Source: http://www.google.com/patents/US6841190?dq=6,621,746
Timestamp: 2017-12-17 12:20:28
Document Index: 492300958

Matched Legal Cases: ['arts 50', 'arts 8', 'arts 15', 'arts 14', 'arts 20', 'arts 13', 'arts 3']

Patent US6841190 - Antisoiling hardcoat - Google Patents
An antisoiling hardcoated film comprising a substantially transparent substrate, a hardcoat layer comprising inorganic oxide particles dispersed in a binder matrix, and an antisoiling layer comprising a perfluoropolyether. The antisoiling layer can be very thin, thus reducing the cost of the perfluoropolyether....http://www.google.com/patents/US6841190?utm_source=gb-gplus-sharePatent US6841190 - Antisoiling hardcoat
Publication number US6841190 B2
Application number US 10/690,425
Also published as CN1446370A, CN1446371A, EP1309847A1, EP1312103A2, EP1312104A2, US6589650, US6660388, US6660389, US20020114934, US20020122925, US20040081764, WO2002012857A1
Publication number 10690425, 690425, US 6841190 B2, US 6841190B2, US-B2-6841190, US6841190 B2, US6841190B2
Inventors Junkang J. Liu, Bettie C. Fong, Bruce D. Kluge
Patent Citations (41), Referenced by (46), Classifications (103), Legal Events (6)
US 6841190 B2
1. A method for making an antisoiling hardcoat comprising coating and curing on a substrate a ceramer coating comprising inorganic oxide particles dispersed in a free-radically polymerizable binder matrix, and coating and curing atop the ceramer coating an antisoiling layer comprising a free-radically polymerizable fluorochemical.
2. A method for making a display element comprising applying to a substantially transparent substrate a curable hardcoat layer comprising inorganic oxide particles dispersed in a free-radically polymerizable binder matrix, curing the hardcoat layer, applying directly to the hardcoat layer a curable antisoiling layer comprising a perfluoropolyether, and polymerizing the antisoiling layer.
3. A method according to claim 2 wherein the perfluoropolyether has the formula:
Y—CaF2aO)b—CaF2a—Y
4. A method according to claim 2 wherein the substrate has first and second major surfaces with the hardcoat being applied to the first major surface, and further comprising applying an adhesive to the second major surface.
5. A method for making a screen protector for an information display, comprising:
a) applying to one side of a substantially transparent generally planar substrate a curable hardcoat layer comprising inorganic oxide particles dispersed in a free-radically polymerizable binder matrix, curing the hardcoat layer, applying directly to the hardcoat layer a curable antisoiling layer comprising a perfluoropolyether, and polymerizing the antisoiling layer; and
6. A method according to claim 5 wherein the perfluoropolyether has the formula:
Y—(CaF2aO)b—CaF2a—Y
7. A method for making screen protectors for portable electronic devices having a display screen, comprising:
a) applying to one side of a substantially transparent generally planar substrate a curable hardcoat layer comprising inorganic oxide particles dispersed in a free-radically polymerizable binder matrix, curing the hardcoat layer, applying to the hardcoat layer a curable antisoiling layer comprising a perfluoropolyether, and curing the antisoiling layer;
b) applying to the other side of the substrate an adhesive layer;
c) forming the coated substrate into a stack of sheets; and
d) cutting the stack so that the sheets will fit the display screen.
8. A method according to claim 7 wherein the perfluoropolyether has the formula:
9. A continuous, roll to roll manufacturing method for making a roughened screen protector sheet for information displays, comprising:
a) depositing a substantially solvent-free, curable ceramer composition comprising inorganic oxide particles dispersed in a free-radically polymemizable binder matrix into the nip region between a substantially transparent substrate and a roll having an average surface roughness of at least 0.1 micrometer;
c) photocuring the ceramer composition through the substrate while the ceramer composition is against the roll;
10. A method according to claim 9, further comprising converting the coated substrate into sheets sized to fit an electronic display device screen.
11. A method according to claim 10, wherein the device comprises a portable device.
12. A method according to claim 10, wherein the device comprises a personal digital assistant.
13. A method according to claim 9, wherein the sheets are formed into a stack.
This application is a divisional of application Ser. No. 09/923,749, filed Aug. 7, 2001, entitled “ANTISOILING HARDCOAT” (now U.S. Pat. No. 6,660,388), which is a continuation-in-part of application Ser. No. 09/633,835, filed Aug. 7, 2000 (now U.S. Pat. No. 6,589,650), the disclosure of which is incorporated by reference herein.
Protective films for PDAs, cellular phones and other display devices are available from many commercial sources including A.R.M. (SECURER™ Screen Protector), CompanionLink Software, Inc. (COMPANIONLINK™ PDA Screen Protector), EC Film (PDA Screen Protector), Fellowes Corporation (WrightRIGHT™ PDA Screen Protector), PerfectData Corporation (SILKYBOARD™ PDA Keyboard and Screen Protector), ROTA Technology Inc. (RT-PDS Screen Protector and RT-MPS Mobile Phone Screen protector), Swann Communications (PDA PLUS™ Screen Protectors), Sanwa Supply Inc. (LCD-PDA Screen Protector) and VSPS (V.S. Protective Shield). Typically these products are sold as single precut sheets of plain plastic film, although some include a textured or tinted surface over at least a portion of the film. Some of the above-mentioned protective films are said to help keep a PDA screen smudge-free. Viewing screen protective devices are also shown in, e.g., U.S. Pat. No. 4,907,090 (Ananian); U.S. Pat. No. 6,059,628 (Yoo et al.); U.S. Pat. No. 6,250,765 (Murakami) and Re. 35,318 (Warman). A touch panel device having a roughened outermost surface is shown in Japanese published patent application (Kokai) No. 2000-020240.
U.S. Pat. No. 6,204,350 (Liu et al.) describes curable coating compositions which comprises alkoxysilane containing fluorinated polymers.
FIG. 2 shows a resistive touch panel display generally identified as 20 in schematic form. Viewing surface 21 permits an observer (not shown in FIG. 2) to see images from imaging device 12. Substrate 22 of display 10 lies atop imaging device 12 and typically is made of glass or a plastic such as polycarbonate or polyethylene terephthalate. The upper surface of substrate 22 is covered with thin layer of an optional hardcoat 24 a, which serves as a primer and adhesion aid for transparent, thin, conductive coating 25 a. A similar thin conductive coating 25 b is adhered to flexible membrane 23 through optional hardcoat 24 b. The upper surface of flexible membrane 23 is coated with hardcoat 26. Hardcoat 26 provides scratch and abrasion resistance to help protect flexible membrane 23 from damage. Hardcoat 26 has an optional roughened upper surface, as in the display of FIG. 1. Antisoiling layer 28 is sufficiently thin so that the roughened upper surface 27 of hardcoat 26 is replicated on viewing surface 21. Antisoiling layer 28 provides oil and ink resistance to help prevent hardcoat 26 from being smudged or otherwise soiled. If desired, an optional antistatic layer can also be provided, as in the display of FIG. 1. Spacers 29 lie atop coating 25 a, and a finite space normally separates the upper surface of coating 25 a and the lower surface of coating 25 b. As will be appreciated by those skilled in the art, contact by a finger or stylus with viewing surface 21 will cause membrane 23 to flex and bring coating 25 b into contact with coating 25 a, enabling a current to flow between these layers. A controller (not shown in FIG. 2) can identify the touch location by comparing current flowing from various electrodes or busbars (also not shown in FIG. 2) printed on the conductive layers 25 a and 25 b.
Those skilled in the art will appreciate that other types of touch-sensitive devices can be used in the invention. For example, the touch-sensitive device can operate via guided acoustic wave, surface acoustic wave or near field imaging. The touch-sensitive device can also operate via a non-contact mechanism such as a scanning infrared sensor, e.g., via provision of a suitable array of light beams and photosensors above the upper face of the display.
FIG. 5 shows a stack 50 of four PDA information display protectors of the type shown in FIG. 3. Stack 50 has a single liner 32 protecting the adhesive layer 34 a of the lowermost information display protector. The remaining information display protectors can be adhered to one another by pressing adhesive layers 34 b, 34 c and 34 d against antisoiling layers 38 a, 38 b and 38 c, respectively. A user can remove the uppermost protector from the stack and adhere it to the screen of a PDA as in FIG. 4. If the thus—applied protector later becomes worn or damaged, it can be peeled off the PDA screen and replaced with another protector from stack 50.
A user can store the stack by adhering it to a display device or to its case or cover. FIG. 6 shows a PDA generally designated as 60. Protector 30 (on substrate 33) has been removed from the top of stack 50 and applied to the screen 42 of PDA 60. Liner 32 has been removed from stack 50 so that stack 50 could be adhered to inside surface 64 of PDA front cover 62. Although not shown in FIG. 6, the stack could instead be adhered to the rear of PDA 60 or to any available surface of a separate PDA case. If the stack 50 contains a relatively low number of protectors (e.g., 10 or less, more preferably 5 or less), it will not unduly obscure underlying printed graphics on the front cover (such as the printed GRAFFITI™ alphabet symbol guide that is supplied with some PDAs) and will not hamper closure of a PDA cover or case if applied to an inside surface thereof. Because the stack 50 can be stored with the PDA, spare protectors 30 are close at hand when needed. This is a much more convenient mode of storage than the typical storage mode for current PDA screen protector products sold as single sheets. When protector 30 on screen 42 becomes worn or damaged, a fresh protector can be removed from stack 50. For example, as shown in FIG. 6, the next protector in stack 50 can be removed by peeling adhesive layer 34 c away from antisoiling layer 38 b.
FIG. 7 shows a removable computer privacy filter generally identified as 70. Louvered light control film 72 permits a viewer to see images from an underlying imaging device 12 through viewing surface 71, while preventing an observer located away from the main viewing axis from seeing such images. Substrate layers 74 are adhered to the upper and lower surfaces of light control film 72 by adhesive layers 73. Hardcoats 75 and 77 help to protect the substrate layers 74 and film 72 from damage, and antisoiling layers 76 and 78 provide oil and ink resistance to help prevent hardcoats 75 and 77 from becoming smudged or otherwise soiled. Hardcoat 77 and its antisoiling layer 78 preferably are roughened in order to provide glare reduction. Because filter 70 may frequently be removed from and replaced on a display, the use of the hardcoat and antisoiling layer on both major surfaces of the filter facilitates handling and cleaning even if the user accidentally grips the front and back of the filter rather than handling it by its edges. An optional antistatic coating (not shown in FIG. 7) can also be employed on or just below one or both major surfaces of the filter if desired.
A variety of binders can be employed in the hardcoat. Preferably the binder is derived from a free-radically polymerizable precursor that can be photocured once the hardcoat composition has been coated upon the substrate. Binder precursors such as the protic group-substituted esters or amides of an acrylic acid described in Bilkadi, or the ethylenically-unsaturated monomers described in Bilkadi et al., are especially preferred. Suitable binder precursors include polyacrylic acid or polymethacrylic acid esters of polyhydric alcohols, such as diacrylic acid or dimethylacrylic acid esters of diols including ethyleneglycol, triethyleneglycol, 2,2-dimethyl-1,3-propanediol, 1,3-cyclopentanediol, 1-ethoxy-2,3-propanediol, 2-methyl-2,4-pentanediol, 1,4-cyclohexanediol, 1,6-hexamethylenediol, 1,2-cyclohexanediol, 1,6-cyclohexanedimethanol, resorcinol, pyrocatechol, bisphenol A, and bis(2-hydroxyethyl) phthalate; triacrylic acid or trimethacrylic acid esters of triols including glycerin, 1,2,3-propanetrimethanol, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,3,6,-hexanetriol, 1,5,10-decanetriol, pyrogallol, phloroglucinol, and 2-phenyl-2,2-methylolethanol; tetraacrylic acid or tetramethacrylic acid esters of tetraols including 1,2,3,4-butanetetrol, 1,1,2,2,-tetramethylolethane, 1,1,3,3,-tetramethylolpropane, and pentaerythritol tetraacrylate; pentaacrylic acid or pentamethacrylic acid esters of pentols including adonitol; hexaacrylic acid or hexamethacrylic acid esters of hexanols including sorbitol, dipentaerythritol, dihydroxy ethyl hydantoin; and mixtures thereof. The binder can also be derived from one or more monofunctional monomers as described in Kang et al. '798. Preferably the binder comprises one or more N,N-disubstituted acrylamide and or N-substituted-N-vinyl-amide monomers as described in Bilkadi et al. More preferably the hardcoat is derived from a ceramer composition containing about 20 to about 80% ethylenically unsaturated monomers and about 5 to about 40% N,N-disubstituted acrylamide monomer or N-substituted-N-vinyl-amide monomer, based on the total weight of the solids in the ceramer composition.
Preferably the inorganic particles, binder and any other ingredients in the hardcoat are chosen so that the cured hardcoat has a refractive index close to that of the substrate. This can help reduce the likelihood of Moiré patterns or other visible interference fringes.
Zc-A-(CF2O)e(CF2CF2−m(CF3)mO)fCF2-A-Zd (II)
wherein each Z is an acrylate or methacrylate group; m is 0 or 1; c and d are 0 to 3 with the proviso that c+d is at least 2; e and f are greater than 5 when M is zero; e can be zero and f is greater than 5 when m is one; and each A is a c+1 or d+1 valent linking group such as. Preferred linking groups A include:
which are commercially available as KRYTOX™ diesters from E. I. du Pont de Nemours Co.
(C 2H5O)2CH3SiC3H6NHCO(CF2O)15(C2F4O)13CF2CONHC3H6SiCH3(OC2H5)2,
(C 2H5O)3SiC3H6NHCO(CF2O)15(C2F4O)13CF2CONHC3H6Si(OC2H5)3,
F(CF(CF 3)CF2O)25CF2CF3, C4H9NHCO(CF2O)15(C2F4O)13CF2CONHC4H9,
CH 2═CHCOOC2H4NHCO(CF2O)15(C2F4O)13CF2CONHC2H4OOCCH═CH2,
CH 2═CHCOOCH2(CF2O)15(C2F4O)13CF2CH2OOCCH═CH2,
(HOCH 2)2CH2NHCO(CF2O)15(C2F4O)13CF2CONHCH2(CH2OH)2,
(C 2H5O)3Si(CH2)3NHCO(CF2CF2O)8CF2CONH(CH2)3Si(OC2H5)3,
(C 2H5O)2CH3Si(CH2)3NHCO(CF2CF2O)8CF2CONH(CH2)3SiCH3(OC2H5)2,
(C2H5O)2CH3Si(CH2)3NHCO(CF2CF2O)14CF2CONH(CH2)3SiCH3(OC2H5)2,
(C 2H5O)3Si(CH2)3NHCO(CF2C(CF3)FO)12CF2CONH(CH2)3Si(OC2H5)3,
(C 2H5O)2CH3Si(CH2)3NHCO(CF2C(CF3)FO)12CF2CONH(CH2)3SiCH3(OC2H5)2,
The antisoiling layer can if desired contain other compatible fluorochemicals such as perfluorinated surfactants, perfluoroalkyl acrylates and perfluoroalkyl methacrylates blended with the perfluoropolyether. Other adjuvants such as soluble or miscible photoinitiators may also be included in the antisoiling layer if desired.
The display element optionally can include an adhesive on the backside of the substrate. Preferably the adhesive is transparent or sufficiently translucent so that it will not unduly hamper viewing of an underlying display device. The adhesive can be derived from a natural product (e.g., a rubber-base adhesive) or can be a synthetic material such as a homopolymer, random copolymer, graft copolymer, or block copolymer. The adhesive can be crosslinked or uncrosslinked, and if desired can have pressure-sensitive properties. An accepted quantitative description for pressure sensitive adhesives (PSAs) is given by the Dahlquist criterion, which indicates that materials having a storage modulus (G′) of less than about 3×105 Pascals (measured at 10 radians/second at room temperature, about 20° to 22° C.) have pressure sensitive adhesive properties while materials having a G′ in excess of this value do not. Non-pressure sensitive adhesives are preferred, especially those that provide selective adhesion, e.g., adhesives that have low tack or are non-tacky with respect to skin but have high tack with respect to a targeted surface such as the surface of a display. Display elements coated with such non-pressure sensitive selective adhesives can be easily handled and applied to a display surface, and can be cleanly removed if needed. Suitable low tack or non-tacky adhesives include those described in U.S. Pat. No. 5,389,438 (Miller et al.), U.S. Pat. No. 5,851,664 (Bennett et al.), U.S. Pat. No. 6,004,670 (Kobe et al.) and U.S. Pat. No. 6,099,682 (Krampe et al.). Thermoplastic block copolymer elastomers (copolymers of segmented A and B blocks or segments, displaying both thermoplastic and elastomeric behavior) are especially preferred. Useful thermoplastic block copolymer elastomers include multi-block copolymers having radial, linear A-B diblock, and linear A-B-A triblock structures, as well as blends of such copolymers. Suitable commercially available thermoplastic block copolymer elastomers include the SOLPRENE™ family of materials (Philips Petroleum Co.), the FINAPRENE™ family of materials (FINA), the TUFPRENE™ and ASAPRENE™ family of materials (Asahi), the STEREON™ family of materials (Firestone Synthetic Rubber & Latex Co.), the EUROPRENE SOL T™ family of materials (Enichem), the VECTOR™ family of materials (Dexco Polymers), and the CARIFLEX TR™ family of materials (Shell Chemical Co.). Other suitable adhesive materials include highly crosslinked acrylic adhesives, silicone polyurea elastomers such as are described in U.S. Pat. No. 5,670,598 (Leir et al.), the SEPTON™ family of materials (Kuraray Co. Ltd.) and the KRATON™ family of materials (Shell Chemical Co.) such as KRATON D-1101, D-1102, D-1107, D-1111, D-1112, D-1113, D-1114PX, D-1116, D-1117, D-1118, D-1119, D-1122X, D-1124, D-1125PX, D-1160, D-1165, D-1161, D-1184, D-1193, D-1300, D-1320X, D-4141, D-4158, D-4433, RP-6485, RP-6409, RP-6614, RP-6906, RP-6912, G-1650, G-1651, G-1652, G-1654, G-1657, G-1701, G-1702, G-1726, G-1730, G-1750, G-1765, G-1780, FG-1901, FG-1921, FG-1924, and TKG-101. Mixtures of adhesive materials can also be used.
Adhesion of the coating layers to the substrate was evaluated by crosshatching the coating with a sharp knife and applying and removing a tape strip to the crosshatched coating, according to ASTM Test Method D3359-97. The amount of coating removed was evaluated using the 5-point scale set out in the Test Method. Peel adhesion was evaluated according to ASTM Test Method D-3330, using an IMASS™ Model SP-2000 peel tester (Imass Inc.) operated at a 2.3 m/min. peel rate (Method A, 180° peel).
A ceramer composition was prepared by first heating 51.5 Parts of the curable binder precursor PETA (pentaerythritol triacrylate) to approximately 49° C. in a reaction vessel. 88 Parts of NALCO™ 2327 colloidal silica sol (a 40% solids, 20 nanometer average particle size silica sol, Nalco Corp.) were added to the PETA. The resulting mixture contained 32.4 parts of colloidal silica particles. 15.6 Parts DMA (N,N-dimethylacrylamide) were next added to the mixture. 0.15 Parts BHT (butylated hydroxytoluene) and 0.02 parts phenothiazine were mixed together and added to the mixture. The mixture was “stripped” by subjecting it to a gentle vacuum distillation (at 100±20 mm Hg and 52°±2° C.) until most of the liquid was removed. A few weight-percent of water remained in the dried product. The resulting dried ceramer precursor was diluted to 50% solids with a 14/1 isopropyl alcohol/distilled water mixture, then further diluted to 25% solids using the same alcohol/water mixture. 0.7 Parts IRGACURE™ 184 photoinitiator (Ciba Specialty Chemicals) were added to the diluted product to provide a photocurable ceramer composition.
The ceramer composition was coated onto 0.04 mm PET film using a Meyer Rod or a gravure roller, at a coating weight sufficient to provide a dried coating thickness of about 3 to about 5 micrometers. The wet coating was dried at 70° C. and cured using a UV H lamp operated at an energy density of 10-60 mJ/cm2 UVC and a nitrogen purge.
An antisoiling layer was applied to the cured hardcoat by dissolving a series of perfluoropolyethers in varying amounts of HFE-7100™ C4F9OCH3 hydrofluoroether solvent (3M) and coating the resulting solutions onto the cured hardcoat samples using a Meyer Rod at a coating weight sufficient to provide a dried coating thickness of about 0.03 to about 0.2 micrometers. The wet coating was dried at 70° C. and cured using a UV H lamp operated at an energy density of 5 mJ/cm2 UVC under a nitrogen purge.
Control or Ceramer Parts of Perfluoropolyether Parts of Photoinitiator Parts of Adjuvant
Example No. coating method (PFPE) in PFPE in PFPE Parts of Solvent
Control 1 None None
(plain PET)
Control 2 Gravure None
Control 3 None 0.1 PFPE-A1 0.0015 R20748 20 HFE14
(No Ceramer)
1 Meyer Rod 0.1 PFPE-A 0.0015 R2074 20 HFE
2 Meyer Rod 0.1 PFPE-A 0.0015 R2074 40 HFE
3 Meyer Rod 0.1 PFPE-B2 0.0015 R2074 40 HFE
4 Meyer Rod 0.1 PFPE-A 0.0015 R2074 0.01 A17412 40 HFE
5 Meyer Rod 0.1 PFPE-A/ 0.0015 R2074 40 HFE
0.01 PFPE-C3
6 Meyer Rod 0.1 PFPE-A/ 0.0015 R2074 40 HFE
0.01 PFPE-D4
7 Gravure 0.1 PFPE-A/ 0.0015 R2074/ 40 HFE
0.1 PFPE-E5 0.004 DEAP9
8 Gravure 0.1 PFPE-F6 20 HFE
9 Gravure 0.1 PFPE-F 40 HFE
10 Gravure 0.1 PFPE-F 0.004 D-117310 40 HFE
11 Gravure 0.1 PFPE-E 0.004 I-18411 40 HFE
12 Gravure 0.1 PFPE-E 0.004 I-184 20 HFE
13 Gravure 0.1 PFPE-E 0.004 I-184 80 HFE
14 Gravure 0.1 PFPE-E 0.004 D-1173 40 HFE
15 Gravure 0.1 PFPE-E 0.004 D-1173 20 HFE
16 Gravure 0.1 PFPE-E 0.004 D-1173 80 HFE
17 Gravure 0.1 PFPE-E 0.004 D-1173 160 HFE
18 Gravure 0.1 PFPE-E 0.004 D-1173 1600 HFE
19 Gravure 0.1 PFPE-E 0.004 D-1173 0.04 A174 40 HFE
20 Gravure 0.1 PFPE-E 0.004 D-1173 0.05 K1514 40 HFE
21 Gravure 0.1 PFPE-E/ 0.004 D-1173 40 HFE
22 Gravure 0.1 PFPE-E/ 0.004 D-1173 40 HFE
23 Gravure 0.1 PFPE-E/ 0.004 D-1173 40 HFE
0.05 PFPE-G6
24 Gravure 0.1 PFPE-H7 0.004 D-1173 40 HFE
1PFPE-A is (C2H5O)2CH3SiC3H6NHCO(CF2O)15(C2F4O)13CF2CONHC3H6SiCH3(OC2H5)2.
2PFPE-B is (C2H5O)3SiC3H6NHCO(CF2O)15(C2F4O)13CF2CONHC3H6Si(OC2H5)3.
3PFPE-C is KRYTOX ™ 1514 perfluoroether fluid F(CF(CF3)CF2O)25CF2CF3 (E. I. DuPont de Nemours & Co.).
4PFPE-D is C4H9NHCO(CF2O)15(C2F4O)13CF2CONHC4H9.
5PFPE-E is CH2═CHCOOC2H4NHCO(CF2O)15(C2F4O)13CF2CONHC2H4OOCCH═CH2.
6PFPE-F is CH2═CHCOOCH2(CF2O)15(C2F4O)13CF2CH2OOCCH═CH2.
7PFPE-G is (HOCH2)2CH2NHCO(CF2O)15(C2F4O)13CF2CONHCH2(CH2OH)2.
8PFPE-H is:.
9R2074 is RHODORSIL ™ 2074 diaryliodonium tetrakis(pentafluorophenylborate) from Rodia.
10DEAP is 2,2-diethoxyacetophenone.
11D-1173 is DAROCURE ™ 1173 2-hydroxy-2-methyl-1-phenyl-propan-1-one from Ciba Specialty Chemicals.
12I-184 is IRGACURE ™ 184 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals).
13A-174 is A-174 gamma-methacryloxypropyl trimethoxysilane (Union Carbide Corp.).
14HFE is HFE-7100 ™ C4F9OCH3 hydrofluoroether solvent (3M).
Example Ink Durability, Steel
No. Repellency Hardness Clarity Cheesecloth Wool
Control A None HB Clear None None
Control B None N Clear None None
Control C 4 ND Clear None None
1 5 ND Clear 2 7
2 5 ND Clear 5 12
3 5 ND Clear 6 14
4 4 ND Clear 60 100
5 5 ND Clear 15 40
6 4 ND Clear 10 30
7 4 ND S. Haze 15 60
8 5 >3H Clear 250 1400
9 5 >3H Clear 200 600
10 2 ND Haze ND ND
11 5 ND Clear 300 450
12 5 ND Clear 200 300
13 5 ND Clear 300 450
14 5 >3H Clear 250 500
15 5 ND Clear >100 >500
16 5 ND Clear 250 500
17 4 ND Clear 100 350
18 1 ND Clear ND ND
19 4 ND Clear 250 800
20 4 ND S. Haze >100 >300
21 5 ND Clear >100 >600
22 4 ND S. Haze 100 200
23 4 ND Clear 300 >600
24 4 ND Clear 100 200
Especially good results were obtained using ethylenically unsaturated perfluoroployethers. Although the antisoiling layers were very thin, they formed coatings having very good and very durable ink repellency.
Using the method of Examples 1-24, display elements were prepared by dissolving varying amounts PFPE-F in HFE-7100 solvent and coating the resulting antisoiling coating solutions onto the cured hardcoat samples at a coating weight sufficient to provide a dried coating thickness of about 0.03 to about 0.2 micrometers. Half of the examples included IRGACURE 184 photoinitiator and half employed no photoinitiator. The wet coatings were dried at 70° C. and cured using a UV H lamp operated at an energy density of 35 mJ/cm2 UVC under a nitrogen purge. Set out below in Table 3 is the amount of perfluoropolyether and photoinitiator for each example, and the observed Durability results.
Example Durability, Durability,
No. PFPE-F, % Photoinitiator, % Cheesecloth Steel Wool
25 0.25 None 200 600
26 0.50 None 250 1400
27 1 None 400 1000
28 2 None 300 2000
29 0.25 4 20 60
30 0.50 4 300 1000
31 1 4 300 1800
32 2 4 400 2500
Using the method of Examples 1-24, display elements were prepared by dissolving a variety of perfluoropolyethers and 0.01% RHODORSIL 2074 photoinitiator in HFE-7100 solvent and coating the resulting antisoiling coating solutions onto the cured hardcoat samples at a coating weight sufficient to provide a dried coating thickness of about 0.08 micrometers. The wet coatings were dried at 70° C. and cured using a UV H lamp operated at an energy density of 12 mJ/cm2 UVC under a nitrogen purge. Set out below in Table 4 is the identity of the perfluoropolyether and the observed Durability results for each example.
Example Durability, Durability, Steel
No. Perfluoropolyether Cheesecloth Wool
33 PFPE-I1 15 50
34 PFPE-J2 6 8
35 PFPE-K3 30 15
36 PFPE-L4 2 12
37 PFPE-M5 8 19
1PFPE-I is (C2H5O)3Si(CH2)3NHCO(CF2CF2O)8CF2CONH(CH2)3Si(OC2H5)3.
2PFPE-J is (C2H5O)2CH3Si(CH2)3NHCO(CF2CF2O)8CF2CONH(CH2)3SiCH3(OC2H5)2.
3PFPE-K is (C2H5O)2CH3Si(CH2)3NHCO(CF2CF2O)14CF2CONH(CH2)3SiCH3(OC2H5)2.
4PFPE-L is (C2H5O)3Si(CH2)3NHCO(CF2C(CF3)FO)12CF2CONH(CH2)3Si(OC2H5)3.
5PFPE-M is (C2H5O)2CH3Si(CH2)3NHCO(CF2C(CF3)FO)12CF2CONH(CH2)3SiCH3(OC2H5)2.
The results shown in Table 4 demonstrate the use of a variety of perfluoropolyethers, applied at a very low coating thickness.
Solution No. Ceramer Solvent Mixture % Solids
1 50 parts 50 parts 8.5
2 85 parts 15 parts 14.45
3 80 parts 20 parts 13.6
Using the method of Examples 1-24 and a No. 18 Meyer rod, each of the ceramer solutions was coated onto 0.13 mm thick PET film. The coated PET substrate was dried at 93° C. for 3 minutes, then cured by passing the coatings twice under UV D lamps operated at an energy density of 400-600 mJ/cm2 UVA. The dried ceramer coating thickness was 1 to 2 micrometers. Some samples coated with Ceramer Solution Nos. 2 or 3 were given a second coat and again cured, resulting in a dried ceramer coating thickness of 2 to 4 micrometers. The ceramer-coated samples were next coated with a perfluoropolyether antisoiling coating solution prepared from 1 part PFPE-F (CH2═CHCOOCH2(CF2O)15(C2F4O)13CF2CH2OOCCH═CH2), 0.04 parts IRGACURE 184 photoinitiator, 93 parts HFE-7100 solvent and 23 parts methyl ethyl ketone solvent. The perfluoropolyether solution was applied at a coating weight sufficient to give a dried antisoiling coat thickness of about 0.05 to 0.1 micrometers. Using the method of Examples 1-24, the antisoiling coats were dried and cured under UV H lamps operated at an energy density of 10-60 mJ/cm2 UVC. Set out below in Table 6 are the ceramer solution numbers, the number of coats of ceramer solution, the ceramer coat thickness, and the conductivity, ink repellency and tape adhesion values for the coated substrates:
Ceramer No. of Ceramer Tape
Solution Ceramer Thickness, Conduc- Ink Adhe-
No. Coats micrometers tivity Repellency sion
1 1 1 to 2 1 × 1012 5 5
2 1 1 to 2 1.5 × 1010 5 5
2 2 2 to 4 7 × 109 5 4
3 1 1 to 2 4 × 1010 5 5
3 2 2 to 4 1.5 × 1010 5 4
A 3-necked reaction vessel was fitted with a vacuum distillation head and condenser, mechanical stirrer, heating mantle, and thermocouple for controlling the heating. The vessel was charged with 6,718 parts NALCO™ 1042 acidic aqueous sol (pH 3.5 sol from ONDEO Nalco Co., containing 34% of 20 nanometer average diameter silica particles), 1,122 parts hydroxyethyl acrylate, 562 parts 3-(trimethoxysilyl)propyl methacrylate, 2 parts butylated hydroxytoluene, and 0.2 parts phenothiazine. The contents were stirred at room temperature for 1 hour, then heated to 55° C. over about 45 min. The pressure in the vessel was slowly reduced using a vacuum pump to remove volatiles without causing undue foaming. As the foaming subsided, full pump vacuum was applied until nearly all volatiles were removed. This required about 6 to 7 hours of distillation. The vacuum was relieved and then 792 parts SR 444 pentaerythritol triacrylate (Sartomer, Inc.) were added to the vessel. Full pump vacuum was re-applied and the remaining volatiles were removed. When distillation was complete, the contents of the vessel were filtered through fine-mesh cheesecloth to provide a 100% solids solvent-free ceramer hardcoat.
% 1st
Substrate/ % Total Surface % 20° 60° 85° Ink Durability, Pencil
Run No. Roughness Reflection Reflection Trans. Haze Clarity Gloss Gloss Gloss Rep. Steel Wool Hard.
Control1 PVC/ND2 7.186 3.999 80.2 28.2 53.6 7.9 38.3 47.8 0 4 2B
39-1 PET/0.36 4.853 2.187 93.9 32.8 58.2 8.9 27.4 57 5 1000 >3H
39-2 PET/0.44 4.068 1.358 93.7 44.8 34.3 3.7 16.9 34 5 500 >3H
39-3 PET/0.57 3.899 1.205 93.6 49.5 29.8 4 15.7 32.7 5 1000 >3H
39-4 PMMA/0.36 4.383 1.46 95.4 32.2 57.6 9.9 28.7 61.4 ND ND ND
39-5 PMMA/0.44 3.833 1.392 95.3 43.9 34.1 4.8 18.7 43.9 ND ND ND
39-6 PMMA/0.57 3.566 1.14 95.2 48.6 29.6 4.6 16.9 38.4 ND ND ND
1WrightRIGHT ™ PDA Screen Protector, Fellowes Corporation.
2ND = Not determined.
The adhesive-coated side of the coated PET films was pressed against a plain paper liner, and the films were then die-cut to a rectangular shape to form custom screen protectors sized to fit just inside the perimeter of the screen of a PALM™ Vx PDA (Palm Computing Corp.) like the PDA shown in FIG. 6. The screen protectors covered nearly the entire screen, leaving a small uncovered area between the curved bottom edge of the screen and the chord extending between the endpoints of the bottom edge. The screen protectors were also hand-trimmed to fit just inside the perimeter of the screen of an IPAQ™ color PDA (Compaq Corp.) like the PDA shown in FIG. 4. The screen protector was removed from the liner and pressed into place over the screen of the PDA, using the edge of a credit card to assist in removing air bubbles from under the film. The film provided substantial indoor and outdoor glare reduction without unduly reducing visibility through the PDA screen. When the screen protector of the invention was not present, light reflections made it difficult to read the screen at some angles. The matte finish on the screen protector made it easier to write on the screen using the PDA stylus, because the stylus point had a reduced tendency to skid across the screen. A pen or pencil could also be used to write on the PDA screen protector. A small amount of ink or graphite transferred to the screen protector, but was readily removed using a tissue without leaving any observable damage on the screen protector surface. In contrast, if a pen or pencil is used to write directly on the unprotected PDA screen, the screen typically will be permanently damaged.
In a series of runs, the backside of the coated film of Example 27 was coated using a knife coater with two different adhesives and dried at 70° C. for 15 minutes. The resulting adhesive-coated samples were applied to glass for varying dwell periods and then evaluated for 180° peel adhesion. Set out below in Table 8 is the run number, adhesive identity, dry adhesive thickness and the measured peel adhesion values.
Adhesive 180° Peel Strength, g/mm of width
Run Adhe- Thickness, 12 hours, 72 hours, 170 hours,
No. sive mm Initial 25° C. 70° C. 70° C.
1 RD-9751 0.03 58 80 110 103
2 RD-975 0.05 74 104 132 127
2 RD-975 0.08 86 117 126 129
3 11072 0.05 6 18 19 14
3 1107 0.08 28 41 39 31
1RD-975 acrylic adhesive (3M).
228% solution of KRATON ™ 1107 elastomer (Shell Chemical Co.) in toluene.
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U.S. Classification 427/64, 427/376.2, 427/419.2, 348/E05.131, 427/164, 348/E05.143, 427/365, 427/385.5, 427/407.1
International Classification C09J201/00, G02B1/10, B32B27/00, C09D7/12, C08G65/333, C09D171/00, G02F1/1335, C09D5/16, B32B7/02, C09K3/00, C09D5/24, C09D129/10, B32B7/12, C09D5/00, G09F9/00, C08G65/336, C09D4/06, G06F1/16, C09D4/00, C09J7/02, G02B21/34, C09D153/00, H01J29/86, H04N5/65, C08L53/00, C08F2/44, C08G65/00, C09D171/02, G01N1/36, H04N5/74, C08F290/06, G06F3/041, C09J153/00, G06F3/033
Cooperative Classification Y10T428/31928, Y10T428/31663, Y10T428/31909, Y10T428/31891, Y10T428/3188, Y10T428/31935, Y10T428/31797, Y10T428/31544, Y10T428/3154, G02B21/34, Y10T428/1429, Y10T428/1424, C09D4/06, Y10T428/24967, Y10T428/1476, Y10T428/2891, Y10T428/265, C09D153/00, C09J7/0239, H04N9/3141, Y10T428/2848, C08F290/06, G06F1/1626, H04N5/65, C08F2/44, Y10T428/24975, Y10T428/28, Y10T428/2495, G01N1/36, C09D4/00, Y10T428/24942, G06F1/1607, C09J2433/00, H01J29/868, Y10T428/2813, Y10T428/25, Y10T428/259, C08L53/00, C08G65/007, C09J153/00, Y10T428/24802, Y10T156/1002, C09D171/02, G06F3/041
European Classification G06F1/16D6, C09D4/00, C08L53/00, C09D4/06, C09J153/00, C09D153/00, C09D171/02, C08G65/00B2F, C08F2/44, G02B21/34, C09J7/02K, C08F290/06, G06F3/041, G06F1/16P3, H01J29/86H2, G01N1/36
Mar 6, 2007 RF Reissue application filed