GB2057362A - Multi-level embossed cellular surface - Google Patents
Multi-level embossed cellular surface Download PDFInfo
- Publication number
- GB2057362A GB2057362A GB7930034A GB7930034A GB2057362A GB 2057362 A GB2057362 A GB 2057362A GB 7930034 A GB7930034 A GB 7930034A GB 7930034 A GB7930034 A GB 7930034A GB 2057362 A GB2057362 A GB 2057362A
- Authority
- GB
- United Kingdom
- Prior art keywords
- inks
- process according
- resinous
- blowing agent
- porous 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.)
- Granted
Links
- 230000001413 cellular effect Effects 0.000 title claims abstract description 5
- 239000000976 ink Substances 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 67
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000000155 melt Substances 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 230000035515 penetration Effects 0.000 claims abstract description 9
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 6
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 6
- 239000012467 final product Substances 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 4
- -1 poly(vinyl chloride) Polymers 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 19
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 17
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 15
- 239000004800 polyvinyl chloride Substances 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 239000004014 plasticizer Substances 0.000 claims description 12
- 229920001944 Plastisol Polymers 0.000 claims description 11
- 239000004999 plastisol Substances 0.000 claims description 11
- 238000005187 foaming Methods 0.000 claims description 7
- 239000004156 Azodicarbonamide Substances 0.000 claims description 5
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical group NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 5
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000012260 resinous material Substances 0.000 abstract description 13
- 239000006260 foam Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 description 31
- 239000000463 material Substances 0.000 description 14
- 239000003381 stabilizer Substances 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 10
- 239000000945 filler Substances 0.000 description 9
- 239000008187 granular material Substances 0.000 description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 7
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000004049 embossing Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 description 2
- 230000003796 beauty Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- SWUYLUYFFADSNR-UHFFFAOYSA-N decyl phenyl hydrogen phosphite Chemical compound CCCCCCCCCCOP(O)OC1=CC=CC=C1 SWUYLUYFFADSNR-UHFFFAOYSA-N 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005474 octanoate group Chemical group 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- LSNDGFYQJRXEAR-UHFFFAOYSA-N benzenesulfonamidourea Chemical compound NC(=O)NNS(=O)(=O)C1=CC=CC=C1 LSNDGFYQJRXEAR-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical group CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
- D06N7/0005—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface
- D06N7/0007—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface characterised by their relief structure
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Laminated Bodies (AREA)
Abstract
A process for making a cellular wear surface by applying to a porous substrate 1 a plurality of thermoplastic resinous inks 3 to 9 developed from binders having different melt viscosities, the inks and substrate comprising a composite structure which also includes a blowing agent. The blowing agent may be either in the substrate or in the inks applied thereto, and penetration of the porous substrate by the inks may be partial or complete. Upon final heating to fuse and foam all the resinous material of this structure, the melt viscosity differences of the resins in the inks provide varying degrees of physical resistance to expansion of the total system in the inked areas, thus producing multi-level design areas on the final product. <IMAGE>
Description
SPECIFICATION
Multi-level embossed cellular surface covering
The invention relates generally to a process for producing resinous composition surface coverings and, more particularly, to a process for forming such a product having a multi-level embossed wear surface wherein multiple inks evolved from vinyl resins having distinguishable differences in their melt viscosities or thermoplastics are printed on a porous substrate to create a design which may extend through at least 5% of the thickness of the layer and can extend through up to 100% thereof. The inks and the substrate comprise a composite structure which also includes a blowing agent.Final heating to fuse the resins and decompose the blowing agent results in a multi-level embossed wear surface because of the varying degrees of physical restriction of foaming of the sheet due to the melt viscosity differences of the resins used in the inks.
Description of the prior art
It is known to enhance the appearance of plastic floor and wall coverings by means of various decorative designs thereon which may extend partially or entirely through the sheet. Further enhancement of the appearance of such sheets has been accomplished by achieving a three-dimensional appearance thereon.
Prior methods of doing this have included mechanical or chemical embossing techniques or inclusion with the granules of a dryblend base layer, for example, an ingredient which can be subsequently removed or altered to produce an embossed effect. It is also known to obtain a textured surface on a resinous surface covering by controlling the fluid viscosity of the printing composition used thereon. The use offoamable inks for this purpose is also old. It is further known to inhibit foaming in selected areas of a foamable resinous sheet by chemically increasing the viscosity of the resinous material in those areas. It is also known to produce an embossed surface covering by using two or more resins having different molecular weights (different melt viscosities) to form the particles which, after being pressed into a sheet, recover to varying heights.
U. S. Patent No. 3,359,352-Powell et al. relates to a method for forming a resinous composition surface covering having a geometric decoration. This is accomplished by depositing a layer of fine granules of resinous composition on the surface of the base, heating to sinner the granules and form a porous layer, printing a design on the sintered layer with a printing composition which will penetrate into the porous composition and then, by heat with or without pressure, forming the printed porous layer into a non-porous layer containing an inlaid design. It is further disclosed by this patent that a textured or embossed product can be obtained by including with the granules a substance which, on further treatment, will create voids in the granular layer.Controlling the amount of printing composition to fill such voids controls the location and depth of the embossing. It is stated in this patent that one way to control the depth of penetration of the printing composition into a sintered dryblend base is by control of the fluid viscosity of the printing composition. Thus, a textured surface may be obtained on the sheet by allowing greater quantities of the printing composition to remain on the surface.
U. S. Patent No. 3,000,754-Zentmyer relates to a surface covering having a multi-level embossed wear surface. The surface covering is formed by applying to a backing particles of two or more polymerized vinyl chloride resins in which the different resins possess a sufficient spread of molecular weights to result in an embossed appearance of the product solely by virtue of the different stress relaxation characteristics of the resins. After the resin particles are hot pressed, the particles of a higher molecular weight resin recover in a vertical direction to an elevation higher than those of a lower molecular weight. This results in a multi-level embossed wear surface on the sheet.
U. S. Patent No. 3,365,353-Witman relates to chemical embossing of foamed decorative surface covering.
In the process of this invention, a foamable resinous plastisol containing a polymerizable monomer is formed into a sheet. There is then applied to the sheet in a predetermined pattern a composition comprising a liquid that will penetrate the sheet and a catalyst that will cause polymerization of said monomer at a temperature in the range above the glass transition temperature of the plasticized vinyl resin and below the decomposition temperature of said resin. The sheet is then heated to a temperature in the range of about 300O-400 F. to fuse the plasticized resin, decompose the blowing agent, and polymerize the monomer. In this process the viscosity of the resinous material in the printed areas of the resinous foamable substrate is increased in situ by producing, through a chemical reaction, a higher viscosity resinous material in the treated areas.
Another process wherein a chemical reaction is utilized to inhibit or prevent expansion of a plastic material in designated areas of a foamable resinous sheet disclosed in U. S. Patent No. 3,453,171-Crowley. In this process, the foregoing is accomplished without regard to the absence or pressure of any activators or other additives which alter the decomposition temperature or activation of the blowing agent. The hardening or modifying agent may be applied to a porous sheet of calendered plasticized vinyl chloride particles and allowed to penetrate. Another method for producing a chemically embossed surface covering is disclosed in
U. S.Patent No. 3,671,283-Crowley wherein a vinyl chloride resin plastisol containing a blowing agent is formed into a thin layer on a supporting material and heated to a temperature below the decomposition temperature of the blowing agent to form a gelled layer therefrom. There is then printed onto the smooth, gelled plastisol surface an aqueous latex composition which contains from about 20%-60% of a vinyl chloride resin. It is stated in the patent that the printing composition is allowed to penetrate the gelled layer to the desired degree, after which the gelled layer is heated to fuse the vinyl chloride resin and decompose the blowing agent and to volatize the water employed in the latex composition in the areas to which it was applied.Full expansion of the sheet material is prevented by the increase in resin content in the treated areas, thereby producing a chemically embossed product. The liquid compositions particularly suitable for use in the invention include aqueous latices containing a polymer which has reduced thermal plasticity characteristics over the surface polymer to which it is being applied, such as having a slightly different structural composition or a higher molecular weight so as to reduce the melt viscosity of the treated areas at the temperature of expansion of the treated surface. For example, in the treatment of a gelled poly(vinyl chloride) surface, it is preferred that the polymer be composed of a vinyl chloride copolymer having the reduced thermoplasticity from the poly(vinyl chloride).
In contrast to the processes of the prior art, the process of this invention overcomes problems associated with prior attempts to produce a decorative, multi-level embossed surface on a resinous sheet. In a process wherefoamable inks were printed side-by-side (butt-printed), many times out-of-register printing resulted in an overblown condition at overlapping printed portions thereof and/or depressed portions (dimples) where the out-of-register printing left areas where no ink was applied. Further, in prior processes where foamable dryblend was printed with non-foamable inks, all printed areas of the finished sheet were the same height.
Prior attempts to vary the elevation of the printed portions included varying the penetration of the ink and/or the fluid viscosity thereof, or by overprinting. The process of the present invention also provides a simple and effective solution to these problems. In still further contrast to prior processes, the process of this invention does not require alteration or treatment of the substrate material; the amount of expansion in the printed areas can be easily regulated; and the process is not limited to the use of resinous or granular substrates since almost any printable porous substrate may be used.
It can thus be seen that the process of this invention provides a relatively simple and inexpensive procedure for producing a highly decorative embossed wear surface on a resinous surface covering without the need for prior mechanical or chemical embossing equipment and techniques.
Summary of the invention
This invention relates to a process for producing a cellular resinous surface covering having a multi-level, embossed decorative wear surface wherein the expansion of foamable plastic material in the system is restricted in particularly designated areas through the use of multiple inks with binders having different melt viscosities. This is accomplished without the use of any special additives or activators in the sheet which alter the decomposition temperature of or activate the blowing agent.
There are three embodiments of the invention. In the first embodiment, a layer of foamable dryblend is formed and then heated at a temperature below the decomposition temperature of the blowing agent in the dryblend to form a porous, cohesive layer. The sheet so formed is then printed on in a design with inks developed from vinyl resins having distinguishable differences in their melt viscosities. The printed sheet is then heated to fuse the resinous material and decompose the blowing agent. Due to the melt viscosity differences of the binders in the inks, physical restriction of foaming in selected areas of the sheet is achieved in varying degrees, thus resulting in an embossed, in-register design on the wear surface in a simple and economical manner.Prior to the final heating step, a clear plastisol coat may be applied over the printed foamable base layer for enhanced beauty and durability of the wear surface.
In the second embodiment of the invention, a mechanically frothed poly(vinyl chloride) foam is used as the porous base layer. The mechanically frothed foam, including a blowing agent, was cast onto a paper backing, cooled, and printed with the previously mentioned inks having different melt viscosities. As in the previous embodiment, prior to the final heating step, a clear plastisol coat may be applied over the printed foamable base layer for enhanced beauty and durability of the wear surface. Again, due to the melt viscosity differences of the binders in the ink, physical retardation of the foaming in selected areas of the sheet was achieved in varying degrees. This results in an embossed, in-register design on the wear surface of the finished product.
In the third embodiment of the invention, a porous, reinforced, non-woven polyester web of the type disclosed in U. S. Patent 3,968,275 was used as the printable base layer. In this embodiment, the blowing agent was incorporated into each ink, printed thereon. After heating to gel the inks, a clear plastisol top coat was applied and the structure heated to fuse the resin of the structure and decompose the blowing agent.
Again, the difference in the melt viscosities of the inks produced a multi-level embossing surface on the structure.
The foregoing process eliminates the need for special equipment and complicated procedures required by the prior art and results in a well-defined, in-register, three-dimensional decorative wear surface on the surface covering with no overblown or depressed out-of-register design areas. The degree of expansion in the printed areas is easy controlled through selection of inks of the desired thermoplasticity which have a varying propensity for limiting expansion of the foamable resinous material.
Brief description of the drawing
Figure 1 is a flow diagram depicting the steps followed in carrying out three embodiments of the process of this invention;
Figure 2 is a cross-sectional view of a portion of the surface covering being formed by the first embodiment of the process of this invention wherein the inks printed thereon to create the design have penetrated into the porous dryblend and a clear resinous top coat has been applied;
Figure 3 is a cross-sectional view showing a portion of the surface covering made by the process of this invention from the structure shown in Figure 2;;
Figure 4 is a cross-sectional view of a portion of the surface covering being formed by the second embodiment of this invention, showing a paper backing, a mechanically frothed resinous material thereon, resinous inks printed on and extending through the thickness of the foamed material which contains a blowing agent, and a resinous top coat;
Figure 5 is a cross-sectional view illustrating a portion of the surface covering by the process of this invention from the structure shown in Figure 4;
Figure 6 is a cross-sectional view illustrating a portion of the surface covering made by a process of this invention and showing a porous, reinforced, non-woven polyester web which has been printed in a design with foamable resinous inks which have penetrated therethrough and a clear resinous top coat; and
Figure 7 is a cross-sectional view illustrating a portion of the surface covering having a multi-level wear surface which was made by the process of this invention from the structure shown in Figure 6.
Description of the preferred embodiments
This invention is usable with substantially any porous substrate into which the inks applied thereto can penetrate. As indicated by the flow diagram of Figure 1, there are three embodiments of the invention.
In the first embodiment of the invention, the manufacturing process begins with the formation of a porous substrate. The formation of the porous substrate begins with the formation of a resinous dryblend. The dryblend is in the form of a free-flowing homogeneous mixture of unfused thermoplastic resin particles, including liquid vinyl plasticizer, filler, pigment, and vinyl stabilizer. If desired, a blowing agent may be included in the dryblend. However, it will be noted that in this invention the blowing agent may be included in the dryblend or in the inks applied thereto. In this embodiment, as described, the blowing agent is in the dryblend.
Poly(vinyl chloride) is the preferred resin for use in forming the surface covering of the present invention, although copolymers of vinyl chloride with minor proportions of other materials such as vinyl acetate, vinylidene chloride, other vinyl esters such as vinyl proprionate vinyl butyrate, as well as alkyl substituted vinyl esters may be used.
The free-flowing mix of resin, plasticizer, blowing agent, stabilizer, pigment, and filler may be readily formed by adding the resin, for example, a homopolymer of vinyl chloride, in the form of discrete particles, along with the vinyl resin plasticizer such as di(2-ethyl hexyl)phthalate, butyl benzyl phthalate, epoxidized soybean oil, or tricresyl phosphate, blowing agent, filler, pigment, and suitable vinyl resin stabilizers to a mixer or blender such as a Henschel blender where they are mixed under moderate heat, for instance at a temperature of about 1 60-220"F., for a period of time to ensure that the liquid plasticizer and the stabilizer become absorbed and thus diffused throughout the resin particles and the blowing agent and the remaining inredients absorbed thereon.Care is taken so that no decomposition of the blowing agent and no fusion of the resin particles occurs during the mixing, and the temperature must be kept below that at which such would occur.
The blowing agent must be thoroughly distributed throughout the resin-plasticizer mixture. A variety of blowing agents is available on the market for incorporation in thermoplastic resins. The preferred blowing agent for poly(vinyl chloride) is azodicarbonamide which normally decomposes at a temperature of about 390"F. in air. This blowing agent is particularly suitable for use in the method of the present invention in view of its relatively high decomposition temperature. Other usable blowing agents with the temperature at which they release gas vigorously in dioctyl phthalate are p,p'-Oxybis (benzenesulfonylhydrazide) - 320"F. and p,p'-Oxybis (benzenesulfonylsemicarbazide) - 425 F.
As a general rule, the preferred minimum decomposition temperature of a blowing agent should be about 300 F., and the blowing agent should decompose below the decomposition temperature of the resin, which in the case of poly(vinyl chloride) would be about 400 F. However, stabilized vinyl resin composition will normally not decompose until even higher temperatures--approaching 450 F.--are reached.
Generally speaking, the addition of fillers and pigments to the mix may be made either initially, at the end of the mixing cycle when the resin particles remain relatively warm, or after the dryblended resin particles have been mixed and cooled. The color of the layers may be controlled over a wide range and substantially transparent or translucent layers may be achieved by omitting the filler and most of all of the pigment from the vinyl dryblend forming the layer. Based on 100 parts by weight of resin, 15 to 80 parts by weight plasticizer, 1 to 5 parts by weight stabilizer, 0 to 10 parts by weight pigment, and 0 to 200 parts by weight filler may be used in forming the free-flowing mixture.
As shown in Figure 2 of the drawings, a foamable layer of unfused thermoplastic granules 1 of dryblend is then formed on a backing 2. The foamable layer may alternatively be formed on a strippable carrier which may be a steel belt, a rubber belt, paper, or a felt having a release coating thereon. If a permanent carrier is used, it may comprise any of the backings normally used as a floor covering backing such as a beater saturated rubber-asbestos sheet, resin-bonded glass webs, bonded synthetic webs, and asphalt-saturated felts. These carriers may be the only final backing or they may be supplemented with other cushioning materials, such as foams and non-woven material.
The next step in the process involves heating the dryblend layer 1 in the range of from about 280"-350"F. to cause partial melting of the resin granules at their points of contact, thereby forming bonds which result in the formation of a cohesive porous layer having a thickness in the range of from about 15 mils to 100 mils.
Bonding of the resinous granules at their points of contact may be effected either by sintering or through activation of a suitable external adhesive coating which may be applied in the final steps of granulation.
After cooling the sintered dryblend layer 1, the next step in the process involves producing a design on the foamable cohesive porous dryblend layer by applying thereto a plurality of inks developed from vinyl resins having distinguishably different melt viscosities, in sufficient amounts to permit penetration thereof into the porous layer to at least about 5% of the thickness thereof. Preferably, as shown in Figure 2, ink-containing portions 3, 4, 5, 6,7,8, and 9 extend substantially clear through the thickness of the dryblend layer 1. The melt viscosity of all of the plastisols from which the inks are developed must be in the range of 100,000 poise to 3,000,000 poise at 380"F. Optionally, about a 10 mil thickness of a clear resinous top coat 10 may be applied.
In this invention, the limits of the molecular weights of usable resins as determined by Gel Permeation
Chromatography are in the range of 50,000 Mw - 200,000 Mw.
The present invention turns on the use of inks developed from two or more polymerized vinyl resins in which the different resins possess a sufficient spread of molecular weights and, therefore, melt viscosities, to offer varying degrees of resistance to expansion of the dryblend and plastisol composition in the areas printed with these inks when the sheet is finally heated to fuse the resins and decompose the blowing agent to result in a multi-level embossed appearance on the wear surfaces of the product.
In reality, the degree of difference in embossed depth depends on: (1) the spead between the difference in melt viscosities, (2) the thickness of the base layer, (3) the penetration of the inks into the base layer, (4) the amount (%) of blowing agent used, and (5) the nature of the base layer. It is preferred that when a thermoplastic base layer is used, the melt viscosity of the base layer corresponds to that of the lowest ink.
It has been found that the molecular weight of the separate resins used in the inks should vary by at least about 7,000 Mw if the embossed appearance is to be distinguishable. At the same time, all the resins used in the inks should have molecular weights falling within the above-stated range of 50,000 - 200,000 Mw. Thus the requisite molecular weights are completely defined.
Figure 3 illustrates an enlarged cross section of the product formed after application of the clear top coat 10 and final heating to fuse the resin and decompose the blowing agent. As shown in Figure 3, in the finished product, ink-containing design elements 3,4,5,6,7,8, and 9 are expanded to different elevations because of the varying degrees of physical resistance to expansion provided by the varying melt viscosities of the resins from which the inks were evolved. Design elements 3,4, 5,6, 7, 8, and 9, of course, may be of any desired color.
Optionally, as shown in Figures 1 and 4, a mechanically frothed resinous material formed in a known manner may be formed into a layer 11 on a carrier which may have a release coating thereon or, optionally, onto a backing material 12, heated, and cooled to form the porous substrate. As indicated, optionally the blowing agent may be included in the mechanically frothed resinous base material 11 or may be in the inks applied to the base material in the subsequent design-producing step. In this embodiment, the blowing agent was included in the mechanically frothed foam. Inked design portions 12, 13, 14, 15, 16, 17, and 18, which extend clear through the thickness of the foam layer 11, were formed by applying differently colored inks having different melt viscosities, as previously described, in side-by-side relationship (butt-printed) thereto.Optionally, a clear, resinous top coat 19 may be applied to the structure followed by heating to fuse all the resinous material and decompose the blowing agent. In this embodiment, as in the previous one, the different melt viscosities of the inks applied to the porous substrate function to restrict foaming of the design elements in varying degrees, thus producing a multi-level embossed surface on the final product shown in
Figure 5.
In the third embodiment of the invention, the porous substrate into which the inks are applied may comprise a non-woven fibrous web 20. In this embodiment, the resinous inks, as previously described, were applied to the porous substrate 20 to form design elements 21,22,23,24,25,26, and 27 in the structure shown in Figure 6 of the drawings. As shown in Figure 7 of the drawings, the final product produced after application of a clear resinous top coat 28 and final heating to fuse the resinous material, and decompose the blowing agent, is a multi-level embossed structure resulting from, as in the previous embodiments, the variations in the restriction of foaming of a structure caused by the different melt viscosities of the inks used in forming the design.
Products which can be manufactured within the scope ofthis invention may include, but are not limited to, floor coverings, wall coverings, drapery and upholstery materials, furniture components, etc. Multi-level sheet products may be manufactured by the method of this invention without the use of chemical or mechanical embossing equipment and techniques, and the embossed areas thereon are in perfect registration with the printed pattern.
The following examples illustrate the three embodiments of the invention. All parts are by weight unless otherwise stated. All molecular weights (Mw) were determined bythe Gel Permeation Chromatography method.
Example I Dryblend granules were prepared by mixing the following components together in a conventional
Henschel dryblending apparatus through a heat history from ambient conditions to approximately 230"F.
1110 C) to ambient conditions.
Ingredients Parts by weight
poly(vinyl chloride) resin 100
alkyl diarlyl phosphates (plasticizer) 75
octyl epoxytallate (plasticizer) 4
zinc-barium octoates decyl phenyl phosphite (stabilizer) 2
*cell stabilizer 1.5
azodicarbonamide (blowing agent) 4
aluminum trihydrate (filler) 150
* A methacrylate cell stabilizer designated "VS-103", commercially available from Air Products and
Chemicals, Inc., Allentown, PA
A base layer of the above composition was cast onto a release paper in a thickness of about 50 mils and
then heated to about 350 F. for 3 minutes to sinter the dryblend mixture. The sintered mixture was then
cooled.
Three resinous inks of the following formulations were prepared.
Ingredients Parts by weight
poly(vinyl chloride) resin (dispersion grade) 100
high Mw
poly(vinyl chloride) resin (dispersion grade) 100
medium Mw
poly(vinyl chloride) resin (dispersion grade) 100
low Mw
calcium carbonate (filler) 40 40 40
C7-, C9-, C11 mixture, phthalate (plasticizer) 30 30 30
alkyl diarlyl phosphates (plasticizer) 30 30 30
octyl epoxytallate (plasticizer) 2 2 2
zinc-barium octoates decyl phenyl phosphite 2 2 2
(stabilizer)
*cell stabilizer 0.5 0.5 0.5
pigment 5 5 5 * A methacrylate cell stabilizer designated "VS-103", commercially available from Air Products and
Chemicals, Inc., Allentown, PA
To the sintered porous dryblend layer, a design pattern was applied using the above inks, each of which
was applied to a separate portion of the pattern in a side-by-side manner (butt printed). In this example, the
penetration of each of the inks was essentially through 100% of the base layer. The structure was then heated
to about 300"F. to gel the inks. About 10 mils of a top coat having the following formulation was applied to the structure.
Ingredients Parts by weight
poly(vinyl chloride) resin (dispersion grade) 100
di(2-ethylhexyl)phthalate 25
2,2,4 trimethyl- 1 ,3-pentanediol dilsobutyrate 17
dibutyl tin maleate 2
The structure was then heated in a hot air impingement oven at 400OF. to produce fusion of the vinyl resin
and decomposition of the blowing agent wherewith a multi-level embossed surface was realized. The
embossed depth increased correspondently to the increased melt viscosity of the applied ink. For the high
melt viscosity ink, the depth was about 35 mils; for the medium melt viscosity ink, the depth was about 15
mils; and for the lower melt viscosity ink, the depth was 0 mils.
Example Il A porous base layerwasformed by mechanically frothing a resinous material having the following composition.
Ingredients Parts by weight poly(vinyl chloride) (dispersion grade) 50 poly(vinyl chloride) (blending grade) 50 di(2-ethylhexyl)phthalate 65 2,2,4trimethyl-1,3 pentanediol diisobutyrate ester 8 dibutyl tin maleate 1 polymethylsiloxane (surfactant) 5 calcium carbonate (filler) 15 azodicarbonamide (blowing agent) 4
About 50 mils of the foamed material of the above formula was cast onto a paper and gelled at about 300"F. for 3 minutes and then cooled. The inks having the formulation given in Example I were then applied to the foamed layer and penetrated substantially through the entire thickness thereof.A top coat having the same formulation as that given in Example I was then applied in a thickness of about 10 mils, after which the structure was heated to about 400"F. to fuse the resinous material and decompose the blowing agent. This resulted in the finished product having a multi-level embossed surface.
Example IIl The base layer, in this example, was a porous, reinforced, non-woven polyester web of the type disclosed in U. S. Patent 3,968,275. Inks having the same formula as given in Example I, but including four parts of the blowing agent, azodicarbonamide, per 100 parts of resin, was incorporated into each of the inks. The inks were applied to the porous base layer in a design and penetrated into the porous layer to a depth of about 40 mils. The structure was then heated to about 300"F. to gel the inks. To the gelled surface, 10 mils of the top coat having the formulation given in Example I was applied, and the structure was then heated in a hot air oven for about 3 minutes at 400"F. to fuse the resinous material and decompose the blowing agent. A multi-level embossed surface was thus achieved on the final product due primarily to the differences in the melt viscosities of the inks used in forming the design in the porous base layer.
Claims (31)
1. A process for forming a decorative, cellular, resinous surface covering having a multi-level embossed wear surface, comprising
(a) producing a printable porous substrate;
(b) producing design areas in said porous substrate by applying a plurality of thermoplastic resinous inks thereto in amounts and fluid viscosities predetermined to result in at least partial penetration through the thickness of the substrate at the points of application, at least one of said inks having a binder of a different melt viscosity from that of another of said inks, said inks and said substrate comprising a composite structure which further includes a blowing agent;;
(c) finally heating the composite structure to fuse the resin and decompose the blowing agent whereby the differences in the melt viscosities of the resinous inks physically restrict foaming in the structure in varying degrees in the areas to which the inks were applied thus producing multi-level embossed design areas on the final product.
2. The process according to claim 1 wherein the inks are plastisols of poly(vinyl chloride) and have a melt viscosity range of from about 100,000 to 3,000,000 poise.
3. The process according to claim 1 wherein the inks are differently pigmented and are printed in side-by-side contact with each other.
4. The process according to claim 3 wherein the entire surface of the porous substrate is printed.
5. The process according to claim 1 wherein the minimum penetration of the inks is about 5% of the thickness of the porous substrate.
6. The process according to claim 1 wherein the inks penetrate through substantially the entire thickness of the porous substrate.
7. The process according to claim 1 wherein the molecular weight difference of the resins used in the inks is at least 7,000.
8. The process according to claim 1 wherein the ratio by weight of the blowing agent to resin in all of the printed areas is substantially uniform.
9. The process according to claim 1 wherein the amounts of solvent and plasticizer in the printed areas of the porous substrate are substantially uniform.
10. The process according to claim 1 wherein the printable porous substrate comprises a sintered layer of unfused resinous particles having a molecular weight range of about 50,000 to 200,000, and wherein the blowing agent is included in said dryblend layer, and the binders of at least some of the thermoplastic resinous inks applied thereto have melt viscosities which are different from that of the dryblend.
11. The process according to claim 10 wherein the melt viscosity of the binder in at least one of the inks is lower than that of the resinous dryblend.
12. The process according to claim 10 wherein the melt viscosity of the binder in at least one of the inks is higher than that of the resinous dryblend.
13. The process according to claim 10 wherein the melt viscosities of the binder in all of the inks are higher than that of the resinous dryblend.
14. The process according to claim 10 wherein the resinous particles are vinyl resin.
15. The process according to claim 14 wherein the vinyl resin is poly(vinyl chloride).
16. The process according to claim 1 wherein at least three of the inks applied to the porous substrate have binders of different melt viscosities.
17. The process according to claim 16 wherein the penetration of each of the inks having binders of different melt viscosities penetrate into the porous substrate of a different degree.
18. The process according to claim 1 wherein the blowing agent is azodicarbonamide.
19. The process according to claim 1 wherein the printable porous layer is composed of adhesively bonded inert particles and wherein the blowing agent is in the resinous inks applied thereto.
20. The process according to claim 1 wherein the printable porous substrate is a glass fiber mat and wherein the blowing agent is in the resinous inks applied thereto.
21. The process according to claim 1 wherein the printed porous substrate is a mechanically foamed resinous plastisol and the blowing agent is included therein.
22. The process according to claim 1 wherein the printed porous substrate is a mechanically foamed resinous plastisol and the blowing agent is in the inks applied thereto.
23. The process according to claim 1 including the application of a clear resinous top coat over the entire design-carrying surface of the printed porous substrate.
24. The product produced by the process of claim 1.
25. The product produced by the process of claim 10.
26. The product produced by the process of claim 19.
27. The product produced by the process of claim 20.
28. The product produced by the process of claim 21.
29. A process as claimed in claim 1, carried out substantially as described with reference to, and as illustrated by, any one or more of the accompanying drawings.
30. A process as claimed in claim 1, carried out substantially as described in any one of the Examples.
31. The product of the process of claim 29 or claim 30.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7930034A GB2057362B (en) | 1979-08-30 | 1979-08-30 | Multi-level embossed cellular surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7930034A GB2057362B (en) | 1979-08-30 | 1979-08-30 | Multi-level embossed cellular surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2057362A true GB2057362A (en) | 1981-04-01 |
| GB2057362B GB2057362B (en) | 1983-06-08 |
Family
ID=10507490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7930034A Expired GB2057362B (en) | 1979-08-30 | 1979-08-30 | Multi-level embossed cellular surface |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2057362B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0449012A1 (en) * | 1990-03-09 | 1991-10-02 | Dai Nippon Insatsu Kabushiki Kaisha | Decorative sheets and processes for producing them |
-
1979
- 1979-08-30 GB GB7930034A patent/GB2057362B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0449012A1 (en) * | 1990-03-09 | 1991-10-02 | Dai Nippon Insatsu Kabushiki Kaisha | Decorative sheets and processes for producing them |
| US5246785A (en) * | 1990-03-09 | 1993-09-21 | Dai Nippon Insatsu Kabushiki Kaisha | Decorative sheets and processes for producing them |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2057362B (en) | 1983-06-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |