WO1998055555A1 - Anti-dew adhesive film - Google Patents
Anti-dew adhesive film Download PDFInfo
- Publication number
- WO1998055555A1 WO1998055555A1 PCT/US1997/017096 US9717096W WO9855555A1 WO 1998055555 A1 WO1998055555 A1 WO 1998055555A1 US 9717096 W US9717096 W US 9717096W WO 9855555 A1 WO9855555 A1 WO 9855555A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dew
- film
- article
- layer
- adhesive
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
Definitions
- This invention pertains to articles that have an anti-dew film bonded to a substrate using an adhesive layer and to methods of making these articles.
- the anti- dew articles are particularly useful on retroreflective articles.
- Retroreflective articles have the unique property of being able to return a substantial portion of incident light back toward the light source over a wide range of incoming light angles.
- a primary use of retroreflective articles is on traffic signs. At night, light from motor vehicle headlights strikes the traffic sign and is retroreflect ⁇ d back to the motor vehicle driver. The bright image displayed by the retroreflective sign makes the sign easier to read and gives motorists more time to react.
- Retroreflective signs are commonly displayed outdoors and thus are frequently exposed to moisture droplets that form on its surface and to weathering conditions such as heat, cold, hail, etc. These environmental conditions can sometimes make it difficult for motor vehicle drivers to read the information on the signs.
- Investigators in the retroreflective art have recognized the existence of these problems for many years. For example, in 1946 Palmquist et al. in U.S. Patent No. 2,407,680 taught the need for weatherproof retroreflective signs and retroreflective articles with exterior water-spreading surfaces to minimize the effects of water droplets. More recently, traffic signs have been used that have an exterior anti-dew film (of the type described by Krautter et al.
- a retroreflective traffic sign in which the pressure sensitive adhesive is made of a cross-linked ester acrylate/acrylic acid with tackifier.
- the present invention provides a durability improved article with an anti- dew film on an exterior surface.
- the inventive article comprises, at least, an anti- dew film, and an adhesive layer disposed on the anti-dew film.
- the adhesive comprises a cross-linked pressure sensitive adhesive (psa).
- the psa is essentially without a tackifying resin because it has been found that the presence of a tackifier in the adhesive layer causes undesirable properties.
- the adhesive layer has a glass transition temperature, T g , below about -15 C.
- T g glass transition temperature
- the anti-dew film has an anisotropic structure with a polymeric base layer and a water-spreading surface film that contains inorganic oxide particles.
- the inorganic particles in the water-spreading layer have a lower thermal expansion coefficient than the polymeric base layer; the anti-dew film is anisotropic in that the water-spreading layer has a different coefficient of thermal expansion than the surface layer.
- changes in temperature cause the anti-dew film to curl.
- the anti-dew film tends to peel off substrates such as retroreflective traffic signs.
- the adhesive of the present invention has sufficient strength to counteract this curling tendency, resulting in more durable dew-resistant articles.
- the invention further provides a method of making a durability improved article with an anti-dew film in which an ester acrylate, a copolymerizable monoethylenic monomer and a cross-linking agent are combined to form a composition that is essentially without tackifiers, and the composition is cured to form a pressure sensitive adhesive.
- the pressure sensitive adhesive is disposed between a substrate and an anti-dew film, wherein the anti-dew film comprises a polymeric base layer and a surface layer wherein inorganic oxide particles occupy at least a portion of the exterior surface.
- the present invention provides an excellent balance of properties and numerous advantages, even after outdoor exposure for several years, including: peel strength, shear strength, clarity/non-phase separation, nonyellowing, nonpeeling, impact resistance, economy and simplicity of construction and preparation, durability at extremes of heat and cold, and lasting dew resistance.
- Fig. 1 is a cross-sectional view of a retroreflective sign according to a preferred embodiment of the invention.
- Fig. 2 is a graph of data showing the increase of shear strength with increasing concentration of cross-linker.
- Fig. 1 shows the order of layers in a preferred embodiment of the invention but is not drawn to scale and does not accurately depict the relative thicknesses of each layer.
- retroreflective sheeting 4 is mounted on backing board 2.
- the retroreflective sheeting is mounted on the backing board by an intervening pressure sensitive adhesive layer (not shown).
- Colored overlay 6 with cutout regions 7 is bonded on the retroreflective layer by another pressure sensitive adhesive (not shown).
- the adhesive layer 8 bonds the anti-dew-film to the retroreflective layer.
- the surface of the anti-dew- film 10 consists of water-spreading layer 12 that contains hydrophilic inorganic oxide particles 14.
- the article of the present invention is a retroreflective traffic sign that contains a layer of retroreflective sheeting.
- retroreflective sheeting examples include ScotchliteTM Reflective Sheeting High Intensity Grade Series 3870, ScotchliteTM Reflective Sheeting Diamond Grade VIP Series 3990, and ScotchliteTM Reflective Sheeting Diamond Grade LDP Series 3970, available from 3M, St. Paul, Minnesota.
- Retroreflective sheeting typically comprises a reflective surface and optical elements.
- the reflective surface serves to reflect incident light, and the optical elements serve to redirect the incident light toward the light source.
- the reflective material may comprise a specular metal reflector such as aluminum or silver (see, for example, U.S. Patent No.
- Optical elements typically come in one of two forms: beaded lens elements and cube corner elements. Examples of retroreflective sheeting that employ beaded lens elements have been disclosed in U.S. Patent Nos. 2,407,680, 3,190,178, 4,025,159, 4,265,938, 4,664,966, 4,682,852, 4,767,659, 4,895,428, 4,896,943, 4,897, 136, 4,983,436, 5,064,272 and 5,066,099.
- the surface of the retroreflective sheeting facing the anti-dew film is a polymeric material, preferably an acrylate, more preferably polymethymethacrylate.
- the surface may be impregnated with color pigments.
- a series of colored High Intensity Grade, Diamond Grade VIP, and Diamond Grade LDP ScotchliteTM retroreflective sheetings in colors such as yellow, orange, brown, blue and green are available from 3M, St. Paul, MN.
- the surface facing away from the anti-dew film is typically coated with an adhesive layer, preferably a pressure sensitive adhesive.
- the back board 2 is typically a metallic, wooden or polymeric material.
- the back board is a rigid material, with aluminum being the most common.
- the inventive article may also have a flexible polymeric material backing material or a combination in which a flexible polymeric material is mounted onto a rigid material such as aluminum or plywood.
- the back board is usually preferred to be opaque.
- Typical examples of commercially available back boards include: a 2 mm (millimeters) thick acid etched and degreased aluminum panel, a high density 2 cm (centimeters) thick plywood, or a 4 mm thick fiberglass-reinforced plastic panel; all these back boards are commonly used in traffic sign industries and are available from the Lyle Sign Company, Eden Prairie, MN.
- the colored overlay 6 is preferably a plastic sheet about 25 ⁇ m to 125 ⁇ , more preferably about 75 ⁇ m in thickness. Cut-outs are made in the overlay layer. Typically the cut-outs are in the shape of letters, numbers or other graphic information. The colored overlay blocks out light of selected wavelengths while the cut-outs allow unimpeded transmission of light to and from the retroreflective sheeting. Colorless regions may substitute for cut-outs in the colored overlay.
- the overlay is preferably an acrylate, more preferably polymethylmethacrylate.
- the overlay is usually adhered to the retroreflective sheeting by an adhesive, preferably a pressure sensitive adhesive.
- the adhesives used to bond the retroreflective sheeting to the substrate or bond the colored overlay to the retroreflective sheeting may include the adhesives described herein or those otherwise known in the art. Indeed, colored overlays with adhesives of the type described herein, with release liners, are commercially available for application to retroreflective sheeting in traffic signs.
- the adhesive layer disposed between the retroreflective sheeting and the colored overlay is preferred to have high clarity and at least moderately good adhesion and shear strength.
- Types of ester acrylates used to make the adhesive layer 8 include the C -
- Cio alkyl esters of acrylic and methacrylic acid preferably comprises acrylate or methacrylate ester monomers including ethyl acrylate, n-butyl acrylate (BA), isobutyl acrylate, 2-methyl butyl acrylate, 2-ethylhexyl acrylate, 2- ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, isooctyl acrylate (IOA), isodecyl acrylate (IDA), isooctyl methacrylate, isononyl acrylate, isodecyl methacrylate, and mixtures thereof.
- BA n-butyl acrylate
- IOA isodecyl acrylate
- IDA isodecyl methacrylate
- isononyl acrylate isodecyl methacrylate
- the ester acrylate may also include hydroxyethyl methacrylate, hexyl acrylate, hexyl methacrylate and may also include, vinyl acetate and combinations thereof with acrylates.
- the ester acrylate is most preferably isooctylacrylate. Preferably about 85 to about 99, more preferably about 87 to about 98, and most preferably about 90 to about 97 weight percent ester acrylate, based on the total weight of resin precursors (i.e. the weight of starting materials not including solvents) is used in forming the adhesive layer .
- Preferred copolymerizable monoethylenic monomers include acrylic acid (AA), methacrylic acid, itaconic acid, crotonic acid, acrylamide, acrylonitrile, methacrylonitrile, N-substituted acrylamides, hydroxy acrylates, N-vinyl pyrrolidinone, maleic anhydride fumaric acid and the like.
- the copolymerizable monoethylenic monomers include N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide, N,N-diethyl acrylamide, N,N-diethyl methacrylamide, N-vinyl caprolactam, and the like.
- the most preferred monoethylenic monomers are acrylic acid and methacrylic acid. Preferably about 1 to about 15, more preferably about 2 to about 12, and most preferably about 3 to about 10 weight percent copolymerizable monoethylenic monomers based on the total weight of resin precursors are used in forming the adhesive layer.
- cross-linking agents examples include those described in U.S. Patent Nos. 3,440,242, 4,418,120 and 3,301 ,835.
- Preferred cross-linking agents are di and tri functional aziridines such as trimethylolpropane-tris-(B-N-aziridinyl)propoionate. Most preferred are bis amides such as N,N-bis-propyleneisophthalimide. As shown in Fig. 2, too little cross- linking agent results in unacceptably low shear strength; on the other hand, too much cross-linking agent causes a loss of adhesion due to interfacial failure.
- cross-linking agent or agents are used in about 0.01 to about 0.1, more preferably about 0.02 to 0.08, and most preferably 0.03 to 0.06 weight percent of solids.
- the cross-linked acrylic pressure sensitive adhesive may be formulated to cross-link with UV or electron beam radiation.
- Typical radiation cross-linked psas are described by Martens in U.S. Patent No. 4, 181,752.
- UV absorbers and hindered amine light stabilizers can be incorporated in the pressure sensitive adhesive to prevent UV degradation in outdoor settings.
- Suitable UV absorbers are benzotriazole compounds including TinuvinTM-328, TinuvinTM-P, and hindered amines include TinuvinTM-292,
- TinuvinTM-144, and TinuvinTM-622LD available from Ciba-Geigy Co., Hawthorne NY.
- Other suitable UV absorbers include benzophenone compounds such as UvinulTM-400, UvinulTM-490 and UvinulTM-N539, available from BASF Co., Clifton NJ.
- Preferably, less than two weight percent of each the UV absorbers and hindered amine light stablizers are incorporated in the pressure sensitive adhesive.
- Kealy and Zenk in U.S. Patent No. 4,418,120 teach that crosslinked
- IOA/AA psas should contain an added tackifying rosin ester to achieve an excellent balance of tack, peel adhesion and shear properties in a psa that adheres well to low energy surfaces.
- tackifiers in the adhesive layer bonding the anti-dew layer results in undesirable properties such as yellowing, peeling, phase separation between adhesive and tackifier, loss of transparency (i.e. cloudiness) with aging, and overall poor durability of the dew resistant retroreflective article.
- the adhesive layer should be substantially free of tackifiers; that is, the tackifier should not be present in amounts sufficient to lower durability of the dew resistant article.
- the tackifier should not be present in amounts sufficient to raise the T g of the psa above about -15 C.
- the adhesive layer preferably has less than 5 weight % of tackifiers. More preferably, the adhesive layer contains no tackifiers.
- Tackifiers are typically naturally occurring materials, which are typically complex mixtures of high-molecular-weight organic acids and related neutral materials.
- Tackifiers include wood resins, or modified forms of such naturally occurring resins, e.g., hydrogenated or esterified resins, polymers of terpene, pinene, etc.
- Tackifiers include dark amber natural gum resin (Nelio N available from Union Camp), pale thermoplastic resin derived from the polymerization of mixed olefins (Super Sta-Tac 80 available from Reichhold Chemicals, Inc.), synthetic polyterpene (Wingtack Plus available from Goodyear), medium soft thermoplastic coumarone-indeme resin R 17 supplied by Neville), te ene-urethane resin (Iso-Terp 95 available from Schenectady Chemicals Inc.), and pentaerythritol ester rosin (Foral 85 available from Hercules).
- the anti-dew layer comprises an organic polymeric base layer and a surface layer containing inorganic oxide particles.
- the inorganic oxide particles are hydrophilic and at least a portion of these particles are exposed to the atmosphere.
- the base layer can contain some inorganic oxide particles but it has a lower concentration than the surface layer.
- the base layer is a polymer, preferably a non-biaxially oriented flexible acrylate, that is essentially free of inorganic oxide particles, and the surface layer contains greater than 90% oxide particles, more preferably greater than 98% oxide particles.
- the inorganic oxide particles are preferably silica, alumia, silicoaluminate or mixtures thereof. Examples of anti-dew layers useable in the present invention include those described in U.S.
- silica particles in the surface layer are treated with an aluminate solution to improve durability.
- the retroreflective articles are made using assembly techniques known in the art.
- retroreflective sheeting with pressure sensitive adhesive and release liner is laminated onto a backboard by removing the release liner and passing the laminate through a nip roller.
- a colored overlay having cut-out regions is then applied over the retroreflective sheeting.
- the colored overlay has an adhesive layer and a release liner over the adhesive layer.
- the colored overlay is kiss cut using electronic cutters and the undesired areas are weeded out.
- a removeable premask tape is often applied to the weeded colored overlay to facilitate transfer to the sign face.
- the release liner is stripped off and the overlay is pressed onto the retroreflective sheeting.
- the adhesive used to apply the anti-dew film can be prepared by mixing appropriate amounts of an ester acrylate(s) and copolymerizable ethylenic monomer(s) in an organic solvent or mixture of organic solvents. A cross-linker is added with mixing. The resulting solution is then coated, preferably by roll coating onto a silicone-coated paper release liner. Solvent is removed by evaporation and the adhesive is cured. In a preferred embodiment, an IOA/AA adhesive with a bis amide cross-linker is cured by heating at about 150 C for about 10 min.
- An anti- dew film is applied onto the adhesive layer, for example by passing through a nip roller.
- the thus-produced anti-dew film with adhesive and release liner can be stored for future use.
- the release liner can be peeled off and the exposed adhesive pressed onto the traffic sign.
- the psa for the anti-dew film preferably has strong adhesion over temperatures ranging from -40 C to 35 C.
- the retroreflective sign preferably exhibits no visual yellowing after 10 years of outdoor exposure.
- the adhesive should retain good clarity.
- the acrylic copolymer in the psa is cross-linked to provide good peel strength and shear strength over service temperatures of -40 C to 35 C.
- the psa should have high transparency, preferably the psa layer is greater than 85% transparent, more preferably greater than 90% transparent to visible light.
- the psa preferably has a T g , as measured by differential scanning calorimetry - ASTM E1356, of less than -15 C, more preferably less than -20 C.
- the psa has a peel strength such that an article with a 3 mil thick adhesive layer has a 90 peel strength of greater than 3, and more preferably greater than 4 lbs/in at 0 C.
- the dew resistant retroreflective signs have an impact resistance such that a 1.39 kg m impact to the back of the sign at -10 C causes no delamination of the dew resistant film, more preferably a 1.39 kg m impact to the back of the sign at -22
- the retroreflective signs have good weatherability such that the sign retains more than 90% retroreflectivity and has a yellowness index of less than 5 after exposure to 3000 hours of repeated cycles of 4 hours UV light at 60°C and 4 hours condensing humidity at 50°C according to ASTM G53.
- EXAMPLES A film curl test was conducted to determine the curling tendency of the anti- dew film caused by variations in temperature.
- An anti-dew film (Folie farblos 99840, from Rohm GmbH, Chemische Fabrik, Germany - the film is an acrylic film about 50 ⁇ m thick with an inorganic oxide coating on the top surface that is about
- the curling behavior shown in Table 1 is caused by the difference in thermal expansion between the acrylic base layer and the silica surface layer, and by internal stresses created during drying of the silica coating.
- the degree of curl can be used to calculate the curling force; see S. Wu, Polymer Interface and Adhesion, Marcel Dekker, Inc., NY, pp. 465-473 (1982).
- the adhesive is designed with sufficient strength to counteract the curling force that may be caused by heating and cooling the retroreflective article.
- Example 1 Samples prepared according to this procedure are referred to as Example 1.
- a comparative example was prepared using the psa taught by Kealy et al., U.S. Pat. No. 4,418,120.
- To a solution of 100 parts by weight IOA:AA (94:6) was added 30 parts rosin ester tackifying resin (Foral 85 - a glycerol ester of stabilized rosin having a softening point of 82°C, available from Hercules, Inc.) to form about a 45% solids mixture in a blend of acetone, toluene and heptane.
- rosin ester tackifying resin Form 85 - a glycerol ester of stabilized rosin having a softening point of 82°C, available from Hercules, Inc.
- the adhesive was laminated to acrylic overlay film to make a film tape.
- the tape was cut into 1.27-cm wide x 8 cm long strips and applied to 3M ScotchliteTM
- Reflective Sheeting (Diamond GradeTM VIP 3990) which was mounted on a 70 mm x 70 mm x 1.0 mm thick aluminum panel.
- the length of adhesive overlap on the reflective sheeting was 2.54 cm giving an overlap area of 3.22 sq. cm.
- the unapplied tail of the film tape was reinforced with ScotchTM filament tape to prevent tearing under load.
- Shear times (at room temperatures) of approximately 5,000 - 15,000 min are desired for good creep and shrinkage resistance of the applied pressure-sensitive overlay film. This range of shear adhesion is obtained with preferred cross-linker levels of about 0.03 to 0.06 parts bisamide per 100 parts acrylic copolymer.
- Test specimens for measuring reverse impact at low temperature were prepared by laminating an anti-dew film with psa on a retroreflective VIP (3990) sheeting (available from 3M, St. Paul, MN) on an aluminum panel of 6in x 6in (15cm x 15cm), having thickness of 0.080in (0.203 cm). All specimens were conditioned at room temperature for at least 24 hours to allow adhesion to fully develop.
- specimens were cooled in a cooler to -8° F (-22°C), 20 F (-7 C) and 40 F (4 C) for overnight prior to the test.
- specimens were placed on a steel metal ring having diameter of 3 " with the anti-dew film and retroreflective sheeting face down.
- a rounded steel bar weighing 1.98 kilograms was raised to 46.5 or 70 cm and let fall freely to punch the backside of the specimen to create an impact force of 0.92 or 1.39 kilograms-meters, respectively. Results are shown in
- inventive films were subjected to a 90° peel test.
- samples were prepared according to Example 1 but with varying film thicknesses.
- the anti- dew films 2.54 cm wide by 20 cm long, were laminated onto HIS 3870 sheeting
- the HIS 3870 sheeting was laminated onto a degreased aluminum plate.
- the anti-dew film was reinforced with ScotchTM filament packaging tape prior to the peel test.
- the prepared specimens were let sit for at least one day, then cooled to the test temperature for at least two hours prior to testing. 90° peel strength was measured according to ASTM D3330-78.
- the cool chamber was attached to the Instron peel tester and Instron cross-head speed was controlled at 10 cm/min. The results are shown in Table 2.
- the reflective panel yellowness index was measured with a Hunter LabScan Spectrocolorimeter, available from Hunterlab, Inc., Reston VA, in accordance with ASTM D1925. Weathering durability of the specimens was tested in a weatherometer in accordance with ASTM G53.
- the light source in the weatherometer was a fluorescent UV lamp with an intensity maximum at 313 cm '1 . Test specimens were remeasured after 3000 hours of repeated cycles of 4 hours UV light at 60°C and 4 hours condensing humidity at 50°C. The results are shown in Table 4.
- the film specimens using the inventive psa (Ex. 1) and the comparative psa both retained better than 90% of retroreflectivity.
- the retroreflective sheeting without a psa or film coating exhibited a yellowness index increase of 4.9 units, the sheeting with the psa of Ex. 1 increased about 5.5 units and the specimen with the comparative psa increased about 10 units.
- the specimen with the comparative psa showed yellowing while the specimens with the inventive psa showed no observable yellowness.
- the yellowness of the comparative example is primarily caused by the UV degradation of the tackifying resin.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97910717A EP0915941A1 (en) | 1997-06-04 | 1997-09-29 | Anti-dew adhesive film |
AU48018/97A AU4801897A (en) | 1997-06-04 | 1997-09-29 | Anti-dew adhesive film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US86897397A | 1997-06-04 | 1997-06-04 | |
US08/868,973 | 1997-06-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998055555A1 true WO1998055555A1 (en) | 1998-12-10 |
Family
ID=25352682
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/017096 WO1998055555A1 (en) | 1997-06-04 | 1997-09-29 | Anti-dew adhesive film |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0915941A1 (en) |
AU (1) | AU4801897A (en) |
CA (1) | CA2258288A1 (en) |
WO (1) | WO1998055555A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10128013A1 (en) * | 2001-06-05 | 2002-12-12 | Uwe Slabke | Using hydrophilic coatings/foils to prevent dew and hoarfrost formation on traffic signs involves applying hydrophilic coating or foil to prevent dew formation in form of dew droplets |
DE102013217785A1 (en) * | 2013-09-05 | 2015-03-05 | Tesa Se | Use of pressure-sensitive adhesive tapes for optical applications |
US9428654B2 (en) | 2004-04-15 | 2016-08-30 | Avery Dennison Corporation | Dew resistant coatings |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5073404A (en) * | 1987-03-09 | 1991-12-17 | Minnesota Mining And Manufacturing Company | Silica coating composition for reflective sheeting |
WO1995032237A1 (en) * | 1994-05-19 | 1995-11-30 | Minnesota Mining And Manufacturing Company | Polymeric article having improved hydrophilicity and a method of making the same |
-
1997
- 1997-09-29 AU AU48018/97A patent/AU4801897A/en not_active Abandoned
- 1997-09-29 CA CA002258288A patent/CA2258288A1/en not_active Abandoned
- 1997-09-29 EP EP97910717A patent/EP0915941A1/en not_active Withdrawn
- 1997-09-29 WO PCT/US1997/017096 patent/WO1998055555A1/en not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5073404A (en) * | 1987-03-09 | 1991-12-17 | Minnesota Mining And Manufacturing Company | Silica coating composition for reflective sheeting |
WO1995032237A1 (en) * | 1994-05-19 | 1995-11-30 | Minnesota Mining And Manufacturing Company | Polymeric article having improved hydrophilicity and a method of making the same |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10128013A1 (en) * | 2001-06-05 | 2002-12-12 | Uwe Slabke | Using hydrophilic coatings/foils to prevent dew and hoarfrost formation on traffic signs involves applying hydrophilic coating or foil to prevent dew formation in form of dew droplets |
US9428654B2 (en) | 2004-04-15 | 2016-08-30 | Avery Dennison Corporation | Dew resistant coatings |
DE102013217785A1 (en) * | 2013-09-05 | 2015-03-05 | Tesa Se | Use of pressure-sensitive adhesive tapes for optical applications |
US9957423B2 (en) | 2013-09-05 | 2018-05-01 | Tesa Se | Use of pressure-sensitive adhesive tapes for optical applications |
Also Published As
Publication number | Publication date |
---|---|
AU4801897A (en) | 1998-12-21 |
EP0915941A1 (en) | 1999-05-19 |
CA2258288A1 (en) | 1998-12-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5861211A (en) | Articles incorporating pressure-sensitive adhesives having improved adhesion to plasticized polyvinyl chloride | |
US6677030B2 (en) | Retroreflective articles having tackified acrylic adhesives for adhesion to curved low surface energy substrates | |
JP4038588B2 (en) | Retroreflective sheeting | |
JP2000500510A (en) | Heat activatable adhesive composition | |
MXPA97006018A (en) | Articles that incorporate adhesives sensitive to lapresion, which have improved adherence to polyvinyl plastify chloride | |
KR19990087235A (en) | Pressure sensitive adhesive | |
US5639530A (en) | Retroreflective articles comprising a non-thermoplastic hydrocarbon elastomer adhesive layer for life saving devices at sea | |
KR20100058505A (en) | Pressure-sensitive adhesive composition having improved initial tack | |
US9321938B2 (en) | Dual crosslinked tackified pressure sensitive adhesive | |
JP4577928B2 (en) | Adhesive composition and retroreflective member using the same | |
EP0915941A1 (en) | Anti-dew adhesive film | |
US20030223137A1 (en) | Reflective sheet, articles made therefrom and methods of using same | |
AU634038B2 (en) | Adhesive-backed film composite which can become permanently bonded to a plasticized substrate | |
MXPA99000236A (en) | Anti-dew adhesive film | |
JPH0343480A (en) | Method for bonding rubber sheet to rigid insulating material | |
JP3811015B2 (en) | Paint, production method thereof, coating film, production method thereof, and pressure-sensitive adhesive sheet | |
KR20060016291A (en) | Retroreflective sheet having the good maintenance of it's shape in irregular surface and method for manufacturing the same | |
JP2004133237A (en) | Retroreflective sheet | |
KR100725696B1 (en) | Tape using retroreflective sheet for traffic lane indication | |
AU702114C (en) | Heat-activatable adhesive composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG |
|
ENP | Entry into the national phase |
Ref document number: 2258288 Country of ref document: CA Ref country code: CA Ref document number: 2258288 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/1999/000236 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1997910717 Country of ref document: EP |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWP | Wipo information: published in national office |
Ref document number: 1997910717 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1997910717 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: JP Ref document number: 1999502351 Format of ref document f/p: F |