DE2923608A1 - ABRASION-RESISTANT DECORATIVE LAYER AND METHOD FOR THE PRODUCTION THEREOF - Google Patents

Description

DR. BERG DIPL.-IWa. SIaPF DIPL.-ING. SCHWABE DR. DR. SANDMAiR

PATENT LAWYERS P.O. Box 860245-8000 Munich 86 German Berg Dipi.-lng. SUpf and Partner, P.O.Box S6024S, MXX) Munich S6 ' Your sign under sign MaueriürcherstraBe Yourref. Ourref. 30 117 lOOOMÜNCHEN «) ll June 1979

Lawyer file number: 30 117

NEVAMAR CORPORATION 0 d e η t ο n, Maryland 21113 / USA

Abrasion-resistant decorative laminate and its method of manufacture

X / R - 12. -

r (019) 918272 Tdefnmme: UdQUZl / 0563 Bank accounts: Hyi »-Bank Munich 4410122850

»« 8273 BERGSTAPFPATENT Munich (BLZ 70020011) Swift Code: HYPO DE MM

** 8274 TELEX: Bayer Vereinsbank Munich 453100 (BLZ 70020270)

»* 3310 0524560BERGd Postscheck Munich 65343-808 (BLZ 70010080)

K-27 / K-27.1

292360ή

The present invention relates to decorative laminate materials with high abrasion resistance.

High pressure decorative panels are usually made by that one has a variety of layers of paper impregnated with various synthetic thermosetting resins stacked on top of one another and cured with the application of heat and pressure. Over a variety of core arches or Inner layers are covered by a printed decoration sheet, over which in the laminate a top layer or an overlay sheet lies is provided, which is almost transparent and creates a protection for the printed sheet.

Abrasion resistance is an important property of laminates. A standard test (NEMA LD 3.01) calls for laminates of type I, that in the laminate according to ^one IOO abrasion cycles not his pattern is destroyed more than 50%. The 50% end point is determined by taking the mean value from the number of cycles in which the pattern shows incipient wear and the number of cycles in which the pattern is completely destroyed.

When a letterpress decoration board is printed in the usual way with a normally 35-40 # resin content in the printed Sheet produced, but without a support sheet

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ORIGINAL INSPECTED

the abrasion resistance is only about 50 to 75 cycles. When specially formulated melamine resins are used in the printed sheet with a resin content of 50 to 55 % , up to about 150 to 200 cycles are occasionally obtained without an overlay sheet, but in this case the laminates tend, and are, to develop surface cracks difficult to manufacture because it is difficult to impregnate the printed sheet uniformly; in addition, they do not meet the minimum requirement of the NEMA standard test of 400 cycles.

Regardless of this, it is desirable to produce a laminate without an overlay sheet that is capable of the To achieve usefulness properties of a laminate using an overlaid layer, and in particular has an abrasion resistance of 400 cycles. In addition, it is desirable to create a laminate, which has an initial wear point of 175 to 200 cycles.

It is desirable to provide these properties without the use of an overlay sheet for the following reasons: (1) The support sheet causes additional costs in the production of the laminate due to the necessary, considerable raw materials, and the losses of raw materials

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materials in the process of its application and handling.

(2) By placing an intermediate layer in the form of the support sheet of substantial thickness between the printed sheet and the eyes of the beholder, the desired visual clarity of the pattern in significant Way impaired.

(3) The edition sheet makes a significant contribution the scrap rate of the laminated products produced. The impregnated, dry support sheet tends to attract small particles of dirt as it is during the drying process static electricity charges developed. This dirt is difficult to detect before lamination and remove, resulting in spoiled laminate panels that cannot be refurbished. In addition, the impregnated, dried layer overlaid in the form of the support sheet is brittle and difficult to handle without breaking. Broken pieces are randomly caught by the support sheet and also lead to visually defective decorative panels .

In addition, laminates that contain an overlay sheet, and particularly those with a relatively high one, show Surface gloss, a tendency to become cloudy very quickly,

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if they are subjected to even moderate abrasion. Understandably, this is uncomfortable where it is shiny Laminates are desired.

It is known that small, hard mineral particles are contained in a sheet of overlay paper or in resin mixtures for impregnation of the patterned printing sheet are dispersed, increase the abrasion resistance of high pressure laminates can. Techniques like these do not eliminate the overlay sheet, but they either increase abrasion resistance, or create an alternating shape of the overlay sheet and accompanying resin.

In an earlier development, a single, ultra-thin coating was applied over the printed sheet, the one Mixture of binder and abrasion-resistant particles contained. Although the laminates made in this way all far superior to earlier attempts, it has now been found that a smaller number of samples, e.g. heavily colored patterns, required to achieve a good initial abrasion, the only ultra-thin Create layer in undesirably high thicknesses, i.e. in thicknesses of up to 8! To 12 lbs / ream (3 »63 to 5» ^ 5 kg / ream) or even up to 16 lbs / ream (7.26 kg / ream).

030021 / OB63 ' ^{/ 6} "

ORIGINAL INSPECTED

Such heavier coatings, but still ultra-thin compared to the prior art, provide superior initial abrasion and superior sliding can test values ₃ are difficult to handle because tools used to cut such laminates pass through quickly the existing amounts of clay become dull.

It was therefore the object of the present invention to provide an improved decorative laminate; a decorative laminate to create, which does not contain a edition sheet, but which nevertheless meets the requirements of Meets NEMA Abrasion Standard tests and also has an initial abrasion point of at least 175 to 200 cycles in the same test delivers; to provide a method by which the printed pattern sheet using the conventional Impregnating and drying devices, as they are generally used in the laminating sector, impregnated will; to provide a method of making laminates that has a significant cost reduction which entails cost and results in a product with an improved appearance that has the potential for an earlier owns unachievable, novel graphic development; and the amount of abrasion resistant material needed to achieve superior abrasion resistance is necessary to

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2323603

without causing excessive tool wear when cutting the product.

These and other objects of the present invention are achieved by using a conventional printed pattern paper sheet first with an ultra-thin coating of a suitable binder and then with an ultra-thin coating that Contains small mineral particles, which have preferably been immobilized by the same binder, coats, and such a printed sheet then normally with a suitable thermosetting resin such as Melamine resin impregnated, and then the printed sheet used for the production of decorative laminates without an overlay sheet. The abrasion-resistant particles are used in smaller quantities and they are more concentrated on the uppermost surfaces of the laminates, compared to an earlier development which gave equivalent wear resistance.

The foregoing and other objects and the nature and advantages of the present invention will be better understood the following detailed description of the preferred embodiments together with the drawings which are not to scale.

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FIGS. 1 to 3 are schematic sectional views of FIG Laminates according to the state of the art.

Figure 4 is a laminate in accordance with embodiments of the parent applications.

Fig. 5 is a flow diagram illustrating a method of making a printed layer in accordance with the present invention Invention shows.

Fig. 6 is a schematic sectional view, not to scale, showing one embodiment of the printed sheet according to the present invention.

Fig. 7 is a schematic, not-to-scale sectional view. which shows a laminate according to the present invention.

The surface of paper, except when pressed against a very smooth surface with high pressure, is pretty rough. When paper is printed on, some of the ink sinks into its top surface and some of it sinks it protrudes beyond this, making the top surface even more irregular. This is the property of Printing paper, in particular some strongly colored patterns have particularly rough surfaces. If according to an earlier Development of the state of the art on which an ultra-thin, abrasion-resistant coating is to be applied the valleys between the knolls where the printing takes place only

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partially filled, with the result that the abrasion-resistant coating on such crests thinner and the surface is somewhat irregular, as this is shown schematically in Fig. h. The tendency of the coating to level out and create a thinner layer over these knobs is particularly evident when the printing inks are made of hydrophobic thermoplastics.

Various solutions have been proposed to overcome this problem.

(1) The provision of a second ultra-thin make coat over the main ultra-thin binder / abrasion resistant particle layer to increase the amount of Melamine resin on the surface of the laminate; and

(2) the provision of such a second ultra-thin make coat underneath the ultra-thin, abrasion-resistant Main layer.

Although both options produce improved results, the second alternative is by far the most superior Results. Therefore, according to the invention, an ultra-thin paper is first applied to the printed or patterned paper Coating of binder, preferably microcrystalline cellulose, with an average thickness of about 0.05

030021/0563 " ^{/ 10} "

applied to 0.3 mils (1.27 to 7.62 microns) (dry), i.e. applied at a rate of about 1/2 to 3 pounds per ream (0.227 to 1.362 kg / ream). This coating showing the inclination, the upper surface of the printed sheet level and also to cover the crests sufficiently to provide a better anchoring base for the abrasion-resistant Layer to form as the ink domes do is then dried. The ultra-thin, abrasion-resistant cover is then applied at a much lower rate without being wasted in the valleys as compared to the embodiments of the earlier development, e.g. abrasion resistant layer is applied at a rate of only 1 to 6 pounds per ream (0.454 to 2.724 kg / ream) a dry top layer 0.02 to 0.2 rails (0.508 to 5.08 microns) thick [usually less than 0.15 mils (3.81 microns) thick] over the first layer that will serve as the substrate.

When the abrasion-resistant preparation containing small mineral particles is applied as a coating without resin on a non-impregnated Printed pattern paper sheet containing an undercoat thereon applied as a layer makes them it is possible that such a paper for the production of decorative laminate materials or decorative panels can be used without a support sheet, whereby

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the laminates obtained are highly abrasion-resistant and only .small amounts of mineral particles can be used without undue wear and tear on the highly colored product caused by the cutting tools.

In its preferred embodiment, there is the coating preparation from a mixture of small particles of alumina or other abrasion-resistant particles with an average Particle size from 20 to 50 microns, and a smaller amount of particles of microcrystalline cellulose, both of which are dispersed in a stable, aqueous slurry are. The small clay particles, which do not interfere with the visual effects in the end product, serve as an abrasion resistant material, and the microcrystalline cellulose particles serve as preferred, temporary ones Binder. Of course, the binder must be combined with the resin system used later in the lamination process, usually a melamine or polyester resin, and the microcrystalline cellulose serves both this function, as well as the stabilization of the small alumina particles on the surface of the printed sheet.

The underlayer is also formed from a temporary binder that has the same properties as the binder the abrasion-resistant layer and preferably the same

_ / ι ο _ 030021/0563

before binders, particularly preferably microcrystalline cellulose is.

Referring to Figure 5, in the preferred operating method conventional non-impregnated printed paper first with the binder material at a rate of about 1/2 to 3 (0.28 to 1.36), preferably about 1.5 to 2.5 lbs / ream (0.68 to 1.14 kg / ream) coated and the Coating leveled and dried. As can be seen schematically in Fig. 6, the binder layer tends to the To level the surface and to fill in the holes, e.g. between the ink dots, including a Coating is created over it; while the average thickness of the make coat up to 0.3 mil (7 * 62 microns) therefore their thickness over the crests will always be much smaller, usually less than 0.1 mil (2.54 microns). The dried layer is then covered with the mixture of the hard mineral particles and binder coated, usually at a rate of about 1 to 6 lbs. per ream (0.45 to 2.72 kg / ream), and the coating at an elevated temperature of at least 140 ° F (60.0 ° C), and preferably 180 ° F (82.22 ° C), such as in a hot air oven, dried to form a thin overlying layer only 0.02-0.2 mils (0.508 up to 508 microns) thick, usually less than 0.15 mils

030021/0563

(3j81 microns) thick.

The resulting abrasion-resistant, coated paper (Fig. 6) is then impregnated with the melamine or polyester resin and dried in a conventional manner, after which it is ready for the lamination process. Based on the comparative weights of the printed sheet and the microcrystalline sheet Cellulose in the ultra-thin coatings on it, and the total amount of melamine resin used as the impregnation in it is calculated to use only 2 to 13 parts of microcrystalline cellulose per 100 parts of resin became.

It is surprising that the coatings that cover the entire Form an ultra-thin layer (consisting of two layers), tightly fitting to the surface of the printed sheet of paper adhere when the paper is later impregnated with melamine resin without significant amounts of the mineral particles either get lost in the impregnation solution or migrate away from the surface of the paper. Another surprising one The property of these coatings is that they prevent the melamine-formaldehyde resin solution from penetrating does not seem to obstruct the inside of the paper; such penetration is essential, or it would be the printed Sheet irregular and insufficient, for example in its

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030021/0563

in the middle, and could possibly be after pressing split.

Referring to Fig. 7, it will be seen that the abrasion-resistant resin impregnated printed sheet bearing an ultra-thin abrasion-resistant coating on its upper surface is conventionally composed for the lamination step except that no overlay sheet is used. The laminate is then cured in a conventional manner with the action of heat and pressure. A surprising property of the ultra-thin coating is that, although its overall thickness (both layers) is so low, it can provide an abrasion resistance in the finished laminate that not only ^{approaches the 1} JOO cycles of the NEMA standard, but also an initial abrasion point of over 175 to 200 cycles.

Another desirable property of the coatings is that that they do not scatter or attenuate light significantly, resulting in a very clear, contoured appearance of the patterns in the finished laminate leads. Also exists because of the extremely ultra-thin nature of the mineral particles containing them Layer no tool wear problem during subsequent machining of the resulting laminates.

030021/0563 " ^{/ 15} "

Without being bound by the following theory, it is believed that the improved properties of the invention can be explained as follows. Particles of microcrystalline cellulose have very strong external forces, which bind other polar substances such as cellulose and clay. Hence it is an aqueous slurry stable from microcrystalline cellulose and clay and does not settle very quickly. When this slurry is used as a Layer is applied to the paper or the sub-ultra-thin binder layer, binds the microcrystalline cellulose apparently the alumina particles to the surface of the paper fibers or to the binder sub-layer, whereby migration of the alumina particles in the direction below the surface is prevented. All, or essentially all clay particles remain on the surface, where they work best, rather than underneath of the surface where they would add relatively little to initial abrasion resistance.

There must be a sufficient amount of small mineral particles to produce the final product with the above discussed, create the desired abrasion resistance, and there must be a sufficient amount of binder present to retain the mineral particles in place on the surface of the ultra-thin sublayer. It was very general

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found that satisfactory results are obtained with about 5 to 10 parts by weight of microcrystalline cellulose to about 20 to 120 parts by weight of clay; it is possible to work outside this range, but there is no benefit and moreover the handling problems become complicated. The amount of water in the slurry is also dictated by practical considerations, since too little water makes the slurry so thick that it is difficult to apply; similarly, too much water makes the slurry so thin that it is difficult to maintain a tolerable thickness during the coating operation. A slurry that contains about 2.5 percent by weight of microcrystalline cellulose and about 28 percent by weight of alumina, based on the water, is stable, ie the alumina does not settle out; however, if greater than 3.5 weight percent microcrystalline cellulose and about 28 weight percent alumina based on the water are used, the slurry becomes highly thixotropic and difficult to apply. A preferred slurry contains about 3/2 % microcrystalline cellulose and about 9 % clay.

The preparation preferably also contains a small amount of wetting agent, preferably a non-ionic wetting agent, a small amount of an additional suspending vehicle such as carboxymethyl cellulose and a small amount of silane. the

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£ 2823808 ΊΑ

The amount of wetting agent is not critical, but only a very small amount is desirable and excess amounts are of no benefit. If an additional suspending binder, such as carboxymethyl cellulose ₃ , is used to help maintain the mineral particles in suspension, it can be used in amounts up to about 50 percent by weight of the amount of microcrystalline cellulose.

When a silane is used, it acts as a coupling agent that chemically bonds the clay or other inorganic particles to the melamine matrix after impregnation and curing, and this creates better initial wear because the clay particles are still mechanically bonded to the melamine are chemically bound to it and therefore remain in place for longer with abrasion. The silane should be selected from those silanes that are compatible with the particular thermosetting laminating resin employed; "For this, silanes with an amino group such as aminopropyltrimethoxysilane or γ-aminopropyltriethoxysilane are particularly effective for use with melamine resins. The amount of silane used need not be large and in fact an amount is as low as 0.5 % based on the weight of the Alumina, effective in increasing the abrasion resistance of the finished laminate; es

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ORIGINAL INSPECTED

a maximum amount of about 2 percent by weight, based on the weight of the clay or other hard part- ' Chen suggested that larger amounts in no way lead to any significantly better results and only increase the cost of raw materials.

It is an important feature of the present invention that the coating using microcrystalline Cellulose as a binder must be dried at an elevated temperature before the printed sheet with the Melamine resin is impregnated. A minimum drying temperature is around 140 ° F (60.0 ° C) fabric temperature, and the preferred drying temperatures are in the range of 160 ° to 180 ° P (71.1 ° to 82.2 ° C) fabric temperature, or above.

With regard to the abrasion-resistant mineral particles, clay is preferred as the material. Silica, which is considered to be wear-resistant Material is known gives considerably poorer results in the present invention compared to alumina, however, it can be used. Other minerals of sufficient hardness, such as zirconium dioxide, cerium oxide, Diamond dust, etc., can work, but are either too expensive or too expensive to use deliver excessive parboiling under certain circumstances

030021/0583 " ^{/ ± 9} "

$ 232390

Shift. Glass beads have been found to be unsuccessful in investigations. Silicon carbide was also used tried but provided excessive color shift although it gave good rub resistance. Mixtures of silica and alumina gave good results.

An important characteristic is the particle size of the mineral. Below 20 microns particle size will be the abrasion resistance poor and the preferred minimum average particle size is about 25 microns. The maximum average Particle size is due to the surface roughness in the object, which disturbs the visual effects influenced, limited. The preferred maximum average size of the abrasion resistant particles is about 50 microns.

The nature of the binder for the mineral particles is a very important feature of the present invention. From all materials tried, microcrystalline cellulose is by far the most satisfactory material. The binder does not have to be solely to maintain the mineral particles in their position on the surface of the sublayer serve the printed sheet, but should also act as a suspending agent in the slurry. The special one The property of microcrystalline cellulose is that it is like a typical suspending agent and

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bildner works, but unlike other agents, it is not water-soluble before or after the suspension and forms a highly porous film through which the thermosetting resin can penetrate. In addition, the binder must be compatible with the laminating resin. In addition, may it neither scatter nor attenuate light in the applied thickness dimensions in the finished laminate.

Other binders that can be used, however give poorer results compared to microcrystalline cellulose, are various typical suspension binders, which anionic acrylic polymers, carboxymethyl cellulose and similar materials such as hydroxypropyl cellulose, Methyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, etc. include. These materials create something better results when mixed with alpha cellulose flakes. However, as indicated above, it is microcrystalline Cellulose is the preferred binder.

Microcrystalline cellulose is a non-fibrous form of purified alpha cellulose in which the cell walls of the Cellulose fibers into fragments ranging in length from a few microns to a few tenths of a micron have been broken into. AVICEL microcrystalline cellulose of type RC 58I is a white, odorless, hygroscopic

030021/0563 " ^{/ 21} "

DP

Powder that is dispersible in water and contains about 11 percent by weight of sodium carboxymethyl cellulose as a protective colloid. Its particle size is less than 0.1 % on a 60 mesh (0.25 mm) screen.

The ultra-thin backsheet is very similar to the ultra-thin, abrasion-resistant top layer, except that it is preferably does not contain abrasion resistant particles. An aqueous slurry that is about 3 to 6 percent by weight microcrystalline Containing cellulose can be satisfactorily formed as a layer over the printed layer a substrate for the ultra-thin, abrasion-resistant layer can be applied. A small amount of wetting agent can be used will.

Those features and advantages of the present invention that are believed to be particularly significant are concern the following:

(1) The mixture aer mineral particles and the microcrystalline cellulose is preferably deposited from a slurry Wasserauf than that they are used as fillers in a resin solution.

(2) Such a slurry is preferably applied as a layer on a non-impregnated printed pattern sheet applied than on an impregnated patterned cover sheet.

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ORIGINAL INSPECTED

(3) The layer is at an elevated temperature of

dried at least 140 ° F (60.0 ° C). ■ (4) The total average layer thickness of both Layer is only 0.07 to 0.5 mils (1.78 to 12.7 microns) with the top abrasion resistant layer being preferred has a maximum layer thickness of 0.2 mils (5.08 microns) rather than an overlay 1 to 2 mils (25.4 to 50.8 microns) thick.

(5) After the layers are applied and dried, the patterned cover sheet is covered with the thermosetting resin preferably impregnated rather than special, difficult using conventional means coating to be controlled with a thick slurry.

(6) The ultra-thin top layer unexpectedly creates high abrasion resistance.

The desirable properties of the binder, all of which are met by the microcrystalline cellulose, are: It acts as a film former; it acts as a binder for mineral particles; it acts as a mineral particle suspending agent in the slurry; it becomes thermosetting during the subsequent process of impregnation Resin not washed out; it is compatible with and permeable to the subsequently applied thermosetting resin;

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ORIGINAL INSPECTED

it is resistant to heat generated during the lamination process; and it scatters or weakens the light in does not affect the laminate. The following examples serve to further illustrate the invention.

Example 1

A — surface coating

An aqueous slurry of Avicel and alumina was applied to an ultra-thin layer at a coating weight as shown in Table I, applied to printed sheets with a highly colored pattern. After drying was an Avicel layer of 2 lbs / ream (0.91 kg / ream) (dry) applied in an ultra-thin layer over the ultra-thin, abrasion-resistant layer and the surface layer dried; the layers were then impregnated with melamine resin, it was ensured that the surface layer had an increased melamine occupancy and the so prepared printed sheets were used to form laminates without any overlay sheet.

B — lower class

The procedure of Example 1-A was repeated with the Except that the 2 lbs / ream (0.91 kg / ream) (dry) ultra-thin Avicel layer is applied directly to the top surface of the printed sheet applied to effect a leveling

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and the ultra-thin, abrasion-resistant layer was applied over the dried Avicel layer, the entire abrasion resistant layer was placed over the swatches where it gave the most benefit and with nothing in the valleys was wasted.

As a comparative example, a laminate was produced which only used the ultra-thin, abrasion-resistant layer. The results are set out in Tables I and II below.

Table I.

Initial wear resistance

Strong dry coating A

Colored weight of the clay of individual surfaces - B

Master containing layer overlay overlay underlayer

(Number) (lbs / ream) (kg / ream) (cycles) (cycles) (cycles)

100 300

"500+

50 400

500+

AN-1-1 6th , 6 (2.72) AN-1-1 5 (2.54) W-8-104 5 , 6 (2.27) W-8-104 5 (2.54)

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Table II

"Sliding Can" test

Dry coating A

weight of alumina of individual surface B

Mister containing layer overlay overlay undercoat (I & unmer) (lbs / ream) (kg / ream) (cycles) (cycles) (cycles)

4,627 6 057

HO 271+

6 500 25 433

40 825+

AN-1-1 6th , 6 (2.72) AN-1-1 5 , 0 (2.54) W-8-104 5 , 5 (2.27) W-8-104 4th (2.04)

From the tables above it can be seen that the base coat is more effective, although the surface coating improves abrasion.

Example 2

A sample of a production trial of base coated paper was made on a slot applicator. The formulations were as follows:

• Lower layer

Water 300 lbs. (136.2 kg)

Avicel RC 581 10 lbs. (4.54 kg)

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ORIGINAL INSPECTED

'rf' 292360a

Abrasion-proof loading

Water 300 lbs. (136.2 kg)

Avicel RC 581 11.2 lbs. (5.09 kg)

CMC 7L 1.4 lbs. (0.64 kg)

Alumina with an average diameter of 30 microns. 30.0 lbs. (13.62 kg)

Silane A-ILOO 0.7 lbs. (0.32 kg)

A heavily printed wood grain swatch, W-8-104, was undercoated with 1.4 lbs / ream (0.64 kg / paes) of Avicel and dried. This was followed by a 4.2 lbs / ream abrasion resistant coating which was also dried. The double-coated paper was treated with melamine-formaldehyde resin to a resin content of 42 to 44 % and a volatile matter content of 5 to 6 %. Laminates with no overlay sheet were pressed using this printed sheet. The initial abrasion of the laminate made from this paper was 510 cycles. The "sliding can" test resulted in over 40,000 strokes. For comparison (see Table I above) had individually coated laminates that only had the ultra-thin, abrasion-resistant layer on the same heavily coated printed sheet, W-8-104, at a rate of 5 lbs / ream (2.27 kg / Ries) contained an initial wear of only 50 cycles.

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Ö30021 / 0563

Sheets of W-8-104 0.050 "(1.27 mm) thick were glued to 3/4" (1.91 cm) piece of cardboard with polyvinyl alcohol glue. A laminate with a single coating, as tested in Table I at 6 lbs / ream (2.72 kg / ream), was rated for "workability" with the double coating at 4.2 lbs / ream (1.91 kg / ream). Ream) compared to about 1.4 lbs / ream (0.64 kg / ream) of the base coating. The single coat formulation contained 86.7 % alumina; therefore it contained 6 lbs / ream (2.72 kg / ream) χ 0.867 = 5 _S 2 lbs / ream (2.36 kg / ream) of clay. The double coating contained 69.2% alumina or 4.2 lbs / ream (1.91 kg / ream) χ 0.692 = 2.9 lbs / ream (1.32 kg / ream) alumina.

Both laminate sheets were made using flat carbide knives processed. The double coating at a little more than 1/2 the weight of the alumina was more than ten times that of the initial abrasion and about 1/10 tool wear.

The present invention provides highly improved results, making it a revolutionary development can be considered in the field of decorative laminate materials as they are a laminate without an overlay sheet manages both the NEMA Abrasion Resistance Standard of at least 400 cycles and one in the same test

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initial wear point of at least 175 to 200 cycles.

It will be readily apparent to one skilled in the art to which the present invention pertains numerous changes of the subject matter described above are possible without departing from the scope of the present invention, and that the invention is not limited to what is shown in the drawings and what is in the description is laid down. It goes without saying that there will be certain additional variations in processing in some Cases will give slightly different results. For example, it usually leads to better results when the laminates of the present invention are molded against a hard surface.

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Claims (34)

DR. BERG DTPL -ING. 3TAPF DIPL.-ING. SCHWABE DR.PR HANDMAlR PATENTANWÄLTE Postfach 860245-8000 Munich 86 *? 3? ^ ft pl & 5? 4 *? y u Dr. ler »Dipl.-Ini. SUpf and Pirtaer, P.O.Box t6 02 45, MOO Munich U Your reference Our reference ^ Q 117 MauerkircherstraBe 45 Yourref. Ourref. 8000 MUNICH 80 Attorney's file no .: 30 117 NEVAMAR CORPORATION patent claims 1. Process for the production of an abrasion-resistant decorative laminate of at least one sub-layer and a decorative trim sheet impregnated with a thermosetting resin, wherein the laminate has increased abrasion resistance without an overlay layer, by coating a decorative trim sheet with an ultra-thin, wet layer of a mixture of (1) an abrasion-resistant, hard mineral with a particle size of 20 to 50 microns and in one to create an abrasion-resistant layer without disturbing influences sufficient amount of clarity, and (2) a binding material for the mineral, X / R β S Q Ö 2 1/0 S 6 3 f (089) 988272 Telefnmme: ww * -i / uwvy ^ Bank accounts: Hypo-Bank Munich 4410122850 988273 BERGSTAPFPATENT Munich (BLZ 70020011) Swift Code: HYPO DE MM 988274 TELEX: Bayer Vereinsbank Munich 453100 (BLZ 70020270) 3310 05 24 560 BERG d Postscheck Munich 653 43-808 (bank code 700 100 80) K-27 / K-27.I 2923808 wherein the binder material has the properties, to withstand subsequent lamination conditions, compatible with the thermosetting resin and after lamination to be substantially transparent along with the resin, the binder material in a sufficient amount is present to bind the abrasion-resistant material to the surface of the decorative trim sheet, the binder / mineral layer is permeable to the thermosetting resin when dry, Drying the mixture on the facing sheet at a temperature sufficient to bond the abrasion-resistant Minerals through the binder to the surface of the decorative trim sheet to create an ultra-thin, dry layer of the mixture on top, Impregnating the coated facing sheet with the thermosetting resin, Arranging the facing sheet impregnated and coated with the resin over the underlayer, Subjecting the assembly to sufficient heat and pressure unification of the underlayer and effecting the trim sheet to create an abrasion resistant decorative laminate thereby characterized in that before the impregnation step, the decorative trim sheet either directly, or the ultra-thin, dry layer of the 03ÖÖ21 / 0563 ~ ³ ' 2923508 Mix with an ultra-thin, wet layer of binder material that has the properties to withstand the subsequent conditions of lamination with the thermosetting resin compatible, permeable to the thermosetting resin in the dry state and together with the resin to be substantially transparent after lamination, coated, and the wet, ultra-thin layer of binder material to create an ultra-thin, dry layer of binder material dries immediately below or above the ultra-thin, dry layer of binder material / mineral mixture. 2. The method according to claim 1, characterized in that the binder is microcrystalline cellulose and the thermosetting resin, melamine-formaldehyde resin and the mixture is dried at a temperature of at least about 140 ° P (60.0 ° C). 3. The method according to claim 2, characterized in that that the abrasion-resistant mineral is clay, silica, or a mixture thereof. 4. The method according to claim 3> characterized in that the layer of binder material is applied directly to the surface of the decorative trim sheet 030021 / 0B63 2923805 and the layer of binder material / mineral mixture is then applied over it. 5. "The method according to claim 4, characterized in that it is marked Ichnet that the binder material / mineral mixture 5 to 10 parts by weight of microcrystalline cellulose to about 20 to 120 parts by weight of clay, along with sufficient water to facilitate the coating process contains, wherein the coating of the mixture is carried out in such a way that after drying an ultra-thin coating having a thickness in the range of 0.02 to about 0.2 mils (0.508 to about 5.08 microns) is ensured, and the Coating of the binder material is carried out so that after drying-an ultra-thin layer with a average thickness of 0.05 to 0.3 mils (1.27 to 7.62 microns) is ensured. 6. The method according to claim 4, characterized in that the binder material / mineral mixture also up to 50 percent by weight, based on the binder material, an additional suspending binder and a small amount of a nonionic surfactant. 7. The method according to claim 4, characterized in that the binder material / mineral mixture 030021/0563 also a silane compatible with the thermosetting resin in an amount sufficient to chemically bond the abrasion-resistant material to the thermosetting resin. 8. The method according to claim 4, characterized in that the drying at a temperature is performed in the range of 240 ° to 270 ° F (115.6 ° to 132.2 ° C). 9. Process for the production of an abrasion-resistant high-pressure decorative laminate according to claim 4, characterized in that the lower layer comprises a plurality of kraft paper sheets impregnated with phenolic resin, and the thermosetting resin contains melamine-formaldehyde resin, and the arrangement for achieving a union of a temperature of about 230 ° to 340 ° F (110.0 ° to 171.1 ° C) and subjected to a pressure of 800 to 1600 psi (56 to 112 kg / cm). 10. The method according to claim 9, characterized in that that the binder material / mineral mixture to create a dry, ultra-thin Layer about 0.02 to 0.15 mils (0.508 to 3.81 microns) thick is applied. 030021/0563 ⁶ 29239Q9 11. The method according to claim 10, characterized in that the binder material / mineral mixture further contains 0.5 to about 2 percent by weight, based on the weight of the clay, of an aminosilane. 12. Process for the production of an abrasion-resistant low-pressure decorative laminate according to claim 1, characterized in that the thermosetting Resin is selected from the group consisting of melamine formaldehyde resin and polyester resin, the layer is made of Binder material directly onto the surface of the decorative trim sheet and the layer of binder / mineral mixture is then applied over it. 13. The method according to claim 12, characterized in that that the underlayer contains a wood particle board, the thermosetting resin melamine-formaldehyde resin lamination at a temperature in the range of about 325 ° to 350 ° P (162.8 ° to 176.7 ° C) and a pressure of about 175 to 225 psi (12.25 to 15.75 kg / cm) and wherein the abrasion resistant mineral, alumina, Silica or a mixture thereof and the binder is microcrystalline cellulose, the microcrystalline Cellulose in the mixture in an amount ranging from about 5 to about 10 parts by weight per about. 20. to 120 weight stones 03ÖÖ21 / 0563 len of the mineral is present and the mixture to create of a dried coating of 0.02 to 0.15 mils (0.508 up to 3.81 microns) thick, drying at a fabric temperature of at least 140 ° P (60.0 ° C) is carried out. 14. The method according to claim 13, characterized in that the mixture is further 0.5 to Contains 2 percent by weight, based on the weight of the clay, of an aminosilane. 15.Printed sheet for use in making decorative laminates with high abrasion resistance, including a paper sheet substrate with one thereon Print pattern, and an ultra-thin, abrasion-resistant coating applied over the print pattern, the ultra-thin, abrasion-resistant coating a mixture of (1) an abrasion-resistant, hard mineral with a particle size of 20 to 50 microns and in one to create a sufficient amount of an abrasion-resistant layer without interfering with the clarity, and (2) a binding material for the mineral, contains that with one of the group consisting of melamine-formaldehyde resin and polyester resin selected thermosetting resin is compatible, the coating being impregnable, 030021/0563 the laminating resin together with the resin after curing is essentially transparent and the binder material in is present in an amount sufficient to bind the abrasion-resistant mineral to the surface of the paper sheet and to stabilize, characterized in that an ultra-thin layer of binder material either directly above the surface of the printed sheet and deeper than the ultra-thin, abrasion-resistant coating, or placed over the abrasion-resistant cover. 16. Printed sheet according to claim 15 »thereby characterized in that the ultra-thin layer of binder material is directly over the surface of the printed And deeper than the ultra-thin, abrasion-resistant cover. 17. Printed sheet according to claim 16, characterized characterized in that it is coated with a thermosetting laminating resin selected from the group consisting of Polyester resin and melamine-formaldehyde resin, impregnated is. 18. Printed sheet according to claim 16, characterized in that the binder material Contains microcrystalline cellulose. 030021/0563 ORIGINAL INSPECTED 19. Printed sheet according to claim 16, characterized in that the abrasion-resistant material Alumina, silica, or mixtures thereof. 20. Printed sheet according to claim 16, characterized in that it is impregnated with melamine resin wherein the abrasion resistant mineral is clay, silica, or mixtures thereof, and the binder material contains microcrystalline cellulose, the ultra-thin, abrasion-resistant coating is 0.02 to 0.15 mils (.508 to 3.8l microns) and 5 to 11 parts by weight of the microcrystalline cellulose to about 20 to 120 parts by weight of the mineral, and the ultra-thin layer of binder material an average thickness of 0.05 to 0.3 mils (1.27 to 7.62 microns). 21. A printed sheet according to claim 20, characterized in that the layer further comprises 0.5 to 2.0 percent by weight, based on the weight of the mineral, contains a silane. 22. Printed sheet according to claim 16, characterized in that the binder material contains a mixture of alpha cellulose flakes and glue. 030021/0563 2923609 23. Abrasion-resistant decorative laminate that meets the requirements of the NEMA abrasion resistance standard and which also performed 175 to 200 cycles after the same test initial abrasion met, with one, laminated on an underlayer, with a thermosetting laminating resin impregnated decorative paneling sheet having a print pattern and one arranged over the print pattern, ultra-thin, abrasion-resistant cover, whereby the ultra-thin, abrasion-resistant cover is a mixture of (1) an abrasion-resistant, hard mineral with a particle size of 20 to 50 microns and in one to create a sufficient amount of an abrasion-resistant layer without interfering with the clarity, and (2) a stabilizing binder material for the mineral, contains, the binder with the by the printed Sheet through impregnated thermosetting resin is compatible and does not affect the clarity, and with the ultra-thin, abrasion-resistant coating on or near the surface of the laminate, characterized in that, that an ultra-thin layer of binder material impregnated with the thermosetting resin either directly above the printed pattern surface of the decoratxons cladding sheet below the ultra-thin, abrasion-resistant coating, or is arranged over the abrasion-resistant coating. 030021/0663 Ή 2923908 24. Abrasion-resistant decorative laminate according to claim 23, characterized in that the ultra-thin layer of binder material lies directly over the surface of the printed sheet, the ultra-thin,
abrasion-resistant coating the top layer of the laminate
forms. 25. Abrasion-resistant decorative laminate according to claim 24, characterized in that the thermosetting resin is melamine-formaldehyde resin. 26. Abrasion-resistant decorative laminate according to claim 25, characterized in that the binder material Contains microcrystalline cellulose. 27. Abrasion-resistant decorative laminate according to claim 26, characterized in that the abrasion-resistant Mineral particles consist of clay, silica, or mixtures thereof. 28. Abrasion-resistant decorative laminate according to claim 24, characterized in that the ultra-thin, abrasion resistant coating 0.02 to 0.15 mils (0.508 to 3.81 microns) thick and the ultra-thin make coat has an average thickness in the range of 0.05 to 0.3 mils (1.27 to 7.62 microns). 030021/0563 ORIGINAL INSPECTED / 13L 2923508 29. High pressure decorative laminate according to claim 24, characterized in that the lower layer • a plurality of impregnated with phenolic resin Sheets of paper and the facing sheet contains a sheet of paper impregnated with melamine resin, the abrasion-resistant Particles contain alumina particles, the binder material contains microcrystalline cellulose, the abrasion-resistant Coating contains about 5 to 10 parts by weight of microcrystalline cellulose to about 20 to 120 parts by weight of clay, and the thickness of the abrasion resistant layer is about 0.02 to 0.2 mils (0.508 to 5.08 microns). 30. High pressure decorative laminate according to claim 29, characterized in that the clay is bonded to the melamine resin with a silane. 31. Abrasion-resistant decorative laminate according to claim 25, characterized in that the abrasion-resistant mineral is clay and the clay is attached to the melamine resin is chemically bonded with a silane. 32. Abrasion-resistant decorative laminate according to claim 23, characterized in that the abrasion-resistant coating contains an amount of binder material which is not greater by weight than the weight of the mineral particles. 030021/0563 33 ♦ Abrasion-resistant decorative laminate according to claim 23, characterized in that the binder material is a mixture of alpha cellulose flakes and Contains glue. 34. Printed sheet according to claim 15, characterized in that the amount of binder material in the abrasion-resistant coating is no greater than the amount by weight of the mineral in the abrasion-resistant coating. 35 Printed sheet for use in the production of decorative laminates with high abrasion resistance, comprising a paper sheet substrate having a print pattern thereon and one applied over the print pattern ultra-thin, abrasion-resistant coating, the ultra-thin, abrasion-resistant coating having a thickness on the order of 0.02 to 0.3 mils (0.508 to 7.62 microns) and a mixture of (1) an abrasion-resistant, hard mineral of small particle size in one to create an abrasion-resistant layer sufficient quantity without interfering with the clarity, and (2) a binding material for the mineral, contains, wherein the binder material is present in an amount sufficient to cover the abrasion resistant mineral 030021/0563 - 2923601 To bind substrate and to stabilize, thereby characterized in that a layer of binder material either directly above the surface of the printed sheet and deeper than the ultra-thin, abrasion-resistant coating, or over the abrasion-resistant cover. 030021/0563