JP2000510065A - Cloud-free image protection layer - Google Patents

Abstract

Abstract: An optically clear, transparent protective layer 12 for transferring from a release liner (not shown) to an imaged substrate is disclosed. This layer has a composition containing a vinyl resin, an optional acrylic resin, an optional plasticizer, and an optional stabilizer. This layer also optionally includes a pressure sensitive adhesive 16 that adheres to the imaged substrate 22 and image 24 by pressure, after which the release liner is peeled off. The release liner has a Sheffield smoothness of 1 to 10. Methods of making and using this layer are also disclosed. Image 26 may be between protective layer 12 and pressure-sensitive adhesive 16.

Description

DETAILED DESCRIPTION OF THE INVENTION Cloud-free image protection layer Field of the invention   The present invention relates to optically haze-free layers for use on images on substrates. Background of the Invention   Made by electrographic process, inkjet process, etc. Released electronic graphics quickly become the preferred method for image formation. I came. Minnesota Mining and Manu, St. Paul, Minnesota Scotchprlnt commercially available from the Manufacturing Company ("3M Company") Electronic Graphics Systems ™ uses electrostatic processes to shape images And transfer the image to a durable substrate. This process is United States No. 5,114,520 (Wang et al.).   Images formed on durable substrates require protection from abrasion and UV light It is. Optics glued on the main surface with a clear, optically cloudy pressure-sensitive adhesive Optically clear and transparent, made of transparent durable film Overlamination is preferably used on images on durable substrates ing. Commercially available clear, clear, overlaminates are not available in Minnesota. 3M's commercial graphic Product numbers 8910, 8911, 8912, 8913, There are 8920, 8930, and 8931 films. Among them, 8913 and 8930 has no optical haze. Some of the clear over-laminates without fogging It contains a vinyl or polyester film covered with a pressure sensitive adhesive, The adhesive is protected with a paper or polyester liner until use. Other clear, clear, overlaminates may be used to cover the hot-melt adhesive Nylon or polyester film and scrim lining to prevent blocking Contains ginger.   Some processors do not use clear, transparent overlaminates 3920, 89, manufactured by 3M's Commercial Graphics Division Of vinyl / acrylic materials such as 20, 9720, 66201 and 2120 Use a cloudless protective coat to protect durable imaged substrates I have. However, when applying liquids to solid surfaces in this way, the climate, Human inconsistency arises.   Optically haze-free transparent overlaminates known in the art are It is very suitable for the usage conditions of Achieving a clear, optically haze-free, transparent overlaminated film Extremely difficult. Summary of the Invention   In the field of electronic graphics, compared to other clear layers known to those skilled in the art. A relatively inexpensive, durable, optically clear, transparent layer on the major surface of the substrate. To protect the image formed It is necessary to This means that the substrate is a perforated film and has an image This is especially true when looking through the hole from a non-surface.   One aspect of the invention is that the layers of the invention have acceptable optical clarity. Formed on a polymeric release liner with favorable surface properties such as An inexpensive, durable, optically clear, transparent layer.   The layer that covers and protects the base material with image is made of vinyl chloride resin, optional acrylic resin, Consisting of a composition containing an optional plasticizer and an optional stabilizer, wherein the composition comprises Has a layer thickness from 0.05 mm (0.002 in.) To about 0.12 mm (0.005 in.) Is formed on a polymeric release liner.   Another aspect of the present invention is the use of low cost images on a durable substrate. This is a method for forming a transparent layer that is durable and durable and has no optical fogging. Layer shape The layer thickness is about 0.05 mm (0.002 in.) To about 0.127 mm (0.005 in.). 2) from an organosol on a first polymer release liner in the range Forming an optically haze-free transparent layer having a pressure-sensitive adhesive area Optionally adhering to the second release liner; and Optionally laminating an area of pressure sensitive adhesive on the exposed surface of the clear layer; Optionally removing the release liner of the first polymer.   Another aspect of the invention covers a durable, imaged substrate. It is an inexpensive, durable, optically clear, transparent layer composite. The complex is , Durable, substrate with image Contains an optically clear, transparent layer that covers The clear transparent layer is as described above.   A feature of the present invention is that a durable, optical Is to form a transparent layer without any haze, where the surface of the polymer release layer Physical properties determine the optical clarity of the layers of the invention.   Another feature of the present invention is a durable, imaging base from the second release layer. The transfer of a durable, optically clear, transparent layer to a material.   An advantage of the present invention is that the optically haze-free transparent from the release layer to the imaged substrate The ability to transfer layers.   Another advantage of the present invention is that a durable, optically clear, transparent layer is less expensive. Qualitative and protection from wear and degradation by ultraviolet light.   Accordingly, the present invention also provides for forming a layer of the present invention on a polymer release liner. And laminating the layer of the present invention to a substrate with an image. To protect the substrate with image.   Embodiments of the present invention will be described with reference to the following drawings. BRIEF DESCRIPTION OF THE FIGURES   FIG. 1 shows a durable, optically fogged version of the present invention fabricated on a polymer release layer. FIG. 3 shows a cross-sectional view of a transparent layer without burrs.   FIG. 2 shows the durability of the invention during the lamination step of the process of the invention. A cross section of an optically clear, transparent layer Show.   FIG. 3 shows the durable, optically fogging of the present invention in combination with an imaging substrate. FIG. 3 shows a cross-sectional view of a transparent layer without a slab.   FIG. 4 shows another embodiment of the present invention in combination with an imaged substrate. 1 shows a cross-sectional view of a durable, optically clear, transparent layer. FIG. Embodiment of the invention   FIG. 1 shows a layer having smooth surface properties, which is useful for forming the optical clarity characteristic of the layer 12. Made of an organosol composition that can be thermally processed on the united release liner 14, 1 shows a product composite 10 on which a permanent, optically clear, transparent layer 12 has been placed. .   Liner 14 is the Technical Association for the Georgia, Atlanta Sheffield Te published by Pulp and Paper Industry (TAPPI) Surface roughness measured according to the test method, TAPPI test T538om-88, from about 1 to about 10 Sheffield, can be made from a polymer release liner material . In selecting the liner 14, the surface of the liner 14 in contact with the layer 12 Properties determine the appearance of the outer surface of layer 12 on a durable imaging substrate Must be aware of Non-limiting examples of release liners include Silicon And urea alkyd coated polyester. Especially The preferred lease liner 14 is on a 0.07 mm polyester film. Urea alkyd coated with a 0.005 mm thick polyurea alkyd compound It is a coated polyester.   The release liner 14 has a thickness of about 100 to about 150, preferably about 120 to about 150. It can have a gloss of 140. Gloss is ASTM Standard NO.D523 etc. Using published techniques known to those skilled in the art, a Gardner 60 ° gloss meter is used. Is measured.   The durable, optically clear, transparent layer 12 is made of vinyl chloride, any additional Contains heat-processable resin, optional plasticizer, and optional stabilizer, where layer 1 Detrimental to the surface of the liner 14 which is responsible for the formation of the optical clarity characteristic of Layer 12 from an organosol having a melting temperature sufficient to heat-process It can be formed on a polymer release liner 14.   Vinyl chloride is an industrial chemical that is commercially available from many sources worldwide . Preferably, the vinyl chloride useful in the present invention is B.C., Cleveland, Ohio. Salt containing Geon vinyl chloride resin marketed by F. Goodrich Chemical Company It is a vinyl chloride resin.   Another resin optionally used in the formation of layer 12 is acrylic resin Are readily available as industrial chemicals from many sources around the world It is. Desirably, acrylics useful in layer 12 are from about 75,000 to about 1 It has a number average molecular weight of 25,000. Preferably, an acrylic resin useful in the present invention Is a molecular weight of about 10 commercially available from ICI Resins, Wilmington, Del. 000 Elavacite acrylic resin.   The composition for layer 12 forms the layer 12 and converts it to a durable, imaged substrate. Optionally, a plasticizer useful for transfer is included. Non-limiting examples of plasticizers include 1,4-butyl Lenglycol; adipic acid; Cyloctyl phthalate; hydrocarbon resin; di (2-ethylhexyl) azelate Dibutyl azelate; dihexyl azelate and the like.   Particularly preferred as a plasticizer in the composition of layer 12 is Vikoflex 7170 available from ATOChem, Philadelphia, N.A. It is a plasticizer.   The composition for layer 12 helps to form layer 12, provides UV resistance, and is durable. Optionally, it contains a stabilizer to aid transfer to the imaging substrate. Unlimited stabilizers A common example is the trademark, available from Hal-stab of Hammond, Indiana. Hal-Lub, Hal-Base, Hal-Carb, Hal-Stab hindered amine light stabilizers, Connectic Ultraviolet trademark Nuostabe V1923, commercially available from Witco, Greenwich Linear Stabilizer, Trademark Co, commercially available from 3M Company of St. Paul, Minn. sorb UV stabilizers and Ciba-Gelgy in Greensboro, North Carolina HAL stabilizers under the trademark Tinuvin sold by the company. Especially of layer 12 Preferred as stabilizers when added to the composition are Tinuvin 1130 from Ciba-Geigy And Tinuvin 292 HAL stabilizer or Nuostabe V1923 stabilizer.   Layer 12 is about 40 to about 60 weight percent vinyl chloride and about 1 to about 1 acrylic resin. From 0 to about 30 weight percent, from about 0 to about 33 weight percent plasticizer, and The stabilizer can have a composition that is from about 0 to about 10 weight percent.   Desirably, layer 12 is about 45 to about 55 weight percent vinyl chloride, acrylic About 15 to about 30 weight percent resin, plasticizer From about 0 to about 20 weight percent and stabilizer from about 0 to about 8 weight percent .   Preferably, layer 12 is about 47 to about 60 weight percent vinyl chloride, acrylic About 16 to about 27 weight percent resin and about 10 to about 20 weight percent plasticizer. And the stabilizer can have a composition that is from about 2 to about 6 weight percent. You.   The composition for layer 12 is prepared by dissolving the components in a solvent such as a ketone or an aromatic compound. And preferred solvents are di-isobutyl ketone, Mineral spirit, methyl ethyl ketone, methyl isobutyl ketone and toluene Ene can be raised, and more preferably, such a solvent is mixed in an equivalent amount. Things. Layer 12 has a dry layer thickness from about 0.04 mm (0.0015 in) to about 0.00 in. Dry coating in the range of about 0.70 to about 1.10 g to obtain 0 mm (0.0030 in) The amount of cloth is applied to the liner 14 by knife or gravure printing. Preferred In other words, the liner 14 has a layer thickness of about 0.5 mm (0.002 in.) To about 1 mm. Layer 12 has a layer thickness of about 0.5 mm (0.002 in.) To about 1 mm.   After application, layer 12 is applied on liner 14 at a temperature of about 90 ° C to about 120 ° C. Dry for about 2 minutes to remove solvent, then at 175 ° C to 205 ° C for 30 seconds Melt in oven for 60 seconds. Complex 10 must then be stored until use But preferably a second area protecting the PSA area and the PSA area. Stored as part of a lamination with lease liner.   FIG. 2 shows the PSA (protected by the second release liner 18). The area 16 is laminated to the opposite major surface with the polymer release liner 14 of the layer 12. The laminated composite body 20 formed by this is shown.   Region 16 and liner 18 are prior to lamination according to techniques well known to those skilled in the art. Combined in another step.   Region 16 is at least as good as, and preferably better than, the optical clarity characteristics of layer 12. Any conventional pressure-sensitive adhesive having improved optical clarity properties. this Non-limiting examples of such adhesives include polyacrylates, polyvinyl ethers, natural rubber , Silicone, rubber, styrene butadiene, cis-polybutadiene, styrene -Isoprene block copolymers. Preferably used in the present invention Adhesives range from about 50/50 to about 90/10, preferably about 75/25. Vinyl with weight percentage ratio and viscosity of 1100-1500 centipoise And acrylic blends.   Region 16 is from about 0.013 mm to about 0.05 mm, preferably from about 0.015 to about 0.05 mm. It can have a layer thickness of 03 mm.   Release liner 18 is made from release liner materials known to those skilled in the art. be able to. Preferably, this release liner material 18 is TAPPI test T53 The surface roughness measured according to 8om-88 is from about 5 to about 40 Sheffield. What to choose for the liner 18 depends on the layer 12 and the PSA region 16 before use during storage. This will affect the look, but this is a consumer favorite material for the layers of the present invention. is there. Non-limiting examples of release liners include silicone-coated polyester, silicone Coated paper, urea alkyd coated polyester, urea alkyd coated paper and so on. Lily Particularly preferred as the liner 18 is RexamRel, Chicago, Illinois. 0.007mm thick silicone coating, commercially available from ease, is 0.07 This is a silicone-coated polyester film provided on a You.   The release liner 18 has about 80 to about 130, preferably about 100 to about 1 It has a glossiness in the range of 30. The gloss level is known to those skilled in the art as ASTM Standard No.D523 Measured with a Gardner 60 ° gloss meter using published techniques known to It is.   After laminating PSA region 16 to layer 12, prior to storage and use, a first polymer release Remove the liner 14.   FIG. 3 shows a final composite containing a layer 12 having a PSA region 16 adhered to its major surface. Shows a cross-sectional view of body 30, where PSA region 16 has image 24 on its major surface. The base material 22 is also adhered.   Layer 12 and PSA region 16 are in contact with the main surface of substrate 22 without wrapping substrate 22.   Preferably, the substrate 22 has the image 24 on one major surface and the image 24 on the opposite major surface. It has an adhesive area 24 (not shown). Layer 12 covers area 24 of the pressure sensitive adhesive. Not suitable for bar.   Image 24 may be formed by any conventional process. In a non-limiting example Is electrographic process, electrophotographic process, electrostatic process, ink And a jet printing process. Scotchprint 8601 transfer paper (trademark) ( 3M Company, St. Paul, Minn.) Is used. In order to maintain the above-mentioned transparency, it is preferable to further perform a surface treatment process. this The process is co-pending U.S. patent application Ser. 577,417, the disclosure of which is incorporated herein by reference. You.   Image 24 may be a toner, ink, or paint, all of which are known to those skilled in the art. Dyes, pigments, or a combination of both.   Preferably, image 24 is at least about 100 ° C., preferably at least about 100 ° C. Contains compositions that can withstand processing temperatures of 105 ° C. This film surface Accepts most inks, pigments, toners, dyes and paints You.   Substrate 22 may be any transparent material known to those skilled in the art of image graphics. It may be a substrate. Non-limiting examples include clear glass, clear acrylic And transparent polycarbonate sheets.   Layer 12 and PSA region 16 are separated from liner 18 on composite 20 by image 24 and substrate 22, a pressure in a range sufficient to adhere PSA region 16 to substrate 22, preferably Transcribed by adding about 1 kg to about 5 kg.   Layer 12 and PSA region 16 are aligned when adhered to image 24 and substrate 22 The thickness may be from about 0.05 mm (0.002 in.) To about 0.13 mm. Preferably, the thickness is from about 0.10 mm to about 0.13 mm.   After layer 12 and PSA region 16 have been applied to image 24 and substrate 22, liner 1 8 can be removed, wound up and recycled for later use.   Conventionally, machinery used to form durable base materials with images It can be used for pressure-sensitive transfer of layer 12 to substrate 22. Unlimited machinery Examples include 3M's Scotchprint 9540 ™ and 9542 Bra And laminators such as hands.   FIG. 4 shows another embodiment of the present invention, where image 26 is the PSA area. Placed on layer 12 of composite 10 prior to bonding of area 16, then transferred layer 1 2 and PSA region 16 with image 26 between layer 12 and PSA region 16 Glued to the material 22 (with or without the second image 24 seen in FIG. 4) The final complex 30 is formed. In this example, Scotchprint Electronic Ima ging system (trademark) and the like. 8601 image Electrostatic image paper such as transfer paper, both are commercially available from 3M , Place a four color toner image from paper on layer 12 and then use PSA area Glue area 16 and peel off liner 14 to leave image 26 on layer 12 The lamination transfer is performed to a durable film. Utility of the invention   The use of layer 12 allows image 24, image 26, or both, and substrate 2 2 provides protection against abrasion and ultraviolet light.   The abrasion of the layer 12 of the invention until the image 24 wears off depends on the type of substrate used. Depending on the type, commercially available from Taber Industries, Tonowanda, NY According to some CS-10 worn wheels, about 500 to about 2000 cycles, preferably about 500 to about 100 The range is 0 cycles.   Layer 12 is applied to image 24 and substrate 22 without affecting the appearance of the image. And provide protection. The layer 18 is optically clear and visually transparent. Like Or, optical clarity means putting a film between your eyes and the vision chart And if not placed, the vision is acceptable as measured by a standard vision test. It is.   The present invention is further described in the following examples. Example Example 1: Preparation of a haze-free protective layer   0.005 mm thick polyurea alkyd on 0.07 mm polyester film On urea alkyd coated polyester with urea polymer coating A protective layer without fogging was formed from the following components.   46.7 weight percent Geon 178 vinyl resin (Cleveland, Ohio) B.F. Goodrich); 17.9 weight percent Elvacite acrylic resin (Dela VICofle at 17.2 weight percent (ICI Resins, Wilmington, Ware); x 7170 plasticizer (ATOChem, Philadelphia, PA); 2.3 layers Tin Percent of Tinuvin 292 HAL Stabilizer, Green, North Carolina 2.3% by weight of Nuostabe V1923 stabilizer (from Ciba-Geigy, Zboro) From Witco, Greenwich, CT) and 13.6 weight percent 2 copies Solvent system comprising di-isobutyl ketone and 1 part mineral spirit.   A 0.127 mm wet layer is applied to the liner with a knife and heated to 120 ° C for 2 minutes. To remove the solvent, then melt in an oven at 175 ° C for 45 seconds and dry. The dry layer thickness was about 0.05 mm. Example 2 Production of an adhesive laminate   An adhesive was prepared from the following ingredients: 69 copies of VYHH (Union Carbide, Danbury, Conn.) Acryloid B8 2 (Rohm and Hass, Philadelphia, PA) 17 parts Paraplex G6 2 (CP Hall, Bedford Park, Illinois) 14 copies   Equivalent amounts of xylol, methyl ethyl ketone and methyl isobutyrate Dissolved in the solvent mixture containing the ketone, and the final solution viscosity is 1100-1600 sec. It was an inchpoise. An area of the solution was placed on a 0.07 mm polyester film at 0.00 Silicone coated polyester lily with 5mm thick silicon coating 0.076 mm wet layer on a liner (Rexam release, Chicago, Illinois) It is applied with a knife and dried at 120 ° C. for 2 minutes to obtain a dry layer thickness of 0.0025 m. m. Example 3 Laminate   Apply the layer on the liner obtained in Example 1 to the adhesive area obtained in Example 2. The laminate shown in FIG. 2 was produced by contact and using a pressure of about 2.3 kg / cm 2.   Following the description of the examples, claims are described.

────────────────────────────────────────────────── ─── Continuation of front page    (81) Designated countries EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, L U, MC, NL, PT, SE), OA (BF, BJ, CF) , CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (KE, LS, MW, SD, S Z, UG), EA (AM, AZ, BY, KG, KZ, MD , RU, TJ, TM), AL, AM, AT, AU, AZ , BB, BG, BR, BY, CA, CH, CN, CZ, DE, DK, EE, ES, FI, GB, GE, HU, I S, JP, KE, KG, KP, KR, KZ, LK, LR , LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, S D, SE, SG, SI, SK, TJ, TM, TR, TT , UA, UG, US, UZ, VN

Claims (1)

[Claims]   1. PVC resin, any acrylic resin, any plasticizer and any stable And a smoothness of about 1 to about 10 in Sheffield value. Covering the substrate with the image formed on the polymer release liner, Layer to protect.   2. Composite in which said layer contains a pressure-sensitive adhesive area and a second release liner The layer of claim 1 which is part of   3. The layer of claim 1, further comprising an acrylic resin.   4. The layer of claim 1, further comprising a plasticizer and a stabilizer.   5. The amount of vinyl chloride resin ranges from about 49 to about 72 weight percent; The amount of the cryl resin ranges from about 9 to about 33 weight percent and the amount of plasticizer is about 0 to about 25 weight percent and the amount of stabilizer is from about 0 to about 8 weight percent. 4. The layer of claim 3 in the range up to cents.   6. The amount of vinyl chloride resin ranges from about 55 to about 65 weight percent; The amount of the cryl resin ranges from about 16 to about 27 weight percent and the amount of plasticizer is In the range of about 10 to about 16 weight percent and the amount of stabilizer is about 2 to about 6 weight percent 5. The layer of claim 4 in the percentage range.   7. 7. The layer of claim 6, wherein said layer has a thickness from about 0.05 mm to about 0.13 mm.   8. The layer is applied at a pressure in the range of about 0.7 kg / sq cm to about 4.2 kg / sq cm. And being adhered on the substrate with image. Layers.   9. (A) a first polymer lily having a gloss in the range of about 110 to about 150 Organosol with two main surfaces on a liner and a transparent layer without optical haze Forming from (B) optionally bonding the area of pressure sensitive adhesive to the second release liner; , (C) optionally providing an area of pressure sensitive adhesive on the exposed major surface of the optically clear, transparent layer Laminating; and (D) optionally removing the first polymer release liner. , The method of forming a layer of claim 1 for protecting an imaging substrate.   10. The method comprises the steps of: transferring the layer after the transfer step and prior to the bonding step. The method of claim 9 further comprising the step of placing an image thereon.   11. A contract further comprising removing the second release liner. The method of claim 9.   12. The laminating step is performed from about 1.7 kg / sq cm to about 4.2 kg / sq cm. 10. The method of claim 9 wherein a pressure in the range is used.   13. The amount of vinyl chloride resin ranges from about 40 to about 60 weight percent; The amount of acrylic resin ranges from about 10 to about 30 weight percent and the amount of plasticizer Ranges from about 0 to about 25 weight percent and the amount of stabilizer is from about 0 to about 8 weight percent. 10. The method of claim 9, wherein the range is up to a percentage.   14． When the amount of the vinyl chloride resin ranges from about 45 to about 55 weight percent. And the amount of acrylic resin ranges from about 15 to about 30 weight percent; The amount of plasticizer ranges from about 10 to about 16 weight percent and the amount of stabilizer is about 10. The method of claim 9, wherein the amount ranges from about 6 to about 6 weight percent.   15. 15. The method of claim 14, wherein said layer has a thickness of about 0.04 mm to about 0.08 mm. Law.   16. 10. The method of claim 9, wherein said imaged substrate is a durable film.   17． The imaged substrate comprises an image, a dielectric layer and a bottom layer. 10. The method of claim 9, which is an electrophotographic paper.   18. The above method further removes the dielectric and bottom layers, making the image durable. Leaving it in contact with an optically clear, transparent layer, Laminating the image and the composite onto a film, and releasing the composite from the composite. Removing the ground liner.   19. Optically cloudy and transparent over imaging substrates containing perforated films A composite comprising a transparent layer, wherein the transparent layer having no optical haze is a composite according to claim 1. A composite containing a layer.   20. Forming the layer of claim 1 on a polymer release liner; Laminating said layer on a substrate with image. Protection method.   21. 21. The image of claim 20, wherein an image is also provided on a major surface of said layer. A method for protecting a substrate with a die.