked display assembly

Similar Documents

Publication Publication Date Title
KR100407736B1 (ko) 활성에너지선경화성조성물을사용하여제조한렌즈시이트
US7163723B2 (en) Liquid crystalline compound and reterdation difference film using the same
EP2275459B1 (fr) Copolymère vinyle aromatique polyfonctionnel, son procédé de fabrication et composition de résine
US9056935B2 (en) Photocurable resin composition, method of fabricating optical film using the same, and optical film including the same
JP2001262011A (ja) 含フッ素硬化性塗液、用途及び製造方法
JP2007056180A (ja) 樹脂成形体、及びその用途
EP2042527B1 (fr) Compositions polymerisables pour articles optiques
JP2006249318A (ja) ディスプレイ用光学フィルム
JP2010191370A (ja) 防眩性コーティング組成物、防眩フィルムおよびその製造方法
JP5307511B2 (ja) 被膜形成用ラジカル重合性樹脂組成物
KR101377651B1 (ko) 위상차 필름 및 위상차 필름 적층체 및 이들의 제조방법
WO1997023524A1 (fr) Materiaux acryliques thermodurcissables a haute temperature de transition vitreuse
KR102155180B1 (ko) 이중 경화 접착제 조성물
JP3482815B2 (ja) 透明導電性シート
JP3940086B2 (ja) フッ素置換脂環基含有（メタ）アクリル酸エステルおよびその硬化物
KR101057352B1 (ko) 플루오렌 에폭시 변성 아크릴레이트, 이를 포함하는광경화형 수지 조성물 및 이로부터 제조된 광학필름
JP2011037941A (ja) 硬化性樹脂組成物、その硬化物、及びプラスチックレンズ
JPH11171941A (ja) 活性エネルギー線硬化性組成物および光学シート
CN113900170A (zh) 一种高辉度抗吸附耐刮伤棱镜膜及其制备方法
JP3509468B2 (ja) 透明導電性シート
JP5181056B2 (ja) ハードコートフィルム又はシート、光学素子及び画像表示装置
JP2003251750A (ja) 干渉斑を低減するコート層を有する光学フィルム
KR20090120275A (ko) 플렉시블 디스플레이 기판 및 그의 제조방법
JP2018150524A (ja) 活性エネルギー線硬化性組成物
JP2002128915A (ja) 破損しにくいプラスチックシート

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA CN JP KR MX SG

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 97523819

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase