CA1290718C - Decorative panel a core and outermost layer of radiation-polymerized resin - Google Patents
Decorative panel a core and outermost layer of radiation-polymerized resinInfo
- Publication number
- CA1290718C CA1290718C CA 518621 CA518621A CA1290718C CA 1290718 C CA1290718 C CA 1290718C CA 518621 CA518621 CA 518621 CA 518621 A CA518621 A CA 518621A CA 1290718 C CA1290718 C CA 1290718C
- Authority
- CA
- Canada
- Prior art keywords
- layer
- paper
- radiation
- resin
- decorative panel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C5/00—Processes for producing special ornamental bodies
- B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
- B44C5/0469—Ornamental plaques, e.g. decorative panels, decorative veneers comprising a decorative sheet and a core formed by one or more resin impregnated sheets of paper
- B44C5/0476—Ornamental plaques, e.g. decorative panels, decorative veneers comprising a decorative sheet and a core formed by one or more resin impregnated sheets of paper with abrasion resistant properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31859—Next to an aldehyde or ketone condensation product
- Y10T428/31862—Melamine-aldehyde
- Y10T428/31866—Impregnated or coated cellulosic material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
- Y10T428/31906—Ester, halide or nitrile of addition polymer
Abstract
ABSTRACT OF THE DISCLOSURE A decorative panel and method therefor. The decorative panel includes a core layer and layers which are decorated on one or both sides of the core layer. At least the outermost layer of the panel on at least one of the two surfaces of the panel is predominantly composed of a synthetic resin which can be one or more components polymerized by radiation and includes unsaturated acrylates and methacrylates. This layer is scratch-resistant at a scratch loading of at least 1.5 N, preferably 2-7 N (DIN 53,799, part 10) and has a low gloss corresponding to a reflectometer value of not more than 50 at an angle of incidence of 85° (DIN 67,530). The panels are made by a process which comprises applying a layer of a liquid synthetic resin polymerizable by radiation and comprising an unsaturated acrylate or an unsaturated methacrylate, to a substrate; applying a film having a surface roughness over the resin layer; transferring the surface roughness to the resin layer; polymerizing the resin layer by exposure to radiation; and compressing the resin layer and the substrate at an elevated temperature and wherein the resin layer includes decoration means.
Description
~9(~7~2'3 DECORATIVE PANEL HAVING
IMPROVED SURFACE PROPERTIES
BACKCROUND OF THE INVENTION
The invention relates to a decorative panel composed of a core layer and a layer decorated on one or both sides and to a process for its production.
Panels of this type are employed for interior or exterior uses in the building industry, being used as clad~ing panels or self-supporting units, depending on their thickness.
The decorative panels used hitherto are, for example, hi~h pressure decorative la~inates ~ .P.D.L.) (DIr~ 19,926), as they are called. They are composed of a stack of paper webs impregnated with resin and compressed under hot conditions, as the core layer, and of a top layer made of resin-impregnated decorative paper. These panels have the disadvantage that they are attacked by mineral acids, especially at concentrations above 10% and at an exposure time longer than lO minutes. In addition, in the standard embodimentr these panels are not adequately resistant to weathering, since the type of resin used in the top layer is sensitive to hydrolysis.
Panels of this type can, therefore, only be used to a limited extent as work benches ln chemical laboratories or for the production of wet cells which have to be .
~ ~ .
~V7~8 cleaned with acids. If they are used for exterior purposes, addi-tional e~pensive measures are necessary to improve their resis~-ance to the effects of weathering.
I,aminates and panels based on plastics, such as poly-ester or acrylate panels, are, however, particularly sensitive to scratching and are not adequately resistant to organic solvents.
For this reason they are also not very suitable for these applica-tions.
Canadian Patent 1,243,271 relates to a decorative panel which is particularly suitable for exterior uses, for interior construction and for the production of special furniture, and which has a surface which is not sensitive to hydrolysis and is adequately resistant to the effects of weathering, mineral acids and organic solvents, and which also has a high surface hardness.
This is composed of a core layer and a decorative layer on one or both sides. At least the outermost layer of the panel on at least one of the two panel surfaces is composed predominantly of a syn-thetic resin formed from one or more components, polymerized by radiation and selected from the group comprising unsaturated acry-lates and methacrylates~ This layer has a particularly high sur-~ace hardness. It is s-till scratch-resistant at a scratch loading of at least 1.5 N, preferably 2 to 7 N (DIN 53,7~9, part 10). In the process for the production of this panel, a liquid surface layer comprising the components which can be polymerized by radia-tion i~ applied to a substrate and is subsequently polymerized by radiation. The panel surface does not have the desired properties until after a further stage in which the surface layer which has been polymerized by radiation is compressed together with the
IMPROVED SURFACE PROPERTIES
BACKCROUND OF THE INVENTION
The invention relates to a decorative panel composed of a core layer and a layer decorated on one or both sides and to a process for its production.
Panels of this type are employed for interior or exterior uses in the building industry, being used as clad~ing panels or self-supporting units, depending on their thickness.
The decorative panels used hitherto are, for example, hi~h pressure decorative la~inates ~ .P.D.L.) (DIr~ 19,926), as they are called. They are composed of a stack of paper webs impregnated with resin and compressed under hot conditions, as the core layer, and of a top layer made of resin-impregnated decorative paper. These panels have the disadvantage that they are attacked by mineral acids, especially at concentrations above 10% and at an exposure time longer than lO minutes. In addition, in the standard embodimentr these panels are not adequately resistant to weathering, since the type of resin used in the top layer is sensitive to hydrolysis.
Panels of this type can, therefore, only be used to a limited extent as work benches ln chemical laboratories or for the production of wet cells which have to be .
~ ~ .
~V7~8 cleaned with acids. If they are used for exterior purposes, addi-tional e~pensive measures are necessary to improve their resis~-ance to the effects of weathering.
I,aminates and panels based on plastics, such as poly-ester or acrylate panels, are, however, particularly sensitive to scratching and are not adequately resistant to organic solvents.
For this reason they are also not very suitable for these applica-tions.
Canadian Patent 1,243,271 relates to a decorative panel which is particularly suitable for exterior uses, for interior construction and for the production of special furniture, and which has a surface which is not sensitive to hydrolysis and is adequately resistant to the effects of weathering, mineral acids and organic solvents, and which also has a high surface hardness.
This is composed of a core layer and a decorative layer on one or both sides. At least the outermost layer of the panel on at least one of the two panel surfaces is composed predominantly of a syn-thetic resin formed from one or more components, polymerized by radiation and selected from the group comprising unsaturated acry-lates and methacrylates~ This layer has a particularly high sur-~ace hardness. It is s-till scratch-resistant at a scratch loading of at least 1.5 N, preferably 2 to 7 N (DIN 53,7~9, part 10). In the process for the production of this panel, a liquid surface layer comprising the components which can be polymerized by radia-tion i~ applied to a substrate and is subsequently polymerized by radiation. The panel surface does not have the desired properties until after a further stage in which the surface layer which has been polymerized by radiation is compressed together with the
- 2 -~907~8 20731-g48 substrate at an elevatea temperature.
However, this decorative panel has the property, whicn is frequently undesirable, of exhibiting a c0rtain degree of gloss. If texturized separating media are used in the final com-pression under heat, it is admittedly possible to give the panel surface a surface structure which is texturized in conformity with the surface of the separating medium, for example a surface struc-ture similar to orange peel, but its surface gloss is, as before, very high. The addition of known delustering agents, such as silicon dioxide pigments, to the outermost surface layer of the panel also does not, for practical purposes, reduce the gloss, since the pigment-containing surface, which is initially still satin-frosted after the radiation polymerization, unaccountably becomes glossy again as soon as the panel is subsequently subject-ed to compression under heat.
SUMMARY OF THE INVENTION
It is therefore an object of the invention to provide a decorative panel which is resistant to weathering, acids and sol-vents and which has a high surface hardness and only a slight surface gloss.
This object is achieved by a decorative panel which comprises a core layer; an outermost layer applied over the core layer, the outermost layer being a synthetic resin polymerized by radiation and comprising an unsaturated acrylate or an unsaturated methacrylate, and further being scratch-resistant at a scratch loading of at least about 1.5 Newtons, pre~erably from about 2 to almost 7 Newtons, as defined by DIN 53,799 part 10 and having a reflectometer value no greater than about 50 at an ~9()718 angle of incidence of 85 as clefined by DIN 67,530; and decoration means ~or forming a decoration covering th~ core layer.
The object of the invention is also achieved by a process for the production of a decorative panel ~hich comprises applying a layer of a llquid synthetic resin polymerizable by radiation and comprising an unsaturated acrylate or an unsaturated :
methacrylate, to a substrate; applying a film having a surface roughness over the resin layer; transferring the surface roughne s ~ -10 to the resin layer; polymerizing the resin layer by exposure to radiation; and compressing the resin layer and the substrate at an elevated temperature and wherein the resin layer~includes decoratlon means.
The object of the invention is further achieved by a process for the production of a decorative~pan~el~which comp~rises applying a first layer containing decorat~ion;means to;~a substrate;
appIying a: second layer over the~lrgt layer, the seoond~layer being a~synthetia~ r~esin polyDerlz~able by radiation and comprls~ing ~ -~
; an unsaturated acrylate or an unsaturated methacrylat~e~, apply~ing~a ~ :
20~ film~having a~surfaae roughness over the second layer; trans-ferring the~surface roughness to thé second layer; polymerizing the~resin~;layer by~exposure to~radiation~;~ and~c~ompressing;the f~irst~and second~layers ~and the~ ubstrate~-at an elevated temperatu~re. ;~
BRIEF;D~SCRIPTION~OF TH~ DRAWIN65 The in~entlon is il~l~ustra~ted~in greater detail~by mean;s of Figs.~ l~to~3a and~the sxampl~ss~below~
)718 2073~-~48 Fig. 1 shows ~he sequence of the process variant described in Example 1, Fig. la shows a partial cross-section through a panel according to Fig. l;
Fig. 2 shows the sequence of the process variant described in Example 2;
4a .
.
~Z~307~
Fig. 3 shows the sequence of the process variant described in Example 3; and Fig. 3a shows a partial cross-section through a panel according to Figs. 2 and 3.
s DETAILED DESCRIPTION OF ~HE PREFERRED EMBODIMENTS
The panel of the invention is a sheet-like unit having a surface shape and surface structure suited to the intended use and which can, for example, also have a bent shape~ Within the scope of the invention, a panel is also to be understood as sheeting.
In the measurement of scratch resistance carried out as specified in DIN 53,7g9, part 10, the force with which a diamond needle produces a visible scratch on the panel surface is determined. This assessment is made immediately ater ~he action of the diamond needle, since, as a result of the elasticity of the surface layer, a slow recovery of the surface deformation can take place after the surface has been subjected to scratching. The scratch resistance is a measure of the surface hardness.
It has been found, surprisingly, that this decorative panel having the special layer of synthetic resin polymerized by radiation on at least one of its external surfaces not only has an excellent resistance to weathering, compared with the panels hitherto known, but, surprisingly, has an improved surface hardness.
~dditionally, it is appreciably less sensitive to acids and organic solvents.
- The reflectometer value is determined using a type RB/Dr. Lange reflectometer as speci~ied in ~IN
67,530 as a measurable indication of the gloss of thP
panel surface. A reflectometer value determined as ~ ~'3~)7~L8 specified in this standard constitutes an optical characteristic value for the surface of a test specimen and bears a relation to the gloss of the surface. It must be borne in mind in this respect that the gloss is not a purely physical quantity, but is also a quantity conditioned by physiological and psychological considerations. Direct measurement of glo~s is, therefore, not possible, but the "gloss powernl that is to say the contribution made by the surface, by virtue lo of its reflectance propertiesr to the creation of the impression of gloss, can, in principle, be measured in a suitable manner. The reflectometer value can be used as a measure of the gloss power, since it is essentially determined by the reflectance properties of the surface.
The reflectometer system defined by this standard is modeled on the layout described in ASTM D
523-67. The 20, 6D and 8~ angles of incidence are chosen arbitrarily.
The 20 geometry of measurement is used for test specimens having a 60 reflectometer value of over 70, while the 85 geometry of measurement is used for test specimens having a 60 reflectometPr value of less than 30.
In the reflectometer, a light source is formed into an image centrally in the aperture of a diaphragm. The light rays strike the panel surface at the prescribed angle of incidence (20~, 60 or 85) and are reflected in a scattered manner~ The light flux passing through the diaphragm is measured by means of photoelectronic detector located behind the diaphragm.
~ The core layer has the substrate function of the panel. It is composed, for example, of wood.
Panels or sheeting made of plastics, for example based on polyvinyl chloride, polyethylene or polystyrene, or 1~907~8 made of metal, for example steel, aluminum, copper, brass or other alloys, are also suitable as the core layer. The layer of synthetic resin polymerized by radiation is located right on the surface of these core layers or is attached to the core layer by means of film glues or glued joints, or preferably by means of adhesion-promoting synthetic re~ins, such as, for example, a phenol-formaldehyde o~ resorcinol-formaldehyde precondensate. Glued joints are merely lo layers of adhesive, while film glues are carrier layers wbich are coated or impregnated with adhesive.
Adhesion promoters are substances which, without themselves being an adhesive, promote the attachment of ~wo different materials.
The core layer can additionally be composed of the sheets of paper, especially sulfate kraft paper, which are customary in ~.P~L. sheets and are impregnated with heat-curable synthetic resin, in particular phenol-formaldehyde resin, and which are compressed under hot conditions. Depending on the panel thickness desired, l to about lO0 she~ts on top of one another are compressed under hot conditions.
The core layer can also be composed of a nonwoven fabric or mats, consolidated under pressure and composed of mineral fibers, glass fibers~ plastic fibers or a mixture of fibers, preferably cellulose.
Cellulose-containing fiber layers are, for example, wood fibers or wood chips distributed in a random manner. The nonwoven fabric or the mat composed of wood and/or cellulose fibers is prepared by applying a synthetic resin to the fibers, drying the resin-coated fibers, shaping the product into a fiber mat and subjecting this mat ~o preliminary co~pression under the influence of pressure (European patent application No.-0,081,147).
If appropriate, there is an underlaycontaining a heat-curable aminoplast or phenoplast resin located on the external surface(s) of this fiber-containing core layer. This underlay is composed, for example, of a pigmented or non-pigmented nonwoven fabric or paper.
Immediately upon the fiber-containing csre layer or on this underlay layer there follows, in a preferred embodiment, a layer of synthetic resin polymerized by radiation, which is decorative, i.e., exhibits a particular optical effect or a decoratiYe effect as a result of added dyestuffs. On the decorative layer of synthetic resin polymerized by radiation there can also be a cleart i.e., transparent and dyestuff-free, layer of synthetic resin polymerized by radiation, which form(s) the outermost surface(s) of the panel; however, it is entirely possible to omit this clear layer of synthetic resin, so that the decorative layer(s) of synthetic resin then form(s) the outermost layer(s).
Instead of the decorative layer of synthetic resin, it is also possible to use a decorative layer based on a dyed and/or printed plastics film or based on paper; this is usually composed of pi~mented, dyed and/or printed decorative paper. The layer, in this case transparent and free from dyestuffs, of synthetic resin polymerized by radiation is located on the plastics film or on the decorative paper. The decorative paper contains a - 30 heat-curable synthetic resin which is customary for this purpose, in particular an aminoplast resin~ and is located on core layers which have been built up from the sulfate kraft paper typical for H~PoL panels or from wood or-cellulose fibers distributed in a random manner and treated with phenolic resins.
lX907~8 The compounds envisaged for the preparation of the uppermost layer of synthetic resin, polymerized by radiation, embrace acrylic acid esters or methacrylic acid esters which can be polymerized by a 5 free radical mechanism by actinic radiation and which are present, on their own or together, in a poly-merizable mixture. The preferred component is a polyfunctional prepolymer, i.e., a polyunsaturated prepolymer. In addition to this predominant component, lo the copolymerizable mixture contains, if appropriate, a further component having a diluting action, which is described as a diluent monomer or diluent oligomer.
The proportion in the mixture of the polyfunctional prepolymer is 50 to 100%, in particular 60 to 90%, by 15 weight of the total weight of copolymerizable components. Prepolymers of a low viscosity (less than 103 poise at 20C) are employed wîthout the monomers or oligomers producing dilution.
The components used have a strong tendency 20 to polymerize by a free radical mechanism under the action of actinic radiation. Suitable actinic radiation is a light in the near UV region or high-energy radiation, for example electron,particle or x-ray radiation. The prepolymer which can 25 be polymerized by free radical mechanism is a polyfunctional, unsaturated aliphatic or aromatic acrylate or methacrylate, preferably an unsaturated polyester acrylate oligomer and especially an aliphatic urethane acrylate oligomer. Although aromatic urethane 30 acrylate ol-igomers also produce scratch-resistant surface coatings, these yellow after some time in exterior applications.
; In addition to the prepolymer, a mono-, di-, tri-, tetra-, penta- or hexaacrylate or -meth-35 acrylate, preferably a diacrylate or triacrylate, is _g_ ~lX907~3 used as an additional suitable monomer or oligomer in the mixture which can be copolymerized by a free radical mechanism. These mono- to hexaacrylates or mono- to hexamethacrylates are esters of polyols having 5 1 to 6 OH groups with acrylic acid or methacrylic acid, respectively, and are therefore also known as polyol acrylates or polyol methacrylates, respectively.
Suitable diacrylates are esters of acrylic acid with aliphatic, dihydric alcohols, in particular ethylene 10 glycol, 1,2-propylene glycol, 1,3-propyleneglycol, butane diols, l,6-hexane diol or neopentylglycol, with aliphatic ether-alcohols, in particular diethylene glycol, dipropylene glycol, dibutylene glycol, polyethylene glycols or polypropylene glycols, with 15 oxyalkylated compounds of the above-mentioned aliphatic alcohols and ether-alcohols or with aromatic dihydroxy compounds, in particular bisphenol A, pyrocatechol, resorcinol, hydroquinone, p-xylyleneglycol or p-hydroxybenzyl alcohol. Preferred diacrylates are 1~6-20 hexanediol diacrylate, tripropylene glycol diacrylateand 1,4-butanediol diacrylate. Preferred triacrylates are trimethylolpropane triacrylate and pentaerythritol triacrylate.
In addition to the urethane acrylate 25 oligomers and unsaturated polyester acrylate oligomers already mentioned, sui~able polyfunctional prepolymers are also epoxy-acrylate and silicone-acrylate oligomers, which are preferably used together with the diacrylates or triacrylates mentioned in the mixture 30 which can be copolymerized by a free radical mechanism.
The prepolymers are c~mpounds known E~ se and are prepared, for example, from hydroxylated ; copolymers in which the hydroxyl groups are distributed statistically along the copolymer chain. Statistically 35 unsaturated acrylic copolymers are obtained from this 1~907~8 copolymer by esterifying the hydroxyl groups witn acrylic acid. Semi-terminal unsaturated acrylic copolymers are prepared by having the hydroxyl group at the end of the chain in the preparation of the 5 hydroxylated copolymers. Urethane acrylate oligomers are prepared by reacting (meth)acrylic acid esters containing hydroxyl groups, for example, hydroxyethyl methacrylate, with polyfunctional isocyanates, preferably diisocyanates. The diisocyanates or 10 polyisocyanates can preferably be reaction products of diols, polyether~diols or poly~ster-diols containing a stoichiometric excess of monomeric diisscyanate or polyisocyanate.
If the polyfunctional prepolymer 15 preponderates in the polymerizable mixture, as the base resin, by virtue of its chemical nature, it determines the properties of the cured surface layer~ The monoacrylate to hexaacrylate or monomethacrylate to hexamethacrylate added makes it possible as a diluent 20 monomer or oligomer, to adjust the viscosity of the mixture to be cured, which is normally within a viscosity range from 20 to 100 poise (20C~, and entirely takes part in the free radical polymerization.
When irradiated, the coating is cured through free 25 radical polymerization between the double bonds of the prepolymer and of the diluent monomer or oligomer which may be present.
If curing is carried out under the influence of UV-light, i~ is necessary to add 30 photoinitiators which facilitate, by the formation of radicals, the initiation of the free radical polymerization. If curing is carried out with electron beams, no photoinitiators are required, however. Most of the photoinitiators contain at least 35 one carbonyl group conjugated with an aromatic ring. A
~ 8 photoinitiator system composed of several components is usually employed.
In addition, the s~nthetic resin which is polymerized by radiation contains, if appropriate, 5 suitable additives such as plasticizers, fillers, dyestuff pigments, agents for improving abrasion resistance and stabilizers, in order to achieve the desired decorative, mechanical and physical surface properties These substances include, for example, 10 barium sulfate, silica, aluminum oxide and light-stable pigments.
The decorative panel is produced by applying the liquid compounds which can be polymerized by radiation to the substrate to be coated, for 15 example, by spraying, casting, a doctor system, a roller or screen printing. If it has been applied to a decorative layer, the layer applied is then transparent~ It can, however, also be decorative itself and it is then colored and is located on a non-20 decorative paper layer or right on the corP layer. Ina further embodiment, an additional layer which can be polymerized by radiation but which, however, is not decorative but transparent, is also applied to this decorative layer of synthetic resin after the curing by 25 radiation.
~ The substrate used for the application of the compounds which can be polymerized by radiation is thus a paper layer, a decorative paper layer or the above~mentioned core layers based on wood, plastics, 30 metal or a stack of further fiber-containing layers which foxms the core of the panel subsequently obtained The fiber-containing layers of the stack, which are preferably composed of sulfa~e kraft paper or of a nonwoven fabric made of wood and/or cellulose 35 fibers, contain the heat-curable, precured resins customary for H.P.L. panels, in particular phenol-formaldehyde resins, whereas the paper sheets which may optionally additionally be present on the stack contain an aminoplast resin or, especially, a phenoplast resin.
5 The content of heat-curable resins is 20 to 250% by weight, relative to the particular layer.
The immersion or impregnation of the fiber-containing layers or the paper layers is carried out, for example, by immersion in a bath of a solution or 10 dispersion containing the heat-curable resin or by application or spraying by means of a metering system.
The solvent or dispersing agent is aqueous alcohol, aqueous acetone or water, depending on the synthetic resin used. It can also contain up to 20% by weight of lS fire retardant agents. The desired amount of resin is then distributed by scraping off or squeezing out, for example, by means of rollers.
The heat-curable resins of the substrate are precured and dried in a customary manner before the 20 application to the intended substrate of the compounds which can be polymerized by radiation.
During the radiation polymerization, the outermost, still liquid, layer composed of compounds which can be polymerized by radiation is covered by a 25 sheet or panel of plastics or paper or a composite film made from several layers of plastics OE layers of plastics and paper, which has a rough surface structure and which must be sufficiently transparent for the - actinic radiation. The film or panel intended for 30 covering must not have a very porous surface, since otherwise there is a risk that the liquia compounds still capable of polymerization by radiation will penetrate into the surface. In this event it is no longer possible to remove the film or panel after 35 pol~merization. This out~rmost liguid layer can itself _ 3_ .
~ 7 ~
be decorative and can contain a dyestuff or can be non-decorative, i.e., transparent, and can then be located on a decorative layer or on a decorative layer of synthetic resin which will be polymerized by radiation~ It is preferable to employ films having a thickness of up to 0.1 mm, since thicker coverings are not adequately transparent for electron beams or UV
radiation, or require relatively long exposure times.
In general, films of a thickness from 20 to 60 /um are 10 used, since, on the one hand, they are adequately transparent for the radiation and, on the other hand, they also have an adequate mechanical stren~th. For the sake of simplicity, they will be described as films or covering fi1ms in the following text.
The plastics film is composed, in parti~ular, of a polyester or polypropylene film which has been oriented by biaxial stretching. The rough structure of the film intended for covering is produced, for example, by the addition of pigments, at 20 least in the neighborhood of its outer surface. This surface rough~ess depends on elevations in the surface of the film, the height of which is, however, only slight in comparison with the thickness of the film and is within the range of a few micrometers at the most.
25 The pigments are composed, for example, of inorganic particles, in particular of aluminum oxide, aluminum sulfate, barium sulfate, calcium carbonate, magnesium carbonate, kaolin, talc, silicon dioxide, titanium dioxide or glass microbeads, or organic plastics 30 particles which are incompatible with the plasti~ of the film and which are dispersed as particles in the film. The pigments usually have a particle ~ize from 0.1 to 20 /um, the average particle size being within the range from 0.1 to 4 /um. Their concentration is 0.01 to 10% by weight, relative to the weight of the 7~
film. The concentration of the pigments in the film and their size is adjusted to suit the desired surface roughness of the plastics film.
The application of the covering film to the 5 liquid layer still capable of polymerization by radiation is effected by first applying this liquid layer to the substrate in the manner described above and then providing it with the covering film, the rough side of the surface of the covering film coming into 10 contact with the liquid, polymerizable layer. It i5 also possible, however, first to apply the liquid, polymerizable layer to the rough side of the surace of the covering film and then to apply the covering film together with this liquid layer to the substrate.
The roughness of the surface is transferred to the surface of the layer to be polymerized by radiation, which then assumes the surface structure of the covering film and obtains a mat appearance~
~his result is all the more surprlsing because the surface gloss of the end produce can, for practical 20 purposes, no longer be reduced by using texturized - separating media in the final compression process.
The polymerization caused by radiation can be initiated by employing a customary source for the formation of free radicals, such as, for example, a 25 photoinitiator, or heat alone is supplied. If the photopolymerizable layer contains photoinitiators, the polymerization is initiated by passage under mercury vapor lamps. The absence of oxygen is not necessary for curing by means of W radiation. It is appropriate 30 for the electron beams used for curing the polymerizable compounds to have an energy corresponding to 150 to 350 KeV. The energy of the electron accelerator is determined by the thickness of the synthetic resin layer ~o be formed~ the dose of 15~
~X~7~8 radiation required and the time of treatment or the speed with which it is carried out.
The devices used for accelerating the electron beams are commercially available. These are 5 the accelerators known as the "scanner type" and the "linear cathode typen. Free radicals are formed by interaction with the components of the polymerizable layer. This curing process is usually carried out at room temperature. For curing by means of electron 10 beams too, it is not necessary for this process to be carried out in an inert atmosphere, i.e., a substantially oxygen-free atmosphere, since the polymerizable surface layer is protected by the plastics film resting on it.
The covering film can be removed after the polymerization effected by radiation. It is also possible, however, not to remove the covering film until the completion of the process, i.e., after the compression under heat, or to use it as a casing for 20 the finished panel. If the substrates are sufficiently flexible, they are rolled up for storage or are immediately cut to the desired size. If the substrate containing the resin polymerized by radiation is only composed of a paper layer, it is laid on a stack of 25 fiber-containing layers forming the core layer. It is also possible additionally to provide the lower ace of the stack with a substrate of this type.
The resulting bundle of layers c~mposed of a ~iber containing core layer and surface layer(s) 30 polymerized by radiation and, if appropriate, intermedi~tely placed layers of paper or decorative paper is compressed under hot conditions, as is customary in the production of ~.P.L panels, to give a decorative panel, in the course of which the heat-35 curable resins ar cured. The temperature is preferably lX~V7~8 120 to 210C, the pressure is within the range from 10 to 100 bar and the treatment time is 1 to 30 minutes.
If, however, the core layer is composed of a wooden, plastics or metal panel, the temperature and the pressure can usually be reduced to values of 80C and 5 bar.
Compression is carried out in a dayli~ht, short cycle or continuous press.
The number and thickness of fiber-containing layers in the core layer or the thickness of the core layer is selected depending on the use of the panel, panel thicknesses of 3 to 25 mm being required for exterior applications, depending on the intended use. If a large numb~r of panels containing layers of synthetic resin polymerized by radiation are stacked one on top of the other in the press, which is of economic advantage if the core layer has a low thickness, the individual panels are separated from one another in each case by means of a separating medium. The separating medium is, for example, a paper layer, a plastics film or a metal plate. If the separating medium has a coarse surface structure, i.e., elevations or indentations, this coarse structure is imparted to the adjacent external layer of the particular panel, the mat fine structure already present being retained.
The degree of gloss on the panel surface, already established by tne radiation process, cannot, for practical purposes, be modified further by means of the separating medium.
The decorative panels produced are, surprisingly, particularly resistant to weathering and extremely scratch-resistant, which could possibly be due to an unforeseeable interaction between the various resins or perhaps also to subsequent crosslinking of the compounds polymerizable by free radicals when 1~9~37~8 compressed under heat. The scratch resistance and the resistance to chemicals are, surprisingly, substantially higher than in the case of a panel which receives a coating of the same compounds which can be S polymerized by radiation, this coating -- without the compression under heat -- only having been polymerized by a free radical mechanism by means of radiation. In addition, the surface of the panel has a considerably reduced gloss, such as cannot be achieved even if delustering agents are used in the surface layer.
Components having identical functions are marked with identical numbers in the figures. In Fig.
l, the sulfate kraft paper l containing partly cured synthetic resin is provided with a liquid layer 2 which contains dyestuff and can be polymerized by radiation.
The layer 2 is covered by the plastics film 3 and is cured by means of electron beams in the apparatus 4~
In Fig. 2, the dyestuff-containing layer 5 is already partly cured by radiation when it is provided with the transparent liquid layer 6 which can be polymerized by radiation. The plastics film 3 is applied to the layer 6. Fig. 3 differs from Fig. l only in that there is also a transparent liquid layer 6 which can be polymerized by radiation located on the plastics film
However, this decorative panel has the property, whicn is frequently undesirable, of exhibiting a c0rtain degree of gloss. If texturized separating media are used in the final com-pression under heat, it is admittedly possible to give the panel surface a surface structure which is texturized in conformity with the surface of the separating medium, for example a surface struc-ture similar to orange peel, but its surface gloss is, as before, very high. The addition of known delustering agents, such as silicon dioxide pigments, to the outermost surface layer of the panel also does not, for practical purposes, reduce the gloss, since the pigment-containing surface, which is initially still satin-frosted after the radiation polymerization, unaccountably becomes glossy again as soon as the panel is subsequently subject-ed to compression under heat.
SUMMARY OF THE INVENTION
It is therefore an object of the invention to provide a decorative panel which is resistant to weathering, acids and sol-vents and which has a high surface hardness and only a slight surface gloss.
This object is achieved by a decorative panel which comprises a core layer; an outermost layer applied over the core layer, the outermost layer being a synthetic resin polymerized by radiation and comprising an unsaturated acrylate or an unsaturated methacrylate, and further being scratch-resistant at a scratch loading of at least about 1.5 Newtons, pre~erably from about 2 to almost 7 Newtons, as defined by DIN 53,799 part 10 and having a reflectometer value no greater than about 50 at an ~9()718 angle of incidence of 85 as clefined by DIN 67,530; and decoration means ~or forming a decoration covering th~ core layer.
The object of the invention is also achieved by a process for the production of a decorative panel ~hich comprises applying a layer of a llquid synthetic resin polymerizable by radiation and comprising an unsaturated acrylate or an unsaturated :
methacrylate, to a substrate; applying a film having a surface roughness over the resin layer; transferring the surface roughne s ~ -10 to the resin layer; polymerizing the resin layer by exposure to radiation; and compressing the resin layer and the substrate at an elevated temperature and wherein the resin layer~includes decoratlon means.
The object of the invention is further achieved by a process for the production of a decorative~pan~el~which comp~rises applying a first layer containing decorat~ion;means to;~a substrate;
appIying a: second layer over the~lrgt layer, the seoond~layer being a~synthetia~ r~esin polyDerlz~able by radiation and comprls~ing ~ -~
; an unsaturated acrylate or an unsaturated methacrylat~e~, apply~ing~a ~ :
20~ film~having a~surfaae roughness over the second layer; trans-ferring the~surface roughness to thé second layer; polymerizing the~resin~;layer by~exposure to~radiation~;~ and~c~ompressing;the f~irst~and second~layers ~and the~ ubstrate~-at an elevated temperatu~re. ;~
BRIEF;D~SCRIPTION~OF TH~ DRAWIN65 The in~entlon is il~l~ustra~ted~in greater detail~by mean;s of Figs.~ l~to~3a and~the sxampl~ss~below~
)718 2073~-~48 Fig. 1 shows ~he sequence of the process variant described in Example 1, Fig. la shows a partial cross-section through a panel according to Fig. l;
Fig. 2 shows the sequence of the process variant described in Example 2;
4a .
.
~Z~307~
Fig. 3 shows the sequence of the process variant described in Example 3; and Fig. 3a shows a partial cross-section through a panel according to Figs. 2 and 3.
s DETAILED DESCRIPTION OF ~HE PREFERRED EMBODIMENTS
The panel of the invention is a sheet-like unit having a surface shape and surface structure suited to the intended use and which can, for example, also have a bent shape~ Within the scope of the invention, a panel is also to be understood as sheeting.
In the measurement of scratch resistance carried out as specified in DIN 53,7g9, part 10, the force with which a diamond needle produces a visible scratch on the panel surface is determined. This assessment is made immediately ater ~he action of the diamond needle, since, as a result of the elasticity of the surface layer, a slow recovery of the surface deformation can take place after the surface has been subjected to scratching. The scratch resistance is a measure of the surface hardness.
It has been found, surprisingly, that this decorative panel having the special layer of synthetic resin polymerized by radiation on at least one of its external surfaces not only has an excellent resistance to weathering, compared with the panels hitherto known, but, surprisingly, has an improved surface hardness.
~dditionally, it is appreciably less sensitive to acids and organic solvents.
- The reflectometer value is determined using a type RB/Dr. Lange reflectometer as speci~ied in ~IN
67,530 as a measurable indication of the gloss of thP
panel surface. A reflectometer value determined as ~ ~'3~)7~L8 specified in this standard constitutes an optical characteristic value for the surface of a test specimen and bears a relation to the gloss of the surface. It must be borne in mind in this respect that the gloss is not a purely physical quantity, but is also a quantity conditioned by physiological and psychological considerations. Direct measurement of glo~s is, therefore, not possible, but the "gloss powernl that is to say the contribution made by the surface, by virtue lo of its reflectance propertiesr to the creation of the impression of gloss, can, in principle, be measured in a suitable manner. The reflectometer value can be used as a measure of the gloss power, since it is essentially determined by the reflectance properties of the surface.
The reflectometer system defined by this standard is modeled on the layout described in ASTM D
523-67. The 20, 6D and 8~ angles of incidence are chosen arbitrarily.
The 20 geometry of measurement is used for test specimens having a 60 reflectometer value of over 70, while the 85 geometry of measurement is used for test specimens having a 60 reflectometPr value of less than 30.
In the reflectometer, a light source is formed into an image centrally in the aperture of a diaphragm. The light rays strike the panel surface at the prescribed angle of incidence (20~, 60 or 85) and are reflected in a scattered manner~ The light flux passing through the diaphragm is measured by means of photoelectronic detector located behind the diaphragm.
~ The core layer has the substrate function of the panel. It is composed, for example, of wood.
Panels or sheeting made of plastics, for example based on polyvinyl chloride, polyethylene or polystyrene, or 1~907~8 made of metal, for example steel, aluminum, copper, brass or other alloys, are also suitable as the core layer. The layer of synthetic resin polymerized by radiation is located right on the surface of these core layers or is attached to the core layer by means of film glues or glued joints, or preferably by means of adhesion-promoting synthetic re~ins, such as, for example, a phenol-formaldehyde o~ resorcinol-formaldehyde precondensate. Glued joints are merely lo layers of adhesive, while film glues are carrier layers wbich are coated or impregnated with adhesive.
Adhesion promoters are substances which, without themselves being an adhesive, promote the attachment of ~wo different materials.
The core layer can additionally be composed of the sheets of paper, especially sulfate kraft paper, which are customary in ~.P~L. sheets and are impregnated with heat-curable synthetic resin, in particular phenol-formaldehyde resin, and which are compressed under hot conditions. Depending on the panel thickness desired, l to about lO0 she~ts on top of one another are compressed under hot conditions.
The core layer can also be composed of a nonwoven fabric or mats, consolidated under pressure and composed of mineral fibers, glass fibers~ plastic fibers or a mixture of fibers, preferably cellulose.
Cellulose-containing fiber layers are, for example, wood fibers or wood chips distributed in a random manner. The nonwoven fabric or the mat composed of wood and/or cellulose fibers is prepared by applying a synthetic resin to the fibers, drying the resin-coated fibers, shaping the product into a fiber mat and subjecting this mat ~o preliminary co~pression under the influence of pressure (European patent application No.-0,081,147).
If appropriate, there is an underlaycontaining a heat-curable aminoplast or phenoplast resin located on the external surface(s) of this fiber-containing core layer. This underlay is composed, for example, of a pigmented or non-pigmented nonwoven fabric or paper.
Immediately upon the fiber-containing csre layer or on this underlay layer there follows, in a preferred embodiment, a layer of synthetic resin polymerized by radiation, which is decorative, i.e., exhibits a particular optical effect or a decoratiYe effect as a result of added dyestuffs. On the decorative layer of synthetic resin polymerized by radiation there can also be a cleart i.e., transparent and dyestuff-free, layer of synthetic resin polymerized by radiation, which form(s) the outermost surface(s) of the panel; however, it is entirely possible to omit this clear layer of synthetic resin, so that the decorative layer(s) of synthetic resin then form(s) the outermost layer(s).
Instead of the decorative layer of synthetic resin, it is also possible to use a decorative layer based on a dyed and/or printed plastics film or based on paper; this is usually composed of pi~mented, dyed and/or printed decorative paper. The layer, in this case transparent and free from dyestuffs, of synthetic resin polymerized by radiation is located on the plastics film or on the decorative paper. The decorative paper contains a - 30 heat-curable synthetic resin which is customary for this purpose, in particular an aminoplast resin~ and is located on core layers which have been built up from the sulfate kraft paper typical for H~PoL panels or from wood or-cellulose fibers distributed in a random manner and treated with phenolic resins.
lX907~8 The compounds envisaged for the preparation of the uppermost layer of synthetic resin, polymerized by radiation, embrace acrylic acid esters or methacrylic acid esters which can be polymerized by a 5 free radical mechanism by actinic radiation and which are present, on their own or together, in a poly-merizable mixture. The preferred component is a polyfunctional prepolymer, i.e., a polyunsaturated prepolymer. In addition to this predominant component, lo the copolymerizable mixture contains, if appropriate, a further component having a diluting action, which is described as a diluent monomer or diluent oligomer.
The proportion in the mixture of the polyfunctional prepolymer is 50 to 100%, in particular 60 to 90%, by 15 weight of the total weight of copolymerizable components. Prepolymers of a low viscosity (less than 103 poise at 20C) are employed wîthout the monomers or oligomers producing dilution.
The components used have a strong tendency 20 to polymerize by a free radical mechanism under the action of actinic radiation. Suitable actinic radiation is a light in the near UV region or high-energy radiation, for example electron,particle or x-ray radiation. The prepolymer which can 25 be polymerized by free radical mechanism is a polyfunctional, unsaturated aliphatic or aromatic acrylate or methacrylate, preferably an unsaturated polyester acrylate oligomer and especially an aliphatic urethane acrylate oligomer. Although aromatic urethane 30 acrylate ol-igomers also produce scratch-resistant surface coatings, these yellow after some time in exterior applications.
; In addition to the prepolymer, a mono-, di-, tri-, tetra-, penta- or hexaacrylate or -meth-35 acrylate, preferably a diacrylate or triacrylate, is _g_ ~lX907~3 used as an additional suitable monomer or oligomer in the mixture which can be copolymerized by a free radical mechanism. These mono- to hexaacrylates or mono- to hexamethacrylates are esters of polyols having 5 1 to 6 OH groups with acrylic acid or methacrylic acid, respectively, and are therefore also known as polyol acrylates or polyol methacrylates, respectively.
Suitable diacrylates are esters of acrylic acid with aliphatic, dihydric alcohols, in particular ethylene 10 glycol, 1,2-propylene glycol, 1,3-propyleneglycol, butane diols, l,6-hexane diol or neopentylglycol, with aliphatic ether-alcohols, in particular diethylene glycol, dipropylene glycol, dibutylene glycol, polyethylene glycols or polypropylene glycols, with 15 oxyalkylated compounds of the above-mentioned aliphatic alcohols and ether-alcohols or with aromatic dihydroxy compounds, in particular bisphenol A, pyrocatechol, resorcinol, hydroquinone, p-xylyleneglycol or p-hydroxybenzyl alcohol. Preferred diacrylates are 1~6-20 hexanediol diacrylate, tripropylene glycol diacrylateand 1,4-butanediol diacrylate. Preferred triacrylates are trimethylolpropane triacrylate and pentaerythritol triacrylate.
In addition to the urethane acrylate 25 oligomers and unsaturated polyester acrylate oligomers already mentioned, sui~able polyfunctional prepolymers are also epoxy-acrylate and silicone-acrylate oligomers, which are preferably used together with the diacrylates or triacrylates mentioned in the mixture 30 which can be copolymerized by a free radical mechanism.
The prepolymers are c~mpounds known E~ se and are prepared, for example, from hydroxylated ; copolymers in which the hydroxyl groups are distributed statistically along the copolymer chain. Statistically 35 unsaturated acrylic copolymers are obtained from this 1~907~8 copolymer by esterifying the hydroxyl groups witn acrylic acid. Semi-terminal unsaturated acrylic copolymers are prepared by having the hydroxyl group at the end of the chain in the preparation of the 5 hydroxylated copolymers. Urethane acrylate oligomers are prepared by reacting (meth)acrylic acid esters containing hydroxyl groups, for example, hydroxyethyl methacrylate, with polyfunctional isocyanates, preferably diisocyanates. The diisocyanates or 10 polyisocyanates can preferably be reaction products of diols, polyether~diols or poly~ster-diols containing a stoichiometric excess of monomeric diisscyanate or polyisocyanate.
If the polyfunctional prepolymer 15 preponderates in the polymerizable mixture, as the base resin, by virtue of its chemical nature, it determines the properties of the cured surface layer~ The monoacrylate to hexaacrylate or monomethacrylate to hexamethacrylate added makes it possible as a diluent 20 monomer or oligomer, to adjust the viscosity of the mixture to be cured, which is normally within a viscosity range from 20 to 100 poise (20C~, and entirely takes part in the free radical polymerization.
When irradiated, the coating is cured through free 25 radical polymerization between the double bonds of the prepolymer and of the diluent monomer or oligomer which may be present.
If curing is carried out under the influence of UV-light, i~ is necessary to add 30 photoinitiators which facilitate, by the formation of radicals, the initiation of the free radical polymerization. If curing is carried out with electron beams, no photoinitiators are required, however. Most of the photoinitiators contain at least 35 one carbonyl group conjugated with an aromatic ring. A
~ 8 photoinitiator system composed of several components is usually employed.
In addition, the s~nthetic resin which is polymerized by radiation contains, if appropriate, 5 suitable additives such as plasticizers, fillers, dyestuff pigments, agents for improving abrasion resistance and stabilizers, in order to achieve the desired decorative, mechanical and physical surface properties These substances include, for example, 10 barium sulfate, silica, aluminum oxide and light-stable pigments.
The decorative panel is produced by applying the liquid compounds which can be polymerized by radiation to the substrate to be coated, for 15 example, by spraying, casting, a doctor system, a roller or screen printing. If it has been applied to a decorative layer, the layer applied is then transparent~ It can, however, also be decorative itself and it is then colored and is located on a non-20 decorative paper layer or right on the corP layer. Ina further embodiment, an additional layer which can be polymerized by radiation but which, however, is not decorative but transparent, is also applied to this decorative layer of synthetic resin after the curing by 25 radiation.
~ The substrate used for the application of the compounds which can be polymerized by radiation is thus a paper layer, a decorative paper layer or the above~mentioned core layers based on wood, plastics, 30 metal or a stack of further fiber-containing layers which foxms the core of the panel subsequently obtained The fiber-containing layers of the stack, which are preferably composed of sulfa~e kraft paper or of a nonwoven fabric made of wood and/or cellulose 35 fibers, contain the heat-curable, precured resins customary for H.P.L. panels, in particular phenol-formaldehyde resins, whereas the paper sheets which may optionally additionally be present on the stack contain an aminoplast resin or, especially, a phenoplast resin.
5 The content of heat-curable resins is 20 to 250% by weight, relative to the particular layer.
The immersion or impregnation of the fiber-containing layers or the paper layers is carried out, for example, by immersion in a bath of a solution or 10 dispersion containing the heat-curable resin or by application or spraying by means of a metering system.
The solvent or dispersing agent is aqueous alcohol, aqueous acetone or water, depending on the synthetic resin used. It can also contain up to 20% by weight of lS fire retardant agents. The desired amount of resin is then distributed by scraping off or squeezing out, for example, by means of rollers.
The heat-curable resins of the substrate are precured and dried in a customary manner before the 20 application to the intended substrate of the compounds which can be polymerized by radiation.
During the radiation polymerization, the outermost, still liquid, layer composed of compounds which can be polymerized by radiation is covered by a 25 sheet or panel of plastics or paper or a composite film made from several layers of plastics OE layers of plastics and paper, which has a rough surface structure and which must be sufficiently transparent for the - actinic radiation. The film or panel intended for 30 covering must not have a very porous surface, since otherwise there is a risk that the liquia compounds still capable of polymerization by radiation will penetrate into the surface. In this event it is no longer possible to remove the film or panel after 35 pol~merization. This out~rmost liguid layer can itself _ 3_ .
~ 7 ~
be decorative and can contain a dyestuff or can be non-decorative, i.e., transparent, and can then be located on a decorative layer or on a decorative layer of synthetic resin which will be polymerized by radiation~ It is preferable to employ films having a thickness of up to 0.1 mm, since thicker coverings are not adequately transparent for electron beams or UV
radiation, or require relatively long exposure times.
In general, films of a thickness from 20 to 60 /um are 10 used, since, on the one hand, they are adequately transparent for the radiation and, on the other hand, they also have an adequate mechanical stren~th. For the sake of simplicity, they will be described as films or covering fi1ms in the following text.
The plastics film is composed, in parti~ular, of a polyester or polypropylene film which has been oriented by biaxial stretching. The rough structure of the film intended for covering is produced, for example, by the addition of pigments, at 20 least in the neighborhood of its outer surface. This surface rough~ess depends on elevations in the surface of the film, the height of which is, however, only slight in comparison with the thickness of the film and is within the range of a few micrometers at the most.
25 The pigments are composed, for example, of inorganic particles, in particular of aluminum oxide, aluminum sulfate, barium sulfate, calcium carbonate, magnesium carbonate, kaolin, talc, silicon dioxide, titanium dioxide or glass microbeads, or organic plastics 30 particles which are incompatible with the plasti~ of the film and which are dispersed as particles in the film. The pigments usually have a particle ~ize from 0.1 to 20 /um, the average particle size being within the range from 0.1 to 4 /um. Their concentration is 0.01 to 10% by weight, relative to the weight of the 7~
film. The concentration of the pigments in the film and their size is adjusted to suit the desired surface roughness of the plastics film.
The application of the covering film to the 5 liquid layer still capable of polymerization by radiation is effected by first applying this liquid layer to the substrate in the manner described above and then providing it with the covering film, the rough side of the surface of the covering film coming into 10 contact with the liquid, polymerizable layer. It i5 also possible, however, first to apply the liquid, polymerizable layer to the rough side of the surace of the covering film and then to apply the covering film together with this liquid layer to the substrate.
The roughness of the surface is transferred to the surface of the layer to be polymerized by radiation, which then assumes the surface structure of the covering film and obtains a mat appearance~
~his result is all the more surprlsing because the surface gloss of the end produce can, for practical 20 purposes, no longer be reduced by using texturized - separating media in the final compression process.
The polymerization caused by radiation can be initiated by employing a customary source for the formation of free radicals, such as, for example, a 25 photoinitiator, or heat alone is supplied. If the photopolymerizable layer contains photoinitiators, the polymerization is initiated by passage under mercury vapor lamps. The absence of oxygen is not necessary for curing by means of W radiation. It is appropriate 30 for the electron beams used for curing the polymerizable compounds to have an energy corresponding to 150 to 350 KeV. The energy of the electron accelerator is determined by the thickness of the synthetic resin layer ~o be formed~ the dose of 15~
~X~7~8 radiation required and the time of treatment or the speed with which it is carried out.
The devices used for accelerating the electron beams are commercially available. These are 5 the accelerators known as the "scanner type" and the "linear cathode typen. Free radicals are formed by interaction with the components of the polymerizable layer. This curing process is usually carried out at room temperature. For curing by means of electron 10 beams too, it is not necessary for this process to be carried out in an inert atmosphere, i.e., a substantially oxygen-free atmosphere, since the polymerizable surface layer is protected by the plastics film resting on it.
The covering film can be removed after the polymerization effected by radiation. It is also possible, however, not to remove the covering film until the completion of the process, i.e., after the compression under heat, or to use it as a casing for 20 the finished panel. If the substrates are sufficiently flexible, they are rolled up for storage or are immediately cut to the desired size. If the substrate containing the resin polymerized by radiation is only composed of a paper layer, it is laid on a stack of 25 fiber-containing layers forming the core layer. It is also possible additionally to provide the lower ace of the stack with a substrate of this type.
The resulting bundle of layers c~mposed of a ~iber containing core layer and surface layer(s) 30 polymerized by radiation and, if appropriate, intermedi~tely placed layers of paper or decorative paper is compressed under hot conditions, as is customary in the production of ~.P.L panels, to give a decorative panel, in the course of which the heat-35 curable resins ar cured. The temperature is preferably lX~V7~8 120 to 210C, the pressure is within the range from 10 to 100 bar and the treatment time is 1 to 30 minutes.
If, however, the core layer is composed of a wooden, plastics or metal panel, the temperature and the pressure can usually be reduced to values of 80C and 5 bar.
Compression is carried out in a dayli~ht, short cycle or continuous press.
The number and thickness of fiber-containing layers in the core layer or the thickness of the core layer is selected depending on the use of the panel, panel thicknesses of 3 to 25 mm being required for exterior applications, depending on the intended use. If a large numb~r of panels containing layers of synthetic resin polymerized by radiation are stacked one on top of the other in the press, which is of economic advantage if the core layer has a low thickness, the individual panels are separated from one another in each case by means of a separating medium. The separating medium is, for example, a paper layer, a plastics film or a metal plate. If the separating medium has a coarse surface structure, i.e., elevations or indentations, this coarse structure is imparted to the adjacent external layer of the particular panel, the mat fine structure already present being retained.
The degree of gloss on the panel surface, already established by tne radiation process, cannot, for practical purposes, be modified further by means of the separating medium.
The decorative panels produced are, surprisingly, particularly resistant to weathering and extremely scratch-resistant, which could possibly be due to an unforeseeable interaction between the various resins or perhaps also to subsequent crosslinking of the compounds polymerizable by free radicals when 1~9~37~8 compressed under heat. The scratch resistance and the resistance to chemicals are, surprisingly, substantially higher than in the case of a panel which receives a coating of the same compounds which can be S polymerized by radiation, this coating -- without the compression under heat -- only having been polymerized by a free radical mechanism by means of radiation. In addition, the surface of the panel has a considerably reduced gloss, such as cannot be achieved even if delustering agents are used in the surface layer.
Components having identical functions are marked with identical numbers in the figures. In Fig.
l, the sulfate kraft paper l containing partly cured synthetic resin is provided with a liquid layer 2 which contains dyestuff and can be polymerized by radiation.
The layer 2 is covered by the plastics film 3 and is cured by means of electron beams in the apparatus 4~
In Fig. 2, the dyestuff-containing layer 5 is already partly cured by radiation when it is provided with the transparent liquid layer 6 which can be polymerized by radiation. The plastics film 3 is applied to the layer 6. Fig. 3 differs from Fig. l only in that there is also a transparent liquid layer 6 which can be polymerized by radiation located on the plastics film
3. In the figures, the guide rollers are marked 7, 8, 9 and lO and the coating devices are marked 11 and 12.
Compressed panels 14 according to the layer arrangements of Figs. l, 2 and 3 can be seen in Figs.
la and 3a. The stack forming the core is marked 13.
In the following examples, the percentages are percent by weight.
~L~90~l8 Example 1 As shown in Fig. 1, a pasty liquid 2 (viscosity 50 poise at 25C) composed of a mi~ture, polymerizable by radiation, of 85 parts by weight of an aliphatic urethane acrylate oligomer as prepolymer, 15 parts by weight of hexane diol diacrylate as diluent monomer and 10 parts by weight of organic dyestuf~
pigments is applied to a sulfate kraft paper 1 which has first been impregnated with a heat-curable phenol-lo formaldehyde resin (amount of resin applied 70%~, afterthe resin has been partly cured by means of rollers, whereupon a continuous film (layer thickness about 80/um) is formed. Immediately afterwards, a delustered, biaxially stretched polypropylene single-ply film 3 containing 8% by weight of calcium carbonateo~ average particle size 3 /um is applied to this film composed of compounds polymeriæable by radiation, and the film is crosslinked in a substantially homogeneous manner by means of electron beams at room temperature without the application of pressure. The dose of radiation absorbed is 60 RGy.
After the plastics film 3 has been removed, the paper 1 with the e~ternal layer 2 of synthetic resin copolymerized by radiation is placed in each case on the external face of a stack 13 composed of 50 superposed sheets of paper. The sheets of paper have previously been impregnated with a heat-curable phenol-formaldehyde resin, and the resin has been partly cured. The bundle of layers is compressed at 150~ and 80 bar for 10 minutes in a press between two texturized metal sheets. A bundle has the following composition:
A first decorative layer 2 ~synthetic resin containing organic dyestuff pigments and polymerized by radiation) as the outer layer on a first previously ~X~071~
impregnated paper layer 1, 50 paper webs (impregnated with a phenol-formaldehyde resin) as the core layer 13, and a second decorative layer 2 (synthetic resin containing organic dyestuff pigments and polymeriz~d by 5 radiation) as the outer layer on a previously impregnated second paper layer 1.
The resulting panel 14, which is 10 mm thick and is decorated on both sides, has a scratch resistance higher than 3.0 N (DIN 53,799, pa~t 10). It 10 is insensitive to hydrolysis and shows no changes after being boiled in water for 100 hours. Its surface is not attacked by concentrated mineral acid during an exposure time of 6 hours (DIN 53,230). The fastness to light of this panel is given rating 8 (DIN 54,004).
15 The resistance of the panel to the effects of weathering is determined as specified in ASTM G 53-84, in which a time cycle of 4 hours UV/4 h CON
- (condensation period) is maintained for 1500 hours ~ a test temperature of 50C. The decorative surfaces 20 exhibit a low surface gloss corresponding to a reflectometer value of 20-22, 60 angle of incidence or to a reflector value 44-45, 85D angle of incidence (DI~J
67,530). After weathering, the panel exhibits no discoloration or change in gloss.
25 ExamPle 2 The viscous, radiation-polymerizable, dyestuff-containing li~uid 2 of Example 1 is applied, as described in Example 1, to a sulfate kraft paper 1 containing precured phenolformaldehyde resin, and is 30 crosslinked in an essentially homogeneous manner by means of electron beams. The dose absorbed is 5 to 10 ~Gy. ~ further layer 6 composed of transparent - i.e., dyestuff-free - radiation-polymerizable liquid which, 97~L8 apart from the dyestuff, contains the same compounds as the layer first applied is applied as shown in Fig. 2, by means of rollers or rotary screen printing, to the surface of the paper on which the decorative layer 5 of synthetic resin polymerized by radiation is located.
This layer 6 forms a continuous film having a layer thickness of about 20 /um. Immediately after the application of this second layer, a biaxially oriented polyethylene terphthalate single-ply film 3 which has been delustered by stretching is placed on the wet layer 6. Curing is carried out analogously to Example l by means of electron beams. The dose of radiation absorbed is 60 ~Gy. After the plastics film 3 has been removed, the paper l containing the external layer 6 of synthetic resin copolymerized by radiation is laid in each case on the outer face of a stack 13 composed of 50 superposed sheets of paper. The sheets of paper have previously been impregnated with a heat-curable phenol-formaldehyde resin and the resin has been partly cured. The bundle of layers is compressed at 150~ and 80 bar for 10 minutes in a press between two sheets of metal. It has the following composition:
- Transparent layer 6 (synthetic resin polymerized by radiation) as the outermost layer, - Decorative l~ayer 5 (synthetic resin containing organic dyestuff pigments and polymerized by radiation), both layers on a previously impregnated paper layer l, 30 - 50 paper webs (impre~nated with a phenol-formaldehyde resin) as the core layer 13, , 7~3 - Decorative layer 5 (synthetic resin containing organic dyestuff pigments and polymerized by radiation), and - Transparent layer 6 (synthetic resin s polymerized by radiation) as the outermost layer, both layers on a previously impregnated paper layer 1.
The resulting decorative panel 14 has a scratch resistance higher than 2.0 N (DIN 53,799, part 10). Its surface is not attacked by concentrated mineral acid during a treatment time of 6 hours~ The fastness to light of this panel is given the rating 8 (DIN 54,004). It has a surface gloss corresponding to a reflectometer value of 22-24, 60 angle of incidence, and a reflectometer value of 44-45, B5 angle of incidence (DIN 67,530).
Exam~le 3 The pasty, dyestuff-containing liquid 2, composed of radiation-polymerizable compounds/ of Example 1 is applied to a sulfate kraft paper 1 which has first been impregnated with a heat-curable phenol-formaldehyde resin (amount of resin applied 70%)of~ich the resin has ~been partially cured,anda continuous film (layer thickness about 80 /um) is formed (cf. Fig.
2s 3). :~
A transparent layer~6 composed of a pastyr dyestuff-free liquid composed of the same radiation-polymerizable compounds is applied (layer thickness ; about ~0 to 40 /um) to a delustered polypropylene plastics film 3. The pa~er 1 and the plasti~s film 3 are then placed one on top of the other in sheet or web ' ' , , , . .
.
~ 71 ~
form, so that the two liquid layers 2 and 6 come into contact with one another. In so doing, care must be taken that inclusions of air are not formed. The polymerizable compounds are crosslinked by means of electron beams which impinge on the liquid layers 2 and 6 through the plastics film 3. The dose absorbed is 60 kGy. After the plastics film 3 has been removed, the paper l containing the polymerized surface layer 2 and 6 is processed further to give a decorative panel 14 by lo compression under heat together with a paper stack 13 as described in Example 2.
The layers of synthetic resin polymerized by radiation in the examples still exhibit relatively low ~alues of scratch resistance within the range rom about 0.7 to 0.9 Newtons before the compression under heat. ~ substantially higher surface hardness in the panel is only obtained, surprisingly, after the layer of synthetic resin polymerized by radiation has been subjected, in accordance with the invention, to compression under heat.
The reflectometer value measured with a Dr.
Lange type RB reflectometer as specified in DIN 67,530 is 45 to 47, 20 angle of incidence, and about 83, 60 angle of incidence, if the delustered plastic~ film is absent when curing with electron beams is carried out.
It falls to values of 37 to 41, 20 angle of incidence, and about 79, 60 angle of incidence, if texturized compression elements which impart to the outermost layer of the panel, for example, a surface structure similar to that of orange peel are used in the compression under heat. Even lower reflectometer values of about 30 to 36, 20 angle of incidence, and about 75, 60 angle of incidence, can be achieved by adding delustering agents to the surface layer. The particularly low gloss values according to the , ~X907~L8 invention can, however, only be achieved by means of the special measures used in the polymerization of the synthetic resin layer.
-2~-,
Compressed panels 14 according to the layer arrangements of Figs. l, 2 and 3 can be seen in Figs.
la and 3a. The stack forming the core is marked 13.
In the following examples, the percentages are percent by weight.
~L~90~l8 Example 1 As shown in Fig. 1, a pasty liquid 2 (viscosity 50 poise at 25C) composed of a mi~ture, polymerizable by radiation, of 85 parts by weight of an aliphatic urethane acrylate oligomer as prepolymer, 15 parts by weight of hexane diol diacrylate as diluent monomer and 10 parts by weight of organic dyestuf~
pigments is applied to a sulfate kraft paper 1 which has first been impregnated with a heat-curable phenol-lo formaldehyde resin (amount of resin applied 70%~, afterthe resin has been partly cured by means of rollers, whereupon a continuous film (layer thickness about 80/um) is formed. Immediately afterwards, a delustered, biaxially stretched polypropylene single-ply film 3 containing 8% by weight of calcium carbonateo~ average particle size 3 /um is applied to this film composed of compounds polymeriæable by radiation, and the film is crosslinked in a substantially homogeneous manner by means of electron beams at room temperature without the application of pressure. The dose of radiation absorbed is 60 RGy.
After the plastics film 3 has been removed, the paper 1 with the e~ternal layer 2 of synthetic resin copolymerized by radiation is placed in each case on the external face of a stack 13 composed of 50 superposed sheets of paper. The sheets of paper have previously been impregnated with a heat-curable phenol-formaldehyde resin, and the resin has been partly cured. The bundle of layers is compressed at 150~ and 80 bar for 10 minutes in a press between two texturized metal sheets. A bundle has the following composition:
A first decorative layer 2 ~synthetic resin containing organic dyestuff pigments and polymerized by radiation) as the outer layer on a first previously ~X~071~
impregnated paper layer 1, 50 paper webs (impregnated with a phenol-formaldehyde resin) as the core layer 13, and a second decorative layer 2 (synthetic resin containing organic dyestuff pigments and polymeriz~d by 5 radiation) as the outer layer on a previously impregnated second paper layer 1.
The resulting panel 14, which is 10 mm thick and is decorated on both sides, has a scratch resistance higher than 3.0 N (DIN 53,799, pa~t 10). It 10 is insensitive to hydrolysis and shows no changes after being boiled in water for 100 hours. Its surface is not attacked by concentrated mineral acid during an exposure time of 6 hours (DIN 53,230). The fastness to light of this panel is given rating 8 (DIN 54,004).
15 The resistance of the panel to the effects of weathering is determined as specified in ASTM G 53-84, in which a time cycle of 4 hours UV/4 h CON
- (condensation period) is maintained for 1500 hours ~ a test temperature of 50C. The decorative surfaces 20 exhibit a low surface gloss corresponding to a reflectometer value of 20-22, 60 angle of incidence or to a reflector value 44-45, 85D angle of incidence (DI~J
67,530). After weathering, the panel exhibits no discoloration or change in gloss.
25 ExamPle 2 The viscous, radiation-polymerizable, dyestuff-containing li~uid 2 of Example 1 is applied, as described in Example 1, to a sulfate kraft paper 1 containing precured phenolformaldehyde resin, and is 30 crosslinked in an essentially homogeneous manner by means of electron beams. The dose absorbed is 5 to 10 ~Gy. ~ further layer 6 composed of transparent - i.e., dyestuff-free - radiation-polymerizable liquid which, 97~L8 apart from the dyestuff, contains the same compounds as the layer first applied is applied as shown in Fig. 2, by means of rollers or rotary screen printing, to the surface of the paper on which the decorative layer 5 of synthetic resin polymerized by radiation is located.
This layer 6 forms a continuous film having a layer thickness of about 20 /um. Immediately after the application of this second layer, a biaxially oriented polyethylene terphthalate single-ply film 3 which has been delustered by stretching is placed on the wet layer 6. Curing is carried out analogously to Example l by means of electron beams. The dose of radiation absorbed is 60 ~Gy. After the plastics film 3 has been removed, the paper l containing the external layer 6 of synthetic resin copolymerized by radiation is laid in each case on the outer face of a stack 13 composed of 50 superposed sheets of paper. The sheets of paper have previously been impregnated with a heat-curable phenol-formaldehyde resin and the resin has been partly cured. The bundle of layers is compressed at 150~ and 80 bar for 10 minutes in a press between two sheets of metal. It has the following composition:
- Transparent layer 6 (synthetic resin polymerized by radiation) as the outermost layer, - Decorative l~ayer 5 (synthetic resin containing organic dyestuff pigments and polymerized by radiation), both layers on a previously impregnated paper layer l, 30 - 50 paper webs (impre~nated with a phenol-formaldehyde resin) as the core layer 13, , 7~3 - Decorative layer 5 (synthetic resin containing organic dyestuff pigments and polymerized by radiation), and - Transparent layer 6 (synthetic resin s polymerized by radiation) as the outermost layer, both layers on a previously impregnated paper layer 1.
The resulting decorative panel 14 has a scratch resistance higher than 2.0 N (DIN 53,799, part 10). Its surface is not attacked by concentrated mineral acid during a treatment time of 6 hours~ The fastness to light of this panel is given the rating 8 (DIN 54,004). It has a surface gloss corresponding to a reflectometer value of 22-24, 60 angle of incidence, and a reflectometer value of 44-45, B5 angle of incidence (DIN 67,530).
Exam~le 3 The pasty, dyestuff-containing liquid 2, composed of radiation-polymerizable compounds/ of Example 1 is applied to a sulfate kraft paper 1 which has first been impregnated with a heat-curable phenol-formaldehyde resin (amount of resin applied 70%)of~ich the resin has ~been partially cured,anda continuous film (layer thickness about 80 /um) is formed (cf. Fig.
2s 3). :~
A transparent layer~6 composed of a pastyr dyestuff-free liquid composed of the same radiation-polymerizable compounds is applied (layer thickness ; about ~0 to 40 /um) to a delustered polypropylene plastics film 3. The pa~er 1 and the plasti~s film 3 are then placed one on top of the other in sheet or web ' ' , , , . .
.
~ 71 ~
form, so that the two liquid layers 2 and 6 come into contact with one another. In so doing, care must be taken that inclusions of air are not formed. The polymerizable compounds are crosslinked by means of electron beams which impinge on the liquid layers 2 and 6 through the plastics film 3. The dose absorbed is 60 kGy. After the plastics film 3 has been removed, the paper l containing the polymerized surface layer 2 and 6 is processed further to give a decorative panel 14 by lo compression under heat together with a paper stack 13 as described in Example 2.
The layers of synthetic resin polymerized by radiation in the examples still exhibit relatively low ~alues of scratch resistance within the range rom about 0.7 to 0.9 Newtons before the compression under heat. ~ substantially higher surface hardness in the panel is only obtained, surprisingly, after the layer of synthetic resin polymerized by radiation has been subjected, in accordance with the invention, to compression under heat.
The reflectometer value measured with a Dr.
Lange type RB reflectometer as specified in DIN 67,530 is 45 to 47, 20 angle of incidence, and about 83, 60 angle of incidence, if the delustered plastic~ film is absent when curing with electron beams is carried out.
It falls to values of 37 to 41, 20 angle of incidence, and about 79, 60 angle of incidence, if texturized compression elements which impart to the outermost layer of the panel, for example, a surface structure similar to that of orange peel are used in the compression under heat. Even lower reflectometer values of about 30 to 36, 20 angle of incidence, and about 75, 60 angle of incidence, can be achieved by adding delustering agents to the surface layer. The particularly low gloss values according to the , ~X907~L8 invention can, however, only be achieved by means of the special measures used in the polymerization of the synthetic resin layer.
-2~-,
Claims (24)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A decorative panel, comprising:
a core layer;
an outermost layer applied over said core layer, said outermost layer being a snythetic resin polymerized by radiation and comprising an unsaturated acrylate or an unsaturated methacrylate, said outermost layer further being scratch-resistant at a scratch loading of at least about 1.5 Newtons as defined by DIN 53,799 part 10 and having a reflectometer value no greater than about 50 at an angle of incidence of 85° as defined by DIN
67,530; and decoration means for forming a decoration covering said core layer.
a core layer;
an outermost layer applied over said core layer, said outermost layer being a snythetic resin polymerized by radiation and comprising an unsaturated acrylate or an unsaturated methacrylate, said outermost layer further being scratch-resistant at a scratch loading of at least about 1.5 Newtons as defined by DIN 53,799 part 10 and having a reflectometer value no greater than about 50 at an angle of incidence of 85° as defined by DIN
67,530; and decoration means for forming a decoration covering said core layer.
2. A decorative panel as claimed in Claim 1, wherein said outermost layer is scratch-resistant at a scratch loading of from about 2 to about 7 Newtons.
3. A decorative panel as claimed in Claim 1, wherein said snythetic resin comprises an epoxy-acrylate or methacrylate oligomer, a silicone-acrylate or methacrylate oligomer, a polyester acrylate or methacrylate oligomer or a urethane acrylate or methacrylate oligomer.
4. A decorative panel as claimed in Claim 3, wherein said outermost layer includes mono-, di-, tri-, tetra-, penta-, or hexaacrylate or -methacrylate polymerized with said synthetic resin.
5. A decorative panel as claimed in Claim 4, wherein said outermost layer includes an acrylate or a methacrylate of a polyol or ether polyol.
- 25a -
- 25a -
6. A decorative panel as claimed in Claim 5, wherein said synthetic resin comprises an epoxy-acrylate oligomer, a silicone-acrylate oligomer or a polyester-acrylate oligomer.
7. A decorative panel as claimed in Claim 4, wherein said synthetic resin comprises said aliphatic urethane acrylate oligomer which has been polymerized by radiation together with a diacrylate or triacrylate.
8. A decorative panel as claimed in Claim 1 which includes an underlay between said core and said outermost layer, said underlay comprising a pigmented or non-pigmented nonwoven fabric or paper and a heat curable aminoplast or phenoplast resin.
9. A decorative panel as claimed in Claim 1, wherein said decoration means is incorporated in said outermost layer.
10. A decorative panel as claimed in Claim 9, wherein said core layer comprises wood, plastic or metal, or a plurality of paper layers, and wherein a layer of paper is positioned between said core layer and said outermost layer.
11. A decorative panel as claimed in Claim 1, wherein said decorative panel includes at least one additional layer between said core layer and said outermost layer, said decoration means being incorporated in said additional layer, and wherein said outermost layer is clear.
12. A decorative panel as claimed in Claim 1, wherein said decoration means comprises a decorative layer between said core layer and said outermost layer, said decorative layer comprising a dyed or printed organic polymer film or paper.
13. A decorative panel as claimed in Claim 1, wherein a separate outermost layer is applied on opposite sides of said core layer.
14. A process for the production of a decorative panel, comprising:
applying a layer of a liquid synthetic resin polymerizable by radiation and comprising an unsaturated acrylate or an unsaturated methacrylate, to a substrate;
applying a film having a surface roughness over said resin layer;
transferring said surface roughness to said resin layer;
polymerizing said resin layer by exposure to radiation;
and compressing said resin layer and said substrate at an elevated temperature, and wherein said resin layer includes decoration means.
applying a layer of a liquid synthetic resin polymerizable by radiation and comprising an unsaturated acrylate or an unsaturated methacrylate, to a substrate;
applying a film having a surface roughness over said resin layer;
transferring said surface roughness to said resin layer;
polymerizing said resin layer by exposure to radiation;
and compressing said resin layer and said substrate at an elevated temperature, and wherein said resin layer includes decoration means.
15. A process as claimed in Claim 14 including the step of removing said film from said resin layer prior to said compressing step.
16. A process as claimed in Claim 14, wherein said substrate comprises a paper or a decorative paper layer, and wherein said compressing step includes compressing said resin layer and said paper or decorative paper layer to a core layer.
17. A process as claimed in Claim 16, wherein said compressing step includes compressing a separate resin layer and paper or decorative paper layer on opposite sides of said core layer, said paper or decorative paper layer being adjacent said core layer.
18. A process as claimed in Claim 14, wherein said compressing step includes compressing said resin layer at a temperature of from about 80 to about 220°C and at a pressure of from about 5 to about 100 bar.
19. A process for the production of a decorative panel, comprising:
applying a first layer containing decoration means to a substrate;
applying a second layer over said first layer, said second layer being synthetic resin polymerizable by radiation and comprising an unsaturated acrylate or an unsaturated methacrylate;
applying a film having a surface roughness over said second layer;
transferring said surface roughness to said second layer;
polymerizing said resin layer by exposure to radiation;
and compressing said first and second layers and said substrate at an elevated temperature.
applying a first layer containing decoration means to a substrate;
applying a second layer over said first layer, said second layer being synthetic resin polymerizable by radiation and comprising an unsaturated acrylate or an unsaturated methacrylate;
applying a film having a surface roughness over said second layer;
transferring said surface roughness to said second layer;
polymerizing said resin layer by exposure to radiation;
and compressing said first and second layers and said substrate at an elevated temperature.
20. A process as claimed in Claim 19, wherein said first layer is a synthetic resin and is partially cured on said substrate prior to application of said second layer.
21. A process as claimed in Claim 19 wherein said film is applied over said second layer prior to applying said second layer over said first layer.
22. A process as claimed in Claim 19, wherein said substrate layer comprises paper, and wherein said compressing step includes compressing said paper layer and said first and second layers onto a core layer.
23. A process as claimed in Claim 22, wherein said compressing step includes compressing separate paper layers and first and second layers on opposite sides of said core layer, said paper layers being adjacent said core layer.
24. A process as claimed in Claim 19, wherein said compressing step includes compressing at least said second layer at a temperature of from about 80 to about 220°C and at a pressure of from about 5 to about 100 bar.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3533737.0 | 1985-09-21 | ||
| DE19853533737 DE3533737A1 (en) | 1985-09-21 | 1985-09-21 | DECORATIVE PLATE WITH IMPROVED SURFACE PROPERTIES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1290718C true CA1290718C (en) | 1991-10-15 |
Family
ID=6281596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 518621 Expired - Lifetime CA1290718C (en) | 1985-09-21 | 1986-09-19 | Decorative panel a core and outermost layer of radiation-polymerized resin |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4789604A (en) |
| EP (1) | EP0216269B1 (en) |
| JP (1) | JP2536853B2 (en) |
| AT (1) | ATE75448T1 (en) |
| AU (1) | AU597272B2 (en) |
| CA (1) | CA1290718C (en) |
| DE (2) | DE3533737A1 (en) |
| ES (1) | ES2002759A6 (en) |
| NO (1) | NO863746L (en) |
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| PL2927017T5 (en) | 2014-04-04 | 2022-06-20 | Flooring Industries Limited, Sarl | Method of covering a substrate |
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| NL2016282B1 (en) | 2016-02-18 | 2017-08-24 | Trespa Int Bv | A decorative panel. |
| US11745475B2 (en) | 2016-08-19 | 2023-09-05 | Wilsonart Llc | Surfacing materials and method of manufacture |
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| WO2019226041A1 (en) * | 2018-05-21 | 2019-11-28 | 5R Technologies Sdn. Bhd. | A natural effect panel and method of fabricating the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3841956A (en) * | 1970-12-03 | 1974-10-15 | Westinghouse Electric Corp | Bonded weather resistant decorative laminate with slightly grained acrylic surface |
| US3874906A (en) * | 1972-09-22 | 1975-04-01 | Ppg Industries Inc | Process for applying polyester-acrylate containing ionizing irradiation curable coatings |
| JPS53142502A (en) * | 1977-05-19 | 1978-12-12 | Okura Industrial Co Ltd | Production of decorative plate |
| DE3010060A1 (en) * | 1980-03-15 | 1981-10-01 | Letron GmbH, 8750 Aschaffenburg | MULTI-LAYERED PLATE HAVING A VARNISH SURFACE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| JPS5723590A (en) * | 1980-07-18 | 1982-02-06 | Shin Meiwa Ind Co Ltd | Charger for body to be carried such as dust |
| JPS587464A (en) * | 1981-07-06 | 1983-01-17 | Showa Electric Wire & Cable Co Ltd | Electrically insulating paint |
| JPS588650A (en) * | 1981-07-08 | 1983-01-18 | バンドー化学株式会社 | Decorative wood |
| DE3147989A1 (en) * | 1981-12-04 | 1983-06-16 | Hoechst Ag, 6230 Frankfurt | DECORATIVE, IN PARTICULAR PLATE-SHAPED MOLDED PART, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF |
| JPS58211448A (en) * | 1982-06-03 | 1983-12-08 | 凸版印刷株式会社 | Manufacture of decorative material |
| US4490409A (en) * | 1982-09-07 | 1984-12-25 | Energy Sciences, Inc. | Process and apparatus for decorating the surfaces of electron irradiation cured coatings on radiation-sensitive substrates |
| JPS59156749A (en) * | 1983-02-25 | 1984-09-06 | 東洋インキ製造株式会社 | Manufacture of decorative board |
| DE3418282A1 (en) * | 1984-05-17 | 1985-11-21 | Hoechst Ag, 6230 Frankfurt | DECORATIVE PLATE WITH IMPROVED SURFACE PROPERTIES |
-
1985
- 1985-09-21 DE DE19853533737 patent/DE3533737A1/en not_active Withdrawn
-
1986
- 1986-09-11 DE DE8686112598T patent/DE3685074D1/en not_active Expired - Lifetime
- 1986-09-11 EP EP19860112598 patent/EP0216269B1/en not_active Expired - Lifetime
- 1986-09-11 AT AT86112598T patent/ATE75448T1/en not_active IP Right Cessation
- 1986-09-19 ES ES8602045A patent/ES2002759A6/en not_active Expired
- 1986-09-19 CA CA 518621 patent/CA1290718C/en not_active Expired - Lifetime
- 1986-09-19 NO NO863746A patent/NO863746L/en unknown
- 1986-09-22 AU AU63036/86A patent/AU597272B2/en not_active Expired
- 1986-09-22 US US06/909,551 patent/US4789604A/en not_active Expired - Lifetime
- 1986-09-22 JP JP22227186A patent/JP2536853B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6299147A (en) | 1987-05-08 |
| NO863746D0 (en) | 1986-09-19 |
| DE3533737A1 (en) | 1987-03-26 |
| AU597272B2 (en) | 1990-05-31 |
| US4789604A (en) | 1988-12-06 |
| AU6303686A (en) | 1987-03-26 |
| DE3685074D1 (en) | 1992-06-04 |
| JP2536853B2 (en) | 1996-09-25 |
| EP0216269A3 (en) | 1988-12-21 |
| EP0216269A2 (en) | 1987-04-01 |
| NO863746L (en) | 1987-03-23 |
| ES2002759A6 (en) | 1988-10-01 |
| EP0216269B1 (en) | 1992-04-29 |
| ATE75448T1 (en) | 1992-05-15 |
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Legal Events
| Date | Code | Title | Description |
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| MKLA | Lapsed | ||
| MKEC | Expiry (correction) | ||
| MKEC | Expiry (correction) |
Effective date: 20121205 |