CA1135657A - Method for forming a decorative vinyl composition surface covering - Google Patents
Method for forming a decorative vinyl composition surface coveringInfo
- Publication number
- CA1135657A CA1135657A CA000334009A CA334009A CA1135657A CA 1135657 A CA1135657 A CA 1135657A CA 000334009 A CA000334009 A CA 000334009A CA 334009 A CA334009 A CA 334009A CA 1135657 A CA1135657 A CA 1135657A
- Authority
- CA
- Canada
- Prior art keywords
- coating
- clear
- printed
- decorative
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
- D06N3/0081—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments by wave energy or particle radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/02—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a matt or rough surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/53—Base coat plus clear coat type
- B05D7/536—Base coat plus clear coat type each layer being cured, at least partially, separately
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/576—Three layers or more the last layer being a clear coat each layer being cured, at least partially, separately
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- Toxicology (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Printing Methods (AREA)
- Finishing Walls (AREA)
Abstract
METHOD FOR PROVIDING PRINTED VINYL COMPOSITION SURFACE COVERINGS
WITH A NUBBLY TEXTURED, RADIATION-CURED WEAR LAYER
Abstract of the Disclosure A method for manufacturing a nubbly textured, decorative vinyl composition surface covering having a high performance, clear, glossy, radiation-cured wear layer overlying a decorative printed vinyl composition substrate. The nubbly textured wear layer is achieved by first overprinting the decorative substrate with nubs of a clear, radiation-curable coating, after which an overall clear, radiation-curable wear layer is applied with the coated, printed substrate being radiation cured to yield a high performance wear layer having a nubbly texture.
WITH A NUBBLY TEXTURED, RADIATION-CURED WEAR LAYER
Abstract of the Disclosure A method for manufacturing a nubbly textured, decorative vinyl composition surface covering having a high performance, clear, glossy, radiation-cured wear layer overlying a decorative printed vinyl composition substrate. The nubbly textured wear layer is achieved by first overprinting the decorative substrate with nubs of a clear, radiation-curable coating, after which an overall clear, radiation-curable wear layer is applied with the coated, printed substrate being radiation cured to yield a high performance wear layer having a nubbly texture.
Description
11`35657 Is~ETHOD FOR PROVIDING PRINTED VINYL CO~OSITION SURFACE COVERINGS
WITH A NUBBLY TEXTURED, RADIATION-CURED ~EAR LAYER
Background of the Invention Field of the Invention The Field of the Invention relates to decorative vinyl composition surface coverings having high performance, clear, glossy, radiation-cured wear layers.
Descri~tion of the Prior Art In recent years, there has been developed in the resilient flooring industry high performance, high gloss coatings which are designed to give the consumer a resilient flooring product which does not require the conventional wax treatments heretofore commonly ~ associated with resilient flooring products of a vinyl composition.
Some of the products have clear, tough, glossy coatings formed with heat and moisture curable urethane based coating compositions. More recently, particularly with vinyl asbestos tile products, but also to a limited extent with sheet vinyl surface coverings, radiation-curable coatings have been developed which also yield tough, glossy, high performance, wear resistant coatings-when applied as wear layers.
In order to minimize any scratching which would take place and thus retain the high degree of gloss, these products are generally pro-vided with an overall nubbly texture. Two prior art methods of achieving this overall nubbly texture have been to either post-emboss the wear layers with a nubbly textured roll or embossing plate or to pre-emboss the vinyl composition substrate with a nubbly textured embossing roll or plate prior to applying the generally viscous, radiation-curable wear coa-ting. Because of the viscous nature of ~P
WITH A NUBBLY TEXTURED, RADIATION-CURED ~EAR LAYER
Background of the Invention Field of the Invention The Field of the Invention relates to decorative vinyl composition surface coverings having high performance, clear, glossy, radiation-cured wear layers.
Descri~tion of the Prior Art In recent years, there has been developed in the resilient flooring industry high performance, high gloss coatings which are designed to give the consumer a resilient flooring product which does not require the conventional wax treatments heretofore commonly ~ associated with resilient flooring products of a vinyl composition.
Some of the products have clear, tough, glossy coatings formed with heat and moisture curable urethane based coating compositions. More recently, particularly with vinyl asbestos tile products, but also to a limited extent with sheet vinyl surface coverings, radiation-curable coatings have been developed which also yield tough, glossy, high performance, wear resistant coatings-when applied as wear layers.
In order to minimize any scratching which would take place and thus retain the high degree of gloss, these products are generally pro-vided with an overall nubbly texture. Two prior art methods of achieving this overall nubbly texture have been to either post-emboss the wear layers with a nubbly textured roll or embossing plate or to pre-emboss the vinyl composition substrate with a nubbly textured embossing roll or plate prior to applying the generally viscous, radiation-curable wear coa-ting. Because of the viscous nature of ~P
- 2 - lJGT-5632 these coatings and because they are usually applied in an on-line process with at least partial curing being almost imrnediately achieved after application, the wear layers generally conform to the nubbly texture of the substrate.
Both the embossing of the substrate and the post-embossing of the wear layer can readily be tolerated where distortion of the decorative substrate is not of real concern. However, for example, where a relatively smooth substrate is first printed with a desired visual design and where it is desirable not to disturb or distort the printed design by using the above-described embossing techniques, then an alternate process must be designed.
Summary of the Invention This invention solves the problem of-providing a decorative substrate with a nubbly textured, radiation-cured wear layer without performing an embossing step. This is achieved by first overprinting the decorative vinyl composition substrate with nubs of a clear, radiation-curable coating, after which an overall clear, radiation-curable wear layer is applied with the overall nubbly, radiation-curable coating being cured to form a glossy~ high performance, nubbly wear layer.
Brief Descri~tion of the Drawing Figure 1 is a schematic drawing illustrating the practice of this invention wherein smooth vinyl asbestos tile substrates are first printed using a flexographic printer to achieve the desired-visual image on the smooth surface, after which print-on nubs are applied and the tile curtain coated and cured.
Figure 2 is a cross-sectional view of a printed decorative tile having a textured glossy wear layer formed in accordance with - this invention.
Detailed Description This invention will be described with reference to the production of so-called "no-wax" vinyl asbestos tile products, al-though it will be equally as obvious to anyone skilled in the art that the practice of the invention is readily adapted to the pro-duction of printed decorative vinyl composition tile and sheet goods wherein at least a portion of the printing is confined to a smooth planar surface of the vinyl composition substrate and wherein it is desired not to distort the printing through an embossing step.
1~3565'7 _ 3 _ ~lGT-5632 For purposes of illustrating the invention, the use of a photopol~erizable coating curable by common W sources will be described, although it will just as obviously be evident to one skilled in the art that the practice of the invention .nay be achieved 5 with the use of any radiation-curable coating utilizing radiation sourees sueh as eleetron beams. The applieation of photoeurable eoatings to printed surfaees sueh as floor eoverings, for example, is described in U. S. Patent 3,840,448, and the application of photo-polymerizable coatings to tile is described in U. S. Patent 3,717,558.
Earlier prior art has suggested that ethylenically unsaturated coatings may be cured by ionizing radiation or light and that sueh eoatings may be used for proteetively eoating impervious artieles such as linoleum (see, for exanple, U. S. Patent 3,o56,760).
Boranian et al., U. S. Patent 3,924,023, describes a process 15 wherein, for example, printed tile products having high performance, wear resistant eoatings may be formed. Ultimately, the performanee of the wear eoat will depend upon the formulation of the W eurable eoating. In their proeess, it is recommended that an on-line process be used wherein a tile-forming blanket is ealendared from the usual 20 vinyl asbestos tile-forming eomposition, the blanket then printed with the desired design, eoated with a W eurable eoating eomposition whieh is then eured after whieh the individual tiles are eut from the cured eoated blanket. Sinee the high performanee eoatings whieh form the elear wear layer are neeessarily extremely expensive compared 25 with the vinyl asbestos composition substrates, any scrap losses can be extremely costly. Aceordingly, the speeifie embodiment deseribed in this invention will deal with a process wherein preformed vinyl asbestos tiles are printed and coated.
Vinyl-asbestos tile formulations are well known in the art, 30 as are the processing conditions for tile formation (see, for example, U. S. Patent 2,773,851 and the above-discussed U. S. Patent 3,924,023).
Exam~les I - III
UV Curable Flexo~ra~hic Inks .
The photopolymerizable oligomer forming the basis for the 35 flexographic ink is formed by reacting the following reactants in a reaction vessel.
_ 4 _ l!GT-5632 .
Ing.redients Grams 4,4' diisocyanato dicyclohexylmethane 29.41 Diol (~nion Carbide PCP0200) A poly- 32.47 caprolactone diol having a i~ of 540 and a Hydroxyl No. of 207 2-Hydroxyethylacrylate 17.87 2-Ethylhexylacrylate ` 13.15 Trimethylolpropane triacrylate 7.03 Dibutyl tin dilaurate 0.02 2,6 Ditertbutyl-4-methylphenol 0.05 .In forming the oligomer, the diol, 2-ethylhexylacrylate and trimethylolpropane triacrylate are first charged into the reaction vessel. The diisocyanate and dibutyl tin dilaurate catalyst are then added and the mixture reacted at 45 to 50C. After the reaction has proceeded for approximately 45 minutes, thé hydroxyethylacrylate is added, continuing the stirring and heating for an additional two hours at which point the isocyanate functionality is constant.
The following inks were then formulated as follows:
Parts by l~eight Example Exar,ple Example Ing~edients I_ II III
Photopolymerizable oligomer29.575.10 33.58 l~onomer diluent (1)31.0060.00 40.00 Cellulose acetate butyrate11.00 11.00 -25 Pi&ments l~hite 20.00 Yellow 25.00 Green 10.00 10.00 Photoinitiators Chlorothioxanthone0.811.30 1.47 Methyldiethanolamine 1.62 2.60 2.95 Silicone flow control agent1.00 1.00 1.00 (Dow Corning DC-57) _ 5 _ 1~5T-5632 ~ ith reference to Fig. 1 of the drawings, a flexographic printer of a commercially available design (Apex ~achine Co.) is schematically sho~l at 5, the unit consisting of three independent printing hezds 6, 7, and 8, one for each color, arranged around a single, rubber-covered offset cylinder 9, which transfers all three colors to the tile 2. The pattern or plate cylinder roll 9 carries conventional molded rubber or photopolymer flexographic plates. The back-up roll 10 is steel. As sho~m in the drawing, the printer 5 and slice feeder 11 which is utilized for feeding the tile beneath into the printer, share a common support frzme and drive. As described above, the three inks I - III are all ~V curable, although it would be obvious that heat curable inks could be used equally as well.
After the inks have been transferred in the desired design to the tile substrate, they are then preferably cured to minimize smearing in subsequent operations, this being accomplished, when using W
curable inks, by placing medium pressure mercury arc la7r.ps at 12. UV
exposure requirements at 180 ft./min. conveyor speed is about 600 watts/inch of line width.
After passing beneath the W lam.ps, print-on nubs are applied to the tile surface to impart the surface texture which plzys an important roll in gloss retention in the finished product. An example of a coating formulation for the print-on nubs is as follows:
Exæm~le IV
The following reactants were charged into a reaction vessel.
Ingredients - Grams Triol (Hooker F-1017-180) Re2ction product of 1 mole glycerol, 3 moles of a 7/3 mixture of adipic acid and isophthalic acid, and 3 moles 1,6 hexanediol ~7 960; Hydroxyl No. 175 93 Diol (Union Carbide PCP0200) A poly-caprolactone diol having a r~.~7 of 540 and a r.7ydroxyl No. of 207 58 2-ethylhexylacrylate 94 Hexanediol diacrylate 62 - 6 - I~GT-5632 .
132.3 grams of 4,4' diisocyanato dicyclohexylmethane and 0.4 grams of dibutyltin dilaurate catalyst were then added and the mixture reacted at 45C. to 50C. After the reaction has proceeded for approximately 45 minutes, 5.8 grams of 2-hydroxyethylacrylate was 5 added continuing the stirring and heating for an additional two hours at which point the isocyanate functionality is constant.
Based on 100 parts by weight of the reaction mixture which is a mixture of the partially capped isocyanate terminated urethane prepolymer and the acrylate diluent mixture, 2.0% by weight of benzo-phenone photoinitiator is added together with 0.1~ by weight of polyethylene glycol siloxane (Dow Corning DC472) and 1/2% by weightof dibutyltin dilaurate catalyst.
At this point, the coating thus formed has a viscosity of approximately 9,000 centipoises at room temperature and is comprised 15 f 35r reactive diluents and 65% partially acrylate capped urethane prepolymer .
The printer 13 for printing on the nubs comprises a magnesium roll 14 which is chemically engraved with the desired nub pattern and used as the top roll in a two-roll printer assembly. The other roll 20 15 is a rubber-covered back-up roll which forces the tile being pro-cessed into intimate contact with the engraved roll. A rubber doctor blade 16 is used to apply the printing composition of ~xample I~ to the engraved roll and to coctor it evenly into the engraved cells as the roll turns. ~s tile passes between the two rolls, the nubbly pattern is transferred to the flexographic printed tile. Adjustments in the engraved roll can be made; and, generally speaking, the nubs produced will range in height from about 2. 5 to 5.0 mils, in this example, an average of about 3. 5 mils.
mhe actual patterns etched into .the magnesium roll have a 30 fine, straight line Ben Day superimposed at 45 to the roll axis which result in ribs formed within the etched areas. mhe preferred rib geometry is about 20/inch, each rib being 4 mils wide at the roll face. The ribs help prevent the doctor blades from scooping coating out of the relatively large nubbly patterned areas. After a tile has 35 been printed, tne coating flows out enough to wash out the rib image.
In addition, the pattern is etched two steps, the second step in register with the first, but smaller in etched area. This provides a 1135~57 _ 7 _ 1?~m-5632 nub pattern cell which is deeper in hc center and which produces a nub having a more rounded top than is produced by a single-step etch.
The nub printing unit 13 operates at about 200 ft./min. To control foaming within the coating pool behind the doctor blades, excess coating is allowed to run off the edges of the print roll to be collected, defoamed, and returned to the printing unit.
The tile, after being ?rinted with the nubs, may then be conveyed directly beneath a curtain coater 17 which applies an overall coating to the nubbled surface of the tile of approximately 3 mils in thickness. In this example, the coating described in ~xarnple IV is also used in the curtain coater.
Generally speaking, the viscosity of the print-on nub coating of ~xample IV and the coating applied by the curtain coater is sufficiently viscous such that a nubbly texture is formed. How-ever, depending upon the viscosity of the print-on nub composition, it may be desirable to subject the nubs to at least a partial W cure by interposing W lam.ps 18 between the print-on nub printer 13 and the curtain coater 17. The texture may be varied by the shape of the cavities in the nub printer and by adjustments in coating viscosities.
The coated tile was passed under four, in line, 200 watt ?er inch, mediuF. pressure mercury lamps, indicated at 19, at a speed of about 16 feet per minute to partially polymerize the coating by photo?ol~ymerizing the ethylenically unsaturated components of the coating formulation. Surprisingly, there was no necessity to use an inerting blanket during the ultraviolet light cure. The coating on the tile, which is tack-free at this point, although not tough and mar-resistant, is then given a final moisture cure by allowing the coating to age at room conditions ~hereby the unreacted isocyanate end groups in the coating react with moist.ure and chain extend and cross-link to form the final durable, tough, glossy clear coat. At average room conditions, the coating develops its optimum properties within about 3 weeks.
It will be equally as obvious to one skilled in the art that the formulation for the printing inks, print-on nubs, and wear coating may be the same or different and that adjustments within given compositions may be made to achieve the desired viscosity required by the process parameters.
11;~5~57 - 8 - ~G'.-5632 In the e~amples given above, the coatings are cured by both a W cure mechanism and also through chain extension of the isocyanic terminated prepolymer by the formation of urea linkages on moisture cure. The latter chain extension results in a somewhat tougher, more scratch resistant coating than is usually achievable wi+h a completely 100% UV curable coating.
The decorative tile thus formed is illustrated in cross-section in Fig. 2. The vinyl-asbestos tile base is represented by numeral 20 with the decorative print 21, nubs 22, and wear coat 23 positioned as shown.
It is equally as obvious to one skilled in the art that electron beam curing or radiation sources other than W light may be used to cure the inks, nubs, and wear coatings, although W cure is generally ?racticed today since it does not require elaborate shielding such as is required with some other radiation sources. As stated above, it would also be possible to use a heat cured ink formulation, substituting a heat source for the UV source just after the printing station. Other modifications will become a?parent to those skilled in the art.
Although the invention has been described relative to the printing znd coating of tile to form a nubbly coated ?roduct, the on-line printing and coating of a tile blanket is readily achieved with suitable modifications in equipment required for ?rinting znd coating wider goods. Also, although the invention has been described with respect to the production of a decorative vinyl tile product, the ?roduction of decorative vinyl sheet goods in accordance with the practice of this invention will also be readily apparent. The inven-tion is of particular utility wherever at 'east a portion of a flat subs'rate is printed and wherein it is desired not to distort the printed image by embossing when forming a nubbly texture. For example, with respect to vinyl asbestos tile substrates, tne tile may firs~ be valley printed with a conventional valley printing roll to yield an embossed colored pattern over z portion of the surface of the tile product, after which the flat areas are subjected to flexographic printing, for example. Where valley printing is utili~ed for pro-ducing at least a portion of the image, the practice of prime coating in accor ance with 3agley et al.,Cdn. Application Serial ~o.
_ 9 _ 11GT-5632 312,443 filed October 2, 1978 has been found desirable, such prime coating preferably being applied after the flexogra~hic printins step and af~er the curing of the ink and prior to the print-on nub printing step.
It will likewise be obvious that other methods of printing or otherwise forming a decorative vinyl composition substrate, such as rotogravure printing a vinyl composition sheet, may be employed in the practice of this invention.
Both the embossing of the substrate and the post-embossing of the wear layer can readily be tolerated where distortion of the decorative substrate is not of real concern. However, for example, where a relatively smooth substrate is first printed with a desired visual design and where it is desirable not to disturb or distort the printed design by using the above-described embossing techniques, then an alternate process must be designed.
Summary of the Invention This invention solves the problem of-providing a decorative substrate with a nubbly textured, radiation-cured wear layer without performing an embossing step. This is achieved by first overprinting the decorative vinyl composition substrate with nubs of a clear, radiation-curable coating, after which an overall clear, radiation-curable wear layer is applied with the overall nubbly, radiation-curable coating being cured to form a glossy~ high performance, nubbly wear layer.
Brief Descri~tion of the Drawing Figure 1 is a schematic drawing illustrating the practice of this invention wherein smooth vinyl asbestos tile substrates are first printed using a flexographic printer to achieve the desired-visual image on the smooth surface, after which print-on nubs are applied and the tile curtain coated and cured.
Figure 2 is a cross-sectional view of a printed decorative tile having a textured glossy wear layer formed in accordance with - this invention.
Detailed Description This invention will be described with reference to the production of so-called "no-wax" vinyl asbestos tile products, al-though it will be equally as obvious to anyone skilled in the art that the practice of the invention is readily adapted to the pro-duction of printed decorative vinyl composition tile and sheet goods wherein at least a portion of the printing is confined to a smooth planar surface of the vinyl composition substrate and wherein it is desired not to distort the printing through an embossing step.
1~3565'7 _ 3 _ ~lGT-5632 For purposes of illustrating the invention, the use of a photopol~erizable coating curable by common W sources will be described, although it will just as obviously be evident to one skilled in the art that the practice of the invention .nay be achieved 5 with the use of any radiation-curable coating utilizing radiation sourees sueh as eleetron beams. The applieation of photoeurable eoatings to printed surfaees sueh as floor eoverings, for example, is described in U. S. Patent 3,840,448, and the application of photo-polymerizable coatings to tile is described in U. S. Patent 3,717,558.
Earlier prior art has suggested that ethylenically unsaturated coatings may be cured by ionizing radiation or light and that sueh eoatings may be used for proteetively eoating impervious artieles such as linoleum (see, for exanple, U. S. Patent 3,o56,760).
Boranian et al., U. S. Patent 3,924,023, describes a process 15 wherein, for example, printed tile products having high performance, wear resistant eoatings may be formed. Ultimately, the performanee of the wear eoat will depend upon the formulation of the W eurable eoating. In their proeess, it is recommended that an on-line process be used wherein a tile-forming blanket is ealendared from the usual 20 vinyl asbestos tile-forming eomposition, the blanket then printed with the desired design, eoated with a W eurable eoating eomposition whieh is then eured after whieh the individual tiles are eut from the cured eoated blanket. Sinee the high performanee eoatings whieh form the elear wear layer are neeessarily extremely expensive compared 25 with the vinyl asbestos composition substrates, any scrap losses can be extremely costly. Aceordingly, the speeifie embodiment deseribed in this invention will deal with a process wherein preformed vinyl asbestos tiles are printed and coated.
Vinyl-asbestos tile formulations are well known in the art, 30 as are the processing conditions for tile formation (see, for example, U. S. Patent 2,773,851 and the above-discussed U. S. Patent 3,924,023).
Exam~les I - III
UV Curable Flexo~ra~hic Inks .
The photopolymerizable oligomer forming the basis for the 35 flexographic ink is formed by reacting the following reactants in a reaction vessel.
_ 4 _ l!GT-5632 .
Ing.redients Grams 4,4' diisocyanato dicyclohexylmethane 29.41 Diol (~nion Carbide PCP0200) A poly- 32.47 caprolactone diol having a i~ of 540 and a Hydroxyl No. of 207 2-Hydroxyethylacrylate 17.87 2-Ethylhexylacrylate ` 13.15 Trimethylolpropane triacrylate 7.03 Dibutyl tin dilaurate 0.02 2,6 Ditertbutyl-4-methylphenol 0.05 .In forming the oligomer, the diol, 2-ethylhexylacrylate and trimethylolpropane triacrylate are first charged into the reaction vessel. The diisocyanate and dibutyl tin dilaurate catalyst are then added and the mixture reacted at 45 to 50C. After the reaction has proceeded for approximately 45 minutes, thé hydroxyethylacrylate is added, continuing the stirring and heating for an additional two hours at which point the isocyanate functionality is constant.
The following inks were then formulated as follows:
Parts by l~eight Example Exar,ple Example Ing~edients I_ II III
Photopolymerizable oligomer29.575.10 33.58 l~onomer diluent (1)31.0060.00 40.00 Cellulose acetate butyrate11.00 11.00 -25 Pi&ments l~hite 20.00 Yellow 25.00 Green 10.00 10.00 Photoinitiators Chlorothioxanthone0.811.30 1.47 Methyldiethanolamine 1.62 2.60 2.95 Silicone flow control agent1.00 1.00 1.00 (Dow Corning DC-57) _ 5 _ 1~5T-5632 ~ ith reference to Fig. 1 of the drawings, a flexographic printer of a commercially available design (Apex ~achine Co.) is schematically sho~l at 5, the unit consisting of three independent printing hezds 6, 7, and 8, one for each color, arranged around a single, rubber-covered offset cylinder 9, which transfers all three colors to the tile 2. The pattern or plate cylinder roll 9 carries conventional molded rubber or photopolymer flexographic plates. The back-up roll 10 is steel. As sho~m in the drawing, the printer 5 and slice feeder 11 which is utilized for feeding the tile beneath into the printer, share a common support frzme and drive. As described above, the three inks I - III are all ~V curable, although it would be obvious that heat curable inks could be used equally as well.
After the inks have been transferred in the desired design to the tile substrate, they are then preferably cured to minimize smearing in subsequent operations, this being accomplished, when using W
curable inks, by placing medium pressure mercury arc la7r.ps at 12. UV
exposure requirements at 180 ft./min. conveyor speed is about 600 watts/inch of line width.
After passing beneath the W lam.ps, print-on nubs are applied to the tile surface to impart the surface texture which plzys an important roll in gloss retention in the finished product. An example of a coating formulation for the print-on nubs is as follows:
Exæm~le IV
The following reactants were charged into a reaction vessel.
Ingredients - Grams Triol (Hooker F-1017-180) Re2ction product of 1 mole glycerol, 3 moles of a 7/3 mixture of adipic acid and isophthalic acid, and 3 moles 1,6 hexanediol ~7 960; Hydroxyl No. 175 93 Diol (Union Carbide PCP0200) A poly-caprolactone diol having a r~.~7 of 540 and a r.7ydroxyl No. of 207 58 2-ethylhexylacrylate 94 Hexanediol diacrylate 62 - 6 - I~GT-5632 .
132.3 grams of 4,4' diisocyanato dicyclohexylmethane and 0.4 grams of dibutyltin dilaurate catalyst were then added and the mixture reacted at 45C. to 50C. After the reaction has proceeded for approximately 45 minutes, 5.8 grams of 2-hydroxyethylacrylate was 5 added continuing the stirring and heating for an additional two hours at which point the isocyanate functionality is constant.
Based on 100 parts by weight of the reaction mixture which is a mixture of the partially capped isocyanate terminated urethane prepolymer and the acrylate diluent mixture, 2.0% by weight of benzo-phenone photoinitiator is added together with 0.1~ by weight of polyethylene glycol siloxane (Dow Corning DC472) and 1/2% by weightof dibutyltin dilaurate catalyst.
At this point, the coating thus formed has a viscosity of approximately 9,000 centipoises at room temperature and is comprised 15 f 35r reactive diluents and 65% partially acrylate capped urethane prepolymer .
The printer 13 for printing on the nubs comprises a magnesium roll 14 which is chemically engraved with the desired nub pattern and used as the top roll in a two-roll printer assembly. The other roll 20 15 is a rubber-covered back-up roll which forces the tile being pro-cessed into intimate contact with the engraved roll. A rubber doctor blade 16 is used to apply the printing composition of ~xample I~ to the engraved roll and to coctor it evenly into the engraved cells as the roll turns. ~s tile passes between the two rolls, the nubbly pattern is transferred to the flexographic printed tile. Adjustments in the engraved roll can be made; and, generally speaking, the nubs produced will range in height from about 2. 5 to 5.0 mils, in this example, an average of about 3. 5 mils.
mhe actual patterns etched into .the magnesium roll have a 30 fine, straight line Ben Day superimposed at 45 to the roll axis which result in ribs formed within the etched areas. mhe preferred rib geometry is about 20/inch, each rib being 4 mils wide at the roll face. The ribs help prevent the doctor blades from scooping coating out of the relatively large nubbly patterned areas. After a tile has 35 been printed, tne coating flows out enough to wash out the rib image.
In addition, the pattern is etched two steps, the second step in register with the first, but smaller in etched area. This provides a 1135~57 _ 7 _ 1?~m-5632 nub pattern cell which is deeper in hc center and which produces a nub having a more rounded top than is produced by a single-step etch.
The nub printing unit 13 operates at about 200 ft./min. To control foaming within the coating pool behind the doctor blades, excess coating is allowed to run off the edges of the print roll to be collected, defoamed, and returned to the printing unit.
The tile, after being ?rinted with the nubs, may then be conveyed directly beneath a curtain coater 17 which applies an overall coating to the nubbled surface of the tile of approximately 3 mils in thickness. In this example, the coating described in ~xarnple IV is also used in the curtain coater.
Generally speaking, the viscosity of the print-on nub coating of ~xample IV and the coating applied by the curtain coater is sufficiently viscous such that a nubbly texture is formed. How-ever, depending upon the viscosity of the print-on nub composition, it may be desirable to subject the nubs to at least a partial W cure by interposing W lam.ps 18 between the print-on nub printer 13 and the curtain coater 17. The texture may be varied by the shape of the cavities in the nub printer and by adjustments in coating viscosities.
The coated tile was passed under four, in line, 200 watt ?er inch, mediuF. pressure mercury lamps, indicated at 19, at a speed of about 16 feet per minute to partially polymerize the coating by photo?ol~ymerizing the ethylenically unsaturated components of the coating formulation. Surprisingly, there was no necessity to use an inerting blanket during the ultraviolet light cure. The coating on the tile, which is tack-free at this point, although not tough and mar-resistant, is then given a final moisture cure by allowing the coating to age at room conditions ~hereby the unreacted isocyanate end groups in the coating react with moist.ure and chain extend and cross-link to form the final durable, tough, glossy clear coat. At average room conditions, the coating develops its optimum properties within about 3 weeks.
It will be equally as obvious to one skilled in the art that the formulation for the printing inks, print-on nubs, and wear coating may be the same or different and that adjustments within given compositions may be made to achieve the desired viscosity required by the process parameters.
11;~5~57 - 8 - ~G'.-5632 In the e~amples given above, the coatings are cured by both a W cure mechanism and also through chain extension of the isocyanic terminated prepolymer by the formation of urea linkages on moisture cure. The latter chain extension results in a somewhat tougher, more scratch resistant coating than is usually achievable wi+h a completely 100% UV curable coating.
The decorative tile thus formed is illustrated in cross-section in Fig. 2. The vinyl-asbestos tile base is represented by numeral 20 with the decorative print 21, nubs 22, and wear coat 23 positioned as shown.
It is equally as obvious to one skilled in the art that electron beam curing or radiation sources other than W light may be used to cure the inks, nubs, and wear coatings, although W cure is generally ?racticed today since it does not require elaborate shielding such as is required with some other radiation sources. As stated above, it would also be possible to use a heat cured ink formulation, substituting a heat source for the UV source just after the printing station. Other modifications will become a?parent to those skilled in the art.
Although the invention has been described relative to the printing znd coating of tile to form a nubbly coated ?roduct, the on-line printing and coating of a tile blanket is readily achieved with suitable modifications in equipment required for ?rinting znd coating wider goods. Also, although the invention has been described with respect to the production of a decorative vinyl tile product, the ?roduction of decorative vinyl sheet goods in accordance with the practice of this invention will also be readily apparent. The inven-tion is of particular utility wherever at 'east a portion of a flat subs'rate is printed and wherein it is desired not to distort the printed image by embossing when forming a nubbly texture. For example, with respect to vinyl asbestos tile substrates, tne tile may firs~ be valley printed with a conventional valley printing roll to yield an embossed colored pattern over z portion of the surface of the tile product, after which the flat areas are subjected to flexographic printing, for example. Where valley printing is utili~ed for pro-ducing at least a portion of the image, the practice of prime coating in accor ance with 3agley et al.,Cdn. Application Serial ~o.
_ 9 _ 11GT-5632 312,443 filed October 2, 1978 has been found desirable, such prime coating preferably being applied after the flexogra~hic printins step and af~er the curing of the ink and prior to the print-on nub printing step.
It will likewise be obvious that other methods of printing or otherwise forming a decorative vinyl composition substrate, such as rotogravure printing a vinyl composition sheet, may be employed in the practice of this invention.
Claims (10)
1. In a method for forming a decorative vinyl composition surface covering wherein a radiation-curable clear wear layer overlies the decorative substrate, the improvement comprising:
(a) overprinting the decorative substrate with nubs of clear, radiation-curable coating;
(b) applying an overall clear., radiation-curable coating composition to form a nubbly textured clear coating on the decorative vinyl composition substrate; and (c) irradiating the coating.
(a) overprinting the decorative substrate with nubs of clear, radiation-curable coating;
(b) applying an overall clear., radiation-curable coating composition to form a nubbly textured clear coating on the decorative vinyl composition substrate; and (c) irradiating the coating.
2. The method in accordance with claim 1 wherein the nubs are subjected to a radiation cure prior to coating with a clear wear layer.
3. The method in accordance with claim 1 wherein the vinyl composition substrate is a printed vinyl asbestos tile.
4. The method in accordance with claim 3 wherein the tile substrate is valley printed prior to being printed with a design on the remaining planar surface thereof.
5. The method in accordance with claims 1 or 2 wherein the nubs are printed onto a tile-forming blanket after consolidating the tile-forming composition and a clear coat after applied.
6. The method in accordance with claims 1 or 2 wherein the decorative vinyl composition surface covering is a printed vinyl sheet good.
7. The method in accordance with claims 1 or 2 wherein the decorative vinyl composition surface covering is a rotogravure printed vinyl composition tile.
8. In a method for forming a decorative, printed, vinyl composition surface covering having a high gloss textured wear layer of a photopolymerized clear coating overlying a decorative, printed, vinyl composition substrate, the improvement comprising:
(a) overprinting the printed substrate with nubs of a clear photopolyermized coating;
(b) applying an overall clear photopolymerized coating to the printed substrate to form a nubbly textured clear coating; and (c) subjecting the textured clear coating to a photo-polymerization source to set the texture and cure the coating.
(a) overprinting the printed substrate with nubs of a clear photopolyermized coating;
(b) applying an overall clear photopolymerized coating to the printed substrate to form a nubbly textured clear coating; and (c) subjecting the textured clear coating to a photo-polymerization source to set the texture and cure the coating.
9. The method in accordance with claim 8 in which a photoinitiator is present in the clear coating and in which the photopolymerization source is a UV light source.
10. The method in accordance with claims 8 or 9 in which the nubs are photopolymerized prior to the application of the overall clear wear layer coating.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US97200278A | 1978-12-21 | 1978-12-21 | |
| US972,002 | 1978-12-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1135657A true CA1135657A (en) | 1982-11-16 |
Family
ID=25519040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000334009A Expired CA1135657A (en) | 1978-12-21 | 1979-08-17 | Method for forming a decorative vinyl composition surface covering |
Country Status (4)
| Country | Link |
|---|---|
| AU (1) | AU526404B2 (en) |
| CA (1) | CA1135657A (en) |
| DE (1) | DE2938292B2 (en) |
| GB (2) | GB2041244B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3043741A1 (en) * | 1980-11-20 | 1982-08-19 | Agrob Anlagenbau GmbH, 8045 Ismaning | METHOD FOR DIRECTLY PRINTING CERAMIC COLORS AND PRINTING MEDIUM HERE |
| DE3129758C2 (en) * | 1981-07-28 | 1984-09-06 | Vsesojuznyj naučno-issledovatel'skij institut trikotažnoj promyšlennosti, Moskva | Process for the production of a decorative material |
| US4595621A (en) * | 1984-10-29 | 1986-06-17 | Armstrong World Industries, Inc. | Simulated embossing on floor covering |
| DE4417784A1 (en) * | 1994-05-20 | 1995-11-23 | Dlw Ag | Pattern printing process for strips or sheets |
| DE4438246C1 (en) * | 1994-10-26 | 1995-12-07 | Metronic Geraetebau | Printing device for printing on compact discs |
| JPH10226148A (en) * | 1997-02-17 | 1998-08-25 | Heidelberger Druckmas Ag | Method for multicolor printing of non-absorbable substance |
| DE20314274U1 (en) * | 2003-09-12 | 2004-05-27 | Faber-Castell Ag | Wood-framed pen for writing, painting, drawing and cosmetic purposes |
| FR2868735B1 (en) | 2004-04-08 | 2007-09-28 | Polygo Sarl | METHOD AND INSTALLATION OF PRINTING THERMOPLASTIC MATERIAL SLABS TO REALIZE REPORTED FLOOR |
| CN112874112B (en) * | 2021-02-07 | 2023-09-01 | 广东赛洁无纺布科技有限公司 | Waterproof composite non-woven fabric |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4047903A (en) * | 1972-09-26 | 1977-09-13 | Hoechst Aktiengesellschaft | Process for the production of abrasives |
| US4070398A (en) * | 1976-10-18 | 1978-01-24 | Eastman Kodak Company | Laminates useful as packaging materials and method for manufacture thereof |
| US4105806A (en) * | 1976-11-19 | 1978-08-08 | American Can Company | Photoinitiator free inks and method |
| US4113895A (en) * | 1976-11-19 | 1978-09-12 | American Can Company | Method for producing multilayered coated substrate |
| DE2721292B2 (en) * | 1977-05-12 | 1980-01-31 | H.J.M. 5460 Linz Tempelaars | Process for the production of a thermosetting synthetic resin coating with a structured surface |
-
1979
- 1979-08-17 CA CA000334009A patent/CA1135657A/en not_active Expired
- 1979-09-03 AU AU50524/79A patent/AU526404B2/en not_active Ceased
- 1979-09-21 DE DE2938292A patent/DE2938292B2/en not_active Withdrawn
- 1979-12-21 GB GB7944065A patent/GB2041244B/en not_active Expired
-
1982
- 1982-12-21 GB GB08236271A patent/GB2116116B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2041244A (en) | 1980-09-10 |
| GB2116116B (en) | 1984-02-22 |
| DE2938292B2 (en) | 1981-07-30 |
| DE2938292A1 (en) | 1980-06-26 |
| AU5052479A (en) | 1980-06-26 |
| GB2041244B (en) | 1983-06-15 |
| GB2116116A (en) | 1983-09-21 |
| AU526404B2 (en) | 1983-01-06 |
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| MKEX | Expiry |