HIGH PRESSURE LAMINATES MADE WITH PAPER CONTAINING CELLULOSE ACETATE

Abstract: A high pressure laminate is made of several layers of paper, including from bottom to top core sheets, a decor sheet and an overlay sheet. The core sheets are either composed of cellulose fibers or composed of 30 to 90 weight percent cellulose acetate fibers and 70 to 10 weight percent cellulose fibers. The core sheets are respectively coated with either a lamination polymer or a plasticizer. The decor sheet is composed of a mixture and a conventional amount of paper making dye. The mixture comprises 30 to 90 weight percent cellulose acetate fibers, 10 to 70 weight percent celluose fibers and 0 to 20 weight percent fillers. The decor sheet is coated with a plasticizer. The overly sheet is composed of cellulose fibers and is coated with a lamination polymer. Upon application of heat and pressure to the several layers a laminate is formed having thermoplastic, properties, improved postformability and a significant reduction in the release of volatile organics during formation.

Description: HIGH PRESSURE LAMINATES MADE WITH PAPER CONTAINING CELLULOSE ACETATE TECHNICAL FIELD This invention relates to high pressure laminates, and more particularly to the composition of core and decor sheets therein for improved postformability of the laminates and methods of preparation thereof. BACKGROUND OF THE INVENTION High pressure laminates are laminated articles typically made of a plurality of core sheets, a decor sheet and an overlay sheet. The sheets are coated with lamination polymers which are typically thermosetting materials, such as melamine or phenolic resins. The core sheets are made from unbleached kraft paper and are dark in color. The number of core sheets used depends on the application requirements, i.e. strength and environment, and the desired thickness of the laminate. Laminates have a thickness ranging from 0.763 to 2.290 mm (0.030 to 0.090 inch) . The core sheets are typically saturated with phenolic resins. The decor sheets are typically made of very heavy paper comprised of cellulose fibers and an opacifying pigment such as titanium oxide. The decor sheets are printed upon with designs to create the decorative pattern of the laminate. The decor sheets are typically saturated with melamine resins. The overlay sheets are clear cellulose sheet which act as a protective layer over the decor sheet. These sheets are usually saturated with melamine resins. The overlay sheets are used optionally depending on the need for protective surfaces. In a typical process for preparing laminates, the sheets are saturated with the appropriate thermoset resins and then stacked. Next they are placed in a press and subjected to temperatures of about 150°c and pressures of about 7584.5 to 8274.0 kPa (1100 to 1200 psi) for a particular period of time. However, during processing the resins release volatiles causing environmental concern. The melamine resins typically release phenolic volatiles and the phenolic resins release formaldehyde volatiles. The laminates that are produced are thermoset products due to the nature of the resins employed in the process. For flat surface applications irreversibility after formation and cure creates no problems. However, some applications have curved surfaces and require that the laminates be flexible to allow for a tailored fit in a particular place. This property is known in the industry as postformability and is measured by the radius of the bend of the laminate in the postfor ing unit. The smaller the radius achievable without cracking, the better the postformability. The current industry standard is 0.635 cm radius which provides only minimal flexibility. Postformability is obtained by only partially curing the laminates prior to application. The partially cured state creates some flexibility in the laminates. After fitting the laminates in place, full cure is completed by the application of heat. Once fully cured the laminate is set and cannot be adjusted. Thus if mistakes are made, the laminates must be discarded and replaced resulting in considerable material waste and higher costs. Thus, there exists a need in the art for a high pressure laminate that does not release any volatiles during processing, that has more flexibility providing for a wider range of applications, and that remains adjustable after full cure. SUMMARY OF THE INVENTION A high pressure laminate comprises a plurality of core sheets, a decor sheet and an overlay sheet. The core sheets are composed of 30 to 90 weight percent cellulose acetate fibers and 70 to 10 weight percent cellulose fibers and are coated with either a lamination polymer or a plasticizer. The decor sheet is composed of a mixture and a conventional amount of paper making dye. The mixture comprises 30 to 90 weight percent cellulose acetate fibers, 10 to 70 weight percent cellulose fibers and 0 to 20 weight percent fillers. The decor sheet is coated with a plasticizer. The overlay sheet is composed of cellulose fibers and is coated with a lamination polymer. Upon application of heat and pressure a laminate is formed having thermo¬ plastic properties, improved postformability and a significant reduction in the release of volatile organics during formation. DETAILED DESCRIPTION OF THE INVENTION A high pressure laminate having improved postformability is made from the application of heat and pressure to layers of various types of sheets of paper. The sheets are made using standard paper aking techniques and chemistry. Some of the sheets comprise cellulose ester fibers in addition to cellulose fibers, such sheet being coated with plasticizer prior to formation of the laminate. The use of heat and pressure convert the layers of sheets into a laminate having thermoplastic properties. The laminate is formed from top to bottom with the following layers: (a) an overlay sheet composed of cellulose fiber, (b) a decor sheet composed of cellulose and cellulose ester fibers, and (c) several core sheets that are either composed of cellulose fibers or cellulose and cellulose ester fibers. The sheets containing only cellulose fibers are coated with a conventional lamination polymer, usually either a melamine or phenolic resin depending on the application. The sheets containing both cellulose and cellulose ester fibers are coated with a plasticizer that is compatible with the particular cellulose ester in the sheet. In one embodiment of the invention only the decor sheet contains both cellulose and cellulose ester fibers, while the core and overlay sheets contain cellulose fibers. The decor sheet is a paper made using conventional papermaking techniques. The decor sheet is composed of a mixture comprising from 30 to 90 weight percent cellulose ester fibers, from 10 to 70 weight percent cellulose fibers and from 0 to 20 weight percent fillers, based on the total weight of the cellulose ester fibers, the cellulose fibers and the fillers. Prior to creating the paper, a conventional amount of a papermaking dye is added to the mixture. This is typically 3.175 kg (7 pounds) of dye per 907.185 kg (2000 pounds) of mixture. The paper, thus created, is coated with a cellulose ester plasticizer prior to layering it with the other sheets. Preferably, the decor sheet comprises from 30 to 70 weight percent cellulose ester fibers, from 15 to 55 weight percent cellulose fibers and from 15 to 20 weight percent fillers. More preferably, the mixture comprises 50 weight percent cellulose ester fibers, 30 weight percent cellulose fibers and 20 weight percent fillers. The fillers are those conventionally used in the papermaking industry for making a sheet of paper opaque. Preferably, the fillers are selected from the group comprising titanium dioxide, clay and calcium carbonate. In another embodiment of the invention the decor sheet and core sheets contain both cellulose and cellulose ester fibers, while only the overlay sheet contains cellulose fibers. The core sheets are composed of from 30 to 90 weight percent cellulose acetate fibers and from 70 to 10 weight percent cellulose fibers. The decor sheet is the same as described above. The core sheets and decor sheet are coated with a plasticizer and the overlay sheet is coated with a lamination polymer prior to layering the sheets together. During the formation of the laminate by the application of heat and pressure to this combination of sheets and coatings, there is a significant reduction in the release of volatile organics due to the elimination of melamine and phenolic resins in two of the three layers. In this embodiment the core sheets are preferably composed of 50 weight percent cellulose acetate fibers and 50 weight percent cellulose fibers and the decor sheet is composed of the mixture comprising 50 weight percent cellulose ester fibers, 30 weight percent cellulose fibers and 20 weight percent fillers. A measure of the thermoplastic nature of the resulting laminates described above is in their postformability. This property is measured as the radius of the laminate bend in a postforming unit, using the formability test method established by NEMA (National Electrical Manufacturers Association) , Standards Publication LD3—1991. For the laminate of the present invention the radius of the laminate bend is preferably less than 0.635 cm (0.25 inches). The cellulose ester fibers are preferably cellulose acetate, cellulose acetate butyrate and cellulose acetate propionate. The more preferred cellulose ester is cellulose acetate. The cellulose acetate fibers utilized in this invention are preferably diester fibers with an acetyl content of 34 to 41 weight percent. The fibers may have a round or trilobal cross section. The fibers may or may not be surface hydrolyzed. The cellulose fibers utilized in the invention are typically standard hardwood or softwood pulp fibers. The preferred cellulose acetate fibers are surface hydrolyzed cellulose acetate fibers. These cellulose acetate fibers have a sheath of regenerated cellulose being from 4 to 15 weight percent of the weight of the cellulose acetate fibers and a core of cellulose acetate. The cellulose acetate fibers contain no substantial crimp, have an average length from 1 to 7 mm, a density from 1.20 to 1.35 gm/cc, a denier from 1 to 30 gm/9,000 meters and a uniform dispersion index of less than 0.15. In another preferred embodiment of the invention the cellulose acetate fibers of the film are not surface treated. These cellulose acetate fibers are uniformly dispersed, have a weighted average length in the range of 1 to 7 mm, have a density in the range of 1.20 to 1.35 gm/cm, have a denier in the range of 1 to 30, have a range of 0.1 to 0.2 weight percent lubricant thereon, exhibit no substantial fibrillation and have a uniform dispersion index of 0.15. The preferred method of preparing these cellulose acetate fibers with no surface treatment is disclosed in U.S. Patent No. 5,505,888 to Mitchell et al. The plasticizer employed in accordance with this invention may be any plasticizer composition that is compatible with cellulose esters and that causes the cellulose ester and cellulose containing paper to convert to a thermoplastic material with the application of heat and pressure. For cellulose acetate, the preferred plasticizers are toluenesulfonamide derivatives, phthalates and triacetin. The amount of plasticizer coated on the decor and/or core sheets is that which is enough to convert the paper to a material having thermoplastic properties and is preferably in the range of 20 to 100 weight percent based on the weight of the cellulose ester fiber. This amount of plasticizer employed is generally an amount which wets the paper such that the plasticizer has penetrated the thickness of the paper, but has not necessarily wetted the paper to the point at which it can contain no more plasticizer. The application of heat and pressure to the layers of sheets is that which is conventional in the preparation of high pressure laminates. Preferably, the temperature is applied at 150°C and the pressure is applied at 620.55 kPa (900 psi). The films of this invention and their preparation are illustrated by the following examples. EXAMPLE 1 The laminate structure was layered from top to bottom with one sheet of industry standard overlay, one sheet of Eastman decor sheet and three sheets of industry standard core sheets. The industry standard overlay and core sheets, available from Nevamar Division of International Paper Co., Inc. at Odenton, Maryland, were made of conventional cellulose fibers and other additives used in standard papermaking processes and were coated with a conventional thermoset bonding resin. The Eastman decor sheet was made of 50 weight percent (wt%) cellulose acetate fibers and 50 wt% cellulose fibers with a basis weight of 45.359 kg per 278.70 m 2 (100 lbs per 3000 ft 2 ). The Eastman decor sheet was not treated in any manner. The laminate was assembled and pressed using a cold—to—cold press cycle. The press temperature was rampled up slowly to 150°C. The press pressure of 6895 kPa (1000 psi) was applied at the outset. The length of exposure at maximum temperature and pressure was 5 minutes. This example demonstrated the comparability of the Eastman decor sheet with the conventional thermoset laminate technology. The resulting laminate as expected had no flexibility. EXAMPLE 2 The laminate structure and the composition of the Eastman decor sheet were the same as that set forth in Example 1. The Eastman decor sheet was treated with an industry standard melamine solution consisting of 52 wt% Cymel 412 (trademark) (a spray— ried melamine resin) , 5 wt% isopropyl alcohol, 0.5 wt% magnesium chloride and 42.5 wt% warm water. The industry standard overlay and core sheets were also coated with the melamine solution. The laminate was assembled and pressed using a cold—to—cold press cycle. The press temperature was rampled up slowly to 163°C. The press pressure of 6895 kPa (1000 psi) was applied at the outset. The length of exposure at maximum temperature and pressure was 3 minutes. This example demonstrated compatibility between the cellulose acetate containing sheets and the melamine resin used in the laminate industry. EXAMPLE 3 The laminate structure and the composition of the Eastman decor sheet were the same as that set forth in Example 1. The industry standard overlay and core sheets were coated with a conventional thermoset bonding resin. The Eastman decor sheet was treated with a diethylphthalate(DEP)/isopropyl alcohol solution. The DEP to cellulose acetate ratio was 1:1 by weight. The isopropyl alcohol was used as a solvent to evenly distribute the DEP within the piece of paper. The alcohol was removed via heat. When utilizing a metering system, the alcohol solvent would be unnecessary. The laminate was assembled and pressed under the identical conditions listed in Example 1. The resulting laminate retained its thermoset nature from the resins in the core and overlay sheets. However, the use of plasticizer on the Eastman decor sheet did provide for increased postformability. EXAMPLE 4 The laminate structure and the composition of the Eastman decor sheet were the same as that set forth in Example 1. The industry standard overlay and core sheets were coated with a conventional thermoset bonding resin. The Eastman decor sheet was treated first with DEP/isopropyl alcohol solution (DEP to cellulose acetate ratio was 1:1 by weight) as set forth in Example 3 and then with a melamine solution identical in composition to that in Example 2. The laminate was assembled and pressed under the identical conditions listed in Example 2. This example was used to prove compatibility between a plasticizer treated cellulose acetate containing paper and an industry standard melamine treatment. EXAMPLE 5 The laminate structure was the same as that set forth in Example 1. The industry standard overlay and core sheets were coated with a conventional thermoset bonding resin. The Eastman decor sheet was made of a mixture of 60 wt% cellulose acetate fibers, 24 wt% cellulose fibers and 16 wt% fillers (titanium dioxide, clay, and calcium carbonate) and a conventional amount of standard paper industry dye [3.175 kg per 907.185 kg (7 lbs per 2000 lbs) mixture]. The sheet had a basis weight of 20.412 kg per 278.70 m 2 (45 lbs per 3000 ft 2 ). The Eastman decor sheet was treated with an ethyltoluenesulfonamide plasticizer at a cellulose acetate to plasticizer ratio of 1:0.65. The laminate was assembled and pressed under the identical conditions listed in Example 1. This example demonstrated that opacity can be obtained using a cellulose acetate containing paper. EXAMPLE 6 The laminate structure was layered from top to bottom with one sheet of industry standard overlay, one sheet of Eastman decor sheet and three sheets of Eastman Kraft core. The industry standard overlay was coated with a conventional thermoset bonding resin. The Eastman decor sheet had the same composition as that set forth in Example 1. The Eastman Kraft core was made of 50 wt% cellulose acetate fibers and 50 wt% cellulose fibers with a basis weight of 68.039 kg per 278.70 m 2 (150 lbs per 3000 ft 2 ). Both papers were treated with DEP/isopropyl alcohol solution. DEP to cellulose acetate ratio was 1:1 by weight. The alcohol was removed via heat. The laminate was assembled and pressed under the identical conditions listed in example 1. This example demonstrated the capability of a cellulose acetate plasticizer treated sheet to function as a core material replacement. EXAMPLE 7 The laminate structure was layered from top to bottom with one sheet of industry standard overlay, one sheet of Eastman decor sheet and three sheets of industry standard core. The overlay and core sheets were coated with a conventional thermoset bonding resin. The Eastman decor sheet had the same composition and was treated in the same manner as that set forth in Example 3. This example was assembled and pressed under the identical conditions outlined in Example 1. After the resulting laminate had conditioned for the appropriate time, it was postformed under the formability test method established by NEMA (National Electrical Manufacturers Association) , Standards Publication LD3—1991. The piece postformed to 0.318 cm radius. This example demonstrated an increase in post¬ formability over conventional high pressure laminates. EXAMPLE 8 The laminate structure was layered with four Eastman decor sheets having the same composition as that in Example 1. The sheets were treated with a triacetin/isopropyl alcohol solution. Triacetin to cellulose acetate ratio was 0.5:1 by weight. The material was pressed under the identical condition set forth in example 1. Af er the resulting laminate had conditioned for the appropriate time, it was postformed under the formability test method established by NEMA (National Electrical Manufacturers Association) , Standards Publication LD3—1991. The laminate postformed to 0.318 cm radius. The high pressure laminates of the present invention made from decor sheets and core sheets comprised of cellulose ester and cellulose fibers and coated with plasticizers provide significant processing and property advantages over the prior art thermoset laminates. In preparing the laminates of the present invention, the substitution of plasticizers for thermoset bonding resins substantially reduces the harmful volatiles released during processing. The laminates having plasticizers as the lamination polymer rather than resins are more flexible for increased postforming capabilities and are also adjustable after cure to allow for corrections in application. Thus, these high pressure laminates are easier to use and result in less material waste. The invention has been described in detail with particular reference to preferred embodiments and methods thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims: - 13 CLAIMS What is claimed is: 1. A high pressure laminate with improved post¬ formability formed by the application of heat and pressure comprising a plurality of core sheets composed of cellulose fibers and coated with a first lamination polymer, a decor sheet composed of a mixture comprising from 30 to 90 wt% cellulose ester fibers, from 10 to 70 wt% cellulose fibers and from 0 to 20 wt% fillers, based on the total weight of said cellulose ester fibers, said cellulose fibers and said fillers, with a conventional amount of a papermaking dye added to said mixture, and coated with a cellulose ester plasticizer, and an overlay sheet composed of cellulose fibers and coated with a second lamination polymer. 3. The high pressure laminate of claim 1 wherein said mixture comprises from 30 to 70 wt% cellulose ester fibers, from 15 to 55 wt% cellulose fibers and from 15 to 20 wt% fillers, based on the total weight of said cellulose ester fibers, said cellulose fibers and said fillers. 4. The high pressure laminate of claim 3 wherein said mixture comprises 50 wt% cellulose ester fibers, 30 wt% cellulose fibers and 20 wt% fillers. 5. The high pressure laminate of claim 3 wherein said fillers are selected from the group comprising titanium dioxide, clay and calcium carbonate. 6. The high pressure laminate of claim 1 wherein said cellulose ester is cellulose acetate. 7. The high pressure laminate of claim 6 wherein said plasticizer is selected from the group comprising toluenesulfonamide derivatives, phthalates and triacetin. 8. The high pressure laminate of claim 1 wherein said decor sheet is coated with said cellulose ester plasticizer in an amount ranging from 20 to 100 wt%, based on the weight of said cellulose ester fibers in said decor sheet. 9. The high pressure laminate of claim 1 having a postformability of less than 0.635 cm radius of the laminate bend in a postforming unit. 10. The high pressure laminate of claim 1 wherein said cellulose ester fibers are uniformly dispersed in said decor sheet, have a weighted average length in the range of 1 to 7 mm, have a density in the range of 1.20 to 1.35 gm/cc, have a denier in the range of 1 to 30, have a range of 0.10 to 0.20 weight percent lubricant thereon and exhibit no substantial fibrillation, and said decor sheet has a uniform dispersion index of less than 0.15. 11. The high pressure laminate of claim 1 wherein said cellulose ester fibers have a sheath of regenerated cellulose being from 4 to 15 weight percent of the weight of said cellulose ester fiber and a core of cellulose ester, contain no substantial crimp, and have an average length from 1 to 7 mm, a density from 1.20 to 1.35 gm/cc, and a denier from 1 to 30 grams per 9,000 meters, and said decor sheet has a uniform dispersion index of less than 0.15. 12. A high pressure laminate comprising a plurality of core sheets composed of from 30 to 90 wt% cellulose acetate fibers and from 70 to 10 wt% cellulose fibers and coated with a plasticizer, a decor sheet composed of a mixture comprising from 30 to 90 wt% cellulose ester fibers, from 10 to 70 wt% cellulose fibers and from 0 to 20 wt% fillers, based on the total weight of said cellulose ester fibers, said cellulose fibers and said fillers, with a conventional amount of a papermaking dye added to said mixture, a cellulose ester plasticizer coated on said decor sheet, and an overlay sheet composed of cellulose fibers and coated with a lamination polymer, whereby upon application of heat and pressure a laminate is formed having thermoplastic properties, improved postformability and a significant reduction in the release of volatile organics during formation. 13. The high pressure laminate of claim 12 wherein the laminate has a postformability of less than 0.635 cm radius of the laminate bend in a postforming unit. 15. The high pressure laminate of claim 14 wherein said core sheets are composed of 50 wt% cellulose acetate fibers and 50 wt% cellulose fibers and said decor sheet is composed of said mixture comprising 50 wt% cellulose ester fibers, 30 wt% cellulose fibers and 20 wt% fillers. 16. The high pressure laminate of claim 12 wherein said cellulose ester fibers of said decor sheet have a sheath of regenerated cellulose and a core of cellulose ester. 17. A process for preparing a high pressure laminate with improved postformability comprising the steps of: a) preparing a decor sheet from a mixture comprising from 30 to 90 wt% cellulose ester fibers, from 10 to 70 wt% cellulose fibers and from 0 to 20 wt% fillers, based on the total weight of said cellulose ester fibers, said cellulose fibers and said fillers, and a conventional amount of papermaking dye, b) coating said decor sheet with a cellulose ester plasticizer, c) coating a plurality of core sheets and an overlay sheet with a lamination polymer, e) layering from top to bottom said coated overlay sheet, said coated decor sheet and said coated core sheets, and f) applying to the layer of sheets from step (e) heat and pressure, and c) removing from said heat and pressure a laminate. 18. The process of claim 17 wherein said decor sheet is prepared from said mixture comprising 30 to 70 wt% cellulose ester fibers, from 15 to 55 wt% cellulose fibers and from 15 to 20 wt% fillers, based on the total weight of said cellulose ester fibers, said cellulose fibers and said fillers. 19. The process of claim 17 wherein said laminate has a postformability measured at less than 0.635 cm radius of the laminate bend in a postforming unit. 21. A process for preparing a high pressure laminate comprising the steps of: a) layering together an overlay sheet coated with a lamination polymer, a decor sheet and a plurality of core sheets, said decor sheets and core sheets composed of from 30 to 90 wt% cellulose acetate fibers, from 10 to 70 wt% cellulose fibers and from 0 to 20 wt% fillers and coated with a plasticizer, b) applying to the layer of sheets in step (a) for a period of time heat of 150°C and pressure of about 6205.5 kPa (900 psi), and c) removing from said heat and pressure a laminate having thermoplastic properties, improved postformability and a significant reduction in the release of volatile organics during formation. 21. The process of claim 20 wherein the laminate has a postformability measured at less than 0.635 cm radius of the laminate bend in a postforming unit. 22. A decorative laminate comprising a plurality of consolidated resin coated fibrous sheets and at least one decor sheet coated with a plasticizer and composed of a mixture comprising 30 to 90 wt% cellulose acetate fibers, 10 to 70 wt% cellulose fibers and 0 to 20 wt% fillers with a conventional amount of a papermaking dye added to said mixture.

Inventors: COX STEPHEN TODD, KENNEDY PAUL JAY, MASSIE GUY FOSTINE JR, MITCHELL MELVIN GLENN, WILLIAMS FREDDIE WAYNE, COX, STEPHEN, TODD, KENNEDY, PAUL, JAY, MASSIE, GUY, FOSTINE, JR., MITCHELL, MELVIN, GLENN, WILLIAMS, FREDDIE, WAYNE
Applicants: EASTMAN CHEM CO, EASTMAN CHEMICAL COMPANY
Application year: 1996
Main classification: D21H27
IPC codes: B32B29, D21H13, D21H19, D21H27