EP0123308A1 - Process for locally matting synthetic coatings, and products obtained - Google Patents
Process for locally matting synthetic coatings, and products obtained Download PDFInfo
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- EP0123308A1 EP0123308A1 EP84104555A EP84104555A EP0123308A1 EP 0123308 A1 EP0123308 A1 EP 0123308A1 EP 84104555 A EP84104555 A EP 84104555A EP 84104555 A EP84104555 A EP 84104555A EP 0123308 A1 EP0123308 A1 EP 0123308A1
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- European Patent Office
- Prior art keywords
- zone
- initiators
- coating
- carried out
- polymerization
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- 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.)
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
- D06N7/0005—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface
- D06N7/0028—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface characterised by colour effects, e.g. craquelé, reducing gloss
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/20—Applying plastic materials and superficially modelling the surface of these materials
- B44C1/205—Applying plastic materials and superficially modelling the surface of these materials chemical modelling
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
- D06N7/0005—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface
- D06N7/0007—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface characterised by their relief structure
- D06N7/0013—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface characterised by their relief structure obtained by chemical embossing (chemisches Prägen)
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
- D06N7/0005—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface
- D06N7/0007—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface characterised by their relief structure
- D06N7/0023—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface characterised by their relief structure obtained by physical means, e.g. differential heating or differential irradiation; masking certain areas during treating
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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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
Definitions
- the present invention relates to a process for locally mattering a synthetic covering surface, more particularly a floor or wall covering based on PVC and the products obtained.
- Said zones can for example be a pattern applied by printing on a coating or an imitation of a joint, in the case of a coating imitating a ceramic tile.
- the matt state of the zone which is obtained by a grain-forming cylinder, disappears in any case partially, during the subsequent possibly local heating of said zone.
- the present invention aims to provide an improved method which makes it possible to obtain a high degree of mattness on the surface of an area of a synthetic coating.
- the object is achieved by a process in which at least one coating or impression containing at least one first polymerization initiator and, in a second zone which can be deposited on a foamable support or not, in a first zone.
- at least one coating based on crosslinkable monomer containing at least one second polymerization initiator at least two initiators being different and triggered either by different effects, or by the same effect for different spectral zones; pre-gelation is carried out; graining is carried out at least locally; only the first zone is polymerized in order to fix its appearance and gelling which, causing the fluidifi cation of the varnish, causes the disappearance of the grainy appearance in the non-crosslinked zone, and possibly expansion and thermal crosslinking.
- spectral zone is meant, in the broadest sense, temperature ranges, frequency ranges and other ranges capable of decomposing the initiator by forming the free radicals or ions necessary for propagation of chains in a polymerization reaction.
- the process of the present invention therefore makes it possible to advantageously separate the polymerization initiations in the zones in question, according to the products used so that the polymerization initiation energy supplied to a first zone cannot initiate the polymerization of the other area.
- a coating based on crosslinkable monomer which contains a thermal polymerization initiator; pregelification is carried out at a temperature such that the decomposition of the thermal initiator is zero or negligible; graining is carried out at least locally, the coating of the first zone is polymerized by initiation under UV radiation in order to fix its appearance and a gelling is carried out which, causing the fluidization of the varnish, causes the disappearance of the grained appearance in the uncrosslinked area, and possibly expansion and thermal crosslinking.
- thermal initiators can be used at different initiation temperatures, or two UV initiators at different UV frequencies of initiation. It is also possible to combine the abovementioned initiators together or to combine them with other polymerization initiators, such as ionic initiators, these can also be combined with one another. It can therefore be seen that the method of the invention allows many variants.
- the first zone can advantageously be a joint between two tiles in the case of a coating imitating the ceramic coating.
- the coating or printing of the first zone can be carried out on a foamable support or on a non-expandable or slightly expandable support.
- At least one of the zones and preferably the zone of the joint in a pattern of tiles may contain an expansion inhibitor.
- the method of the invention also has the advantage of allowing graining of the entire surface, without having to provide a particular grain roller controlled in accordance with the pattern or the decoration of the coating, since the area which is not polymerized after graining will be fluidized during the subsequent gelation treatment and will be smoothed by surface tension.
- Particularly preferred compounds are 1,4-butylene glycol dimethacrylate and and trimethylolpropane trimethacrylate.
- 1,1,3,3-tetramethylbutyl hydroperoxide, cumyl hydroperoxide, 2,5-dimethylhexane 2,5-dihydroperoxide, t-butyl hydroperoxide and peroxide are preferred.
- azo compounds of the AIBN (azo-bisisobutyronitrile) type or inorganic compounds comprising the peroxide bond are also possible to use, as initiators, azo compounds of the AIBN (azo-bisisobutyronitrile) type or inorganic compounds comprising the peroxide bond.
- AIBN azo-bisisobutyronitrile
- UV polymerization initiator preferably use Merck products DAROCUR ® 1173 or DAROCUR ® ll16 at a rate of 1 to 50%, preferably 20% by weight, of the ink or the cut.
- TMA trimellitic anhydride
- the coating containing the crosslinkable monomer as well as the initiator of the second zone, in the particular case the thermal initiator, contains 1 to 50%, preferably 11% by weight of monomer comprising at least two chain propagation sites, optionally mixed with monomers having a chain propagation site.
- said second zone can be initiated directly or by means of a radiative energy transfer agent, so that each of the initiations can be triggered by its own physicochemical effect.
- a radiative energy transfer agent so that each of the initiations can be triggered by its own physicochemical effect.
- the initiation of polymerization of the second zone by direct radiative route or by means of an energy transfer agent can be carried out by X-ray, an electron beam or by t-radiation.
- the energy transfer agent In order for the energy transfer agent to be able to fully exert its effect, it must act on a product for which sufficient mobility of the crosslinkable monomer is ensured.
- This condition is best achieved from the hot industrial point of view by subjecting the product to an oven, preferably the oven in which gelation and / or possible expansion is carried out in a conventional manner or immediately upon leaving this oven when the product is still at a sufficient temperature.
- an oven preferably the oven in which gelation and / or possible expansion is carried out in a conventional manner or immediately upon leaving this oven when the product is still at a sufficient temperature.
- the polymerization can be brought about in the first zone by the techniques described above, and then the polymerization in the second zone by the appropriate physicochemical means, and this without significant modifications to the production lines of flooring. existing.
- the different initiation effects used in the respective zones will of course be chosen so as to have sufficiently different initial effects to obtain the desired effect. For example, it might be difficult to master an operation in which two different UV initiators, i.e. triggered by different UV radiation ranges, would be used because the separation of the effects in the UV spectrum would be difficult to achieve.
- the support consists of a substrate 1 and a coating at the rate of 50D g / m 2 of a foamable plastisol 2.
- a foamable plastisol 2 On this coating of foamable plastisol, one deposits ( Figure 2), in one or more stages, in a first zone, according to a decoration imitating the design of a tiling joint 3, a conventional ink containing an expansion inhibitor and approximately 20% of a UV initiator DAROCUR @ 1173 or 1116 and, according to a decorative pattern any 4, an ink containing a UV initiator
- the ink can be replaced by a cut, that is to say a solution without dye or pigment, depending on the decorative effects which it is desired to obtain.
- This deposit is advantageously done by a gravure printing technique.
- FIG. 4 represents the graining step by means of a graining cylinder, over the entire surface, at a temperature which does not allow the polymerization of the plastisol, that is to say at a temperature higher than 100 ° C, under a pressure depending on the degree of matte desired.
- the pre-gelation and graining steps can be carried out in a single step, using an adequately heated graining cylinder.
- Passage under a UV lamp 7 makes it possible to crosslink the area containing the U.V. initiator so that the (grained) state of this area is fixed by the crosslinking.
- the product obtained is passed, for one minute to two minutes and thirty seconds, in an oven at approximately 200 ° C., intended to expand the foamable coating 2 in places which do not contain an expansion inhibitor and to polymerize the area containing the thermal initiator.
- the zone which has not been polymerized during the UV initiation undergoes during gelling, a fluidification which has the effect of smoothing the grained surface, while the grained and crosslinked zone during the initiation UV maintains its grainy (mat) state.
- the product shown in FIG. 6 is obtained.
- Example 2 The procedure is as in Example 1, with the difference however that the ink used contains 1 to 20% of benzoyl peroxide dissolved in the minimum amount of ether or methyl ethyl ketone.
- the coating deposited on the entire surface contains, as in Example 1, the other thermal initiator: cumyl hydroperoxide and the desired effect will in this case be caused by varying the initiation temperatures different from the initiators used.
- a first heat treatment (pre-gelling) is indeed carried out at 120 ° C, followed by graining and finally a gelling and expansion step at 180-200 ° C which can be accompanied by mechanical smoothing .
- Example 2 The procedure is as in Example 2, using 1 to 20% of azoisobutyronitrile (AIBN) dissolved in the minimum amount of methyl ethyl ketone and added to the ink.
- AIBN azoisobutyronitrile
- Example 2 The procedure is as in Example 1, replacing the PVC with a copolymer of PVC (95%) and polyvinyl acetate (5%), all the other parts remaining equal.
- the pregelling is advantageously carried out on a cylinder at 130 ° C., this temperature can even be exceeded as a function of the running speed of the product.
Abstract
Le procédé comporte le dépôt sur un support moussable ou non (2), dans une première zone (3), d'une enduction ou impression contenant au moins un premier initiateur de polymérisation et, dans une deuxième zone (5) qui peut éventuellement comprendre partiellement la première zone, d'une enduction à base de monomère réticulable contenant au moins un deuxième initiateur de polymérisation, au moins deux initiateurs étant différents et déclenchés soit par des effects différents soit par un même effet pour des zones spectrales différentes, une prégélification et au moins localement un grainage; une polymérisation de la première zone afin de fixer son aspect et une gélification qui, causant la fluidification du vernis, provoque la disparition de l'aspect grainé dans la zone non réticulée, et éventuellement une expansion et une réticulation thermique. Application à la réalisation de revêtements de murs et de sols.The method comprises depositing on a foamable or non-foamable support (2), in a first zone (3), a coating or impression containing at least a first polymerization initiator and, in a second zone (5) which may optionally include partially the first zone, of a coating based on crosslinkable monomer containing at least a second polymerization initiator, at least two initiators being different and triggered either by different effects or by the same effect for different spectral zones, pregelification and at least locally graining; a polymerization of the first zone in order to fix its appearance and a gelling which, causing the fluidization of the varnish, causes the disappearance of the grainy appearance in the non-crosslinked zone, and possibly an expansion and a thermal crosslinking. Application to the production of wall and floor coverings.
Description
La présente invention concerne un procédé destiné à matter localement une surface de revêtement synthétique, plus particulièrement un revêtement de sol ou mural à base de PVC et les produits obtenus.The present invention relates to a process for locally mattering a synthetic covering surface, more particularly a floor or wall covering based on PVC and the products obtained.
La majorité des revêtements plastiques ne présentent pas au niveau de leur surface, une différence suffisante de brillance-matité pour donner à certaines zones de la surface un aspect particulier. Lesdites zones peuvent par exemple être un motif appliqué par impression sur un revêtement ou une imitation de joint, dans le cas d'un revêtement imitant un carrelage céramique.The majority of plastic coatings do not have a sufficient difference in gloss-mattness at their surface to give certain areas of the surface a particular appearance. Said zones can for example be a pattern applied by printing on a coating or an imitation of a joint, in the case of a coating imitating a ceramic tile.
Généralement l'état mat de la zone, qui est obtenu par un cylindre graineur, disparaît en tout cas partiellement, lors du chauffage ultérieur éventuellement local de ladite zone.Generally the matt state of the zone, which is obtained by a grain-forming cylinder, disappears in any case partially, during the subsequent possibly local heating of said zone.
Dans les documents US-A-4,273,819 et FR-A-2.531.009 on a décrit diverses techniques visant à réaliser une mati- fication locale.In the documents US-A-4,273,819 and FR-A-2,531,009, various techniques have been described aimed at carrying out local matification.
La présente invention vise à fournir un procédé amélioré qui permet d'obtenir un degré de matité élevé à la surface d'une zone d'un revêtement synthétique.The present invention aims to provide an improved method which makes it possible to obtain a high degree of mattness on the surface of an area of a synthetic coating.
Suivant l'invention, le but est atteint par un procédé dans lequel on dépose sur un support moussable ou non, dans une première zone, au moins une enduction ou impression contenant au moins un premier initiateur de polymérisation et, dans une deuxième zone qui peut éventuellement comprendre partiellement la première zone, au moins une enduction à base de monomère réticulable contenant au moins un deuxième initiateur de polymérisation, au moins deux initiateurs étant différents et déclenchés soit par des effets différents, soit par un même effet pour des zones spectrales différentes; on effectue une prégélification; on effectue au moins localement un grainage; on ne polymérise que la première zone afin de fixer son aspect et effectue une gélification qui, causant la fluidification du vernis, provoque la disparition de l'aspect grainé dans la zone non réticulée, et éventuellement une expansion et une réticulation thermique.According to the invention, the object is achieved by a process in which at least one coating or impression containing at least one first polymerization initiator and, in a second zone which can be deposited on a foamable support or not, in a first zone. optionally partially comprising the first zone, at least one coating based on crosslinkable monomer containing at least one second polymerization initiator, at least two initiators being different and triggered either by different effects, or by the same effect for different spectral zones; pre-gelation is carried out; graining is carried out at least locally; only the first zone is polymerized in order to fix its appearance and gelling which, causing the fluidifi cation of the varnish, causes the disappearance of the grainy appearance in the non-crosslinked zone, and possibly expansion and thermal crosslinking.
Par zone spectrale, on entend, au sens le plus large, des plages de températures, des plages de fréquences et autres plages capables de décomposer l'initiateur en formant les radicaux libres ou ions nécessaires à une propagation de chaînes dans une réaction de polymérisation.By spectral zone is meant, in the broadest sense, temperature ranges, frequency ranges and other ranges capable of decomposing the initiator by forming the free radicals or ions necessary for propagation of chains in a polymerization reaction.
Le procédé de la présente invention permet donc de séparer avantageusement les initiations de polymérisation dans les zones en question, suivant les produits utilisés de telle sorte que l'énergie d'initiation de polymérisation apportée à une première zone ne puisse initier la polymérisation de l'autre zone.The process of the present invention therefore makes it possible to advantageously separate the polymerization initiations in the zones in question, according to the products used so that the polymerization initiation energy supplied to a first zone cannot initiate the polymerization of the other area.
Cette séparation des effets permet donc de polymériser une zone et de fixer son aspect, puis de polymériser la deuxième zone sans altérer l'aspect de la première zone.This separation of effects therefore makes it possible to polymerize an area and to fix its appearance, then to polymerize the second area without altering the appearance of the first area.
Ceci s'applique donc particulièrement bien à l'obtention de degrés de matité différents; ainsi, suivant une première variante du procédé de l'invention, on dépose sur un support moussable ou non, dans une première zone, une encre ou une coupure contenant un initiateur de polymérisation et pouvant contenir un inhibiteur de moussage et, dans une deuxième zone qui peut éventuellement comprendre au moins partiellement la première zone, une enduction à base de monomère réticulable, qui contient un initiateur de polymérisation thermique; on effectue une prégélification à une température telle que la décomposition de l'initiateur thermique soit nulle ou négligeable; on effectue au moins localement un grainage, on polymérise le revêtement de la première zone par initiation sous un rayonnement U.V. afin de fixer son aspect et on effectue une gélification qui, causant la fluidification du vernis, provoque la disparition de l'aspect grainé dans la zone non réticulée, et éventuellement une expansion et une réticulation thermique.This therefore applies particularly well to obtaining different degrees of dullness; thus, according to a first variant of the process of the invention, an ink or a cut containing a polymerization initiator and which may contain a foaming inhibitor and, in a second zone, is deposited on a foamable support or not, in a first zone. which may optionally comprise at least partially the first zone, a coating based on crosslinkable monomer, which contains a thermal polymerization initiator; pregelification is carried out at a temperature such that the decomposition of the thermal initiator is zero or negligible; graining is carried out at least locally, the coating of the first zone is polymerized by initiation under UV radiation in order to fix its appearance and a gelling is carried out which, causing the fluidization of the varnish, causes the disappearance of the grained appearance in the uncrosslinked area, and possibly expansion and thermal crosslinking.
Cette technique n'est évidemment pas limitée aux initiateurs thermiques et/ou U.V. Suivant l'invention, on peut utiliser deux initiateurs thermiques différents à températures d'initiation différentes, ou deux initiateurs U.V. à fréquences U.V. d'initiation différentes. On peut également combiner entre eux les initiateurs précités ou les combiner avec d'autres initiateurs de polymérisation, tels les initiateurs ioniques, ceux-ci pouvant également être combinés entre eux. On voit donc que le procédé de l'invention permet de nombreuses variantes.This technique is obviously not limited to Thermal and / or UV initiators According to the invention, two different thermal initiators can be used at different initiation temperatures, or two UV initiators at different UV frequencies of initiation. It is also possible to combine the abovementioned initiators together or to combine them with other polymerization initiators, such as ionic initiators, these can also be combined with one another. It can therefore be seen that the method of the invention allows many variants.
Il faut également noter que la première zone peut avantageusement être un joint entre deux carrelages dans le cas d'un revêtement imitant le revêtement céramique. Elle peut cependant également représenter un motif quelconque. De ce fait, l'enduction ou l'impression de la première zone peut être effectuée sur un support moussable ou sur un support non expansible ou peu expansible.It should also be noted that the first zone can advantageously be a joint between two tiles in the case of a coating imitating the ceramic coating. However, it can also represent any reason. Therefore, the coating or printing of the first zone can be carried out on a foamable support or on a non-expandable or slightly expandable support.
Suivant un mode d'exécution complémentaire, l'une des zones au moins et de préférence la zone du joint dans un motif de carrelages peut contenir un inhibiteur d'expansion.According to a complementary embodiment, at least one of the zones and preferably the zone of the joint in a pattern of tiles may contain an expansion inhibitor.
Le procédé de l'invention présente également l'avantage de permettre un grainage de toute la surface, sans devoir prévoir un cylindre graineur particulier commandé en concordance avec le motif ou le décor du revêtement, puisque la zone qui n'est pas polymérisée après grainage sera fluidifiée au cours du traitement ultérieur de gélification et se lissera par tension superficielle.The method of the invention also has the advantage of allowing graining of the entire surface, without having to provide a particular grain roller controlled in accordance with the pattern or the decoration of the coating, since the area which is not polymerized after graining will be fluidized during the subsequent gelation treatment and will be smoothed by surface tension.
A titre d'exemple de monomères convenant pour la mise en pratique de l'invention, on peut citer les composés suivants (énumération non limitative) :
- diméthacrylate d'éthylèneglycol,
- diacrylate d'éthylèneglycol,
- diméthacrylate de diéthylèneglycol,
- diacrylate de diéthylèneglycol,
- diméthacrylate de triéthylèneglycol,
- diacrylate de triéthylèneglycol,
- diméthacrylate de tétraéthylèneglycol,
- diacrylate de tétraéthylèneglycol,
- diméthacrylate de polyéthylèneglycol,
- diacrylate de polyéthylèneglycol,
- diméthacrylate de 1,3-butylèneglycol,
- diméthacrylate de 1,4-butylèneglycol,
- diacrylate de 1,3-butylèneglycol,
- diacrylate de 1,4-butylèneglycol,
- diacrylate de 1,4-butanediol,
- diméthacrylate de 1,6-hexanediol,
- diacrylate de 1,6-hexanediol,
- diacrylate de néopentylglycol,
- diméthacrylate de néopentylglycol,
- diméthacrylate (éthoxylé) de bisphénol A,
- divinylbenzène,
- divinyltoluène,
- triméthacrylate de triméthylolpropane,
- triacrylate de triméthylolpropane,
- triacrylate de pentaérythritol,
- triméthacrylate de glycéryle,
- tétracrylate de pentaérythritol,
- tétraméthacrylate de pentaérythritol,
- diméthacrylate de 1,4-butanediol.
- ethylene glycol dimethacrylate,
- ethylene glycol diacrylate,
- diethylene glycol dimethacrylate,
- diethylene glycol diacrylate,
- triethylene glycol dimethacrylate,
- triethylene glycol diacrylate,
- tetraethylene glycol dimethacrylate,
- tetraethylene glycol diacrylate,
- polyethylene glycol dimethacrylate,
- polyethylene glycol diacrylate,
- 1,3-butylene glycol dimethacrylate,
- 1,4-butylene glycol dimethacrylate,
- 1,3-butylene glycol diacrylate,
- 1,4-butylene glycol diacrylate,
- 1,4-butanediol diacrylate,
- 1,6-hexanediol dimethacrylate,
- 1,6-hexanediol diacrylate,
- neopentylglycol diacrylate,
- neopentylglycol dimethacrylate,
- bisphenol A (ethoxylated) dimethacrylate,
- divinylbenzene,
- divinyltoluene,
- trimethylolpropane trimethacrylate,
- trimethylolpropane triacrylate,
- pentaerythritol triacrylate,
- glyceryl trimethacrylate,
- pentaerythritol tetracrylate,
- pentaerythritol tetramethacrylate,
- 1,4-butanediol dimethacrylate.
A ces composés qui possèdent au moins deux sites de propagation, on peut ajouter une certaine quantité de composés monomères comportant un site de propagation.To these compounds which have at least two propagation sites, it is possible to add a certain quantity of monomeric compounds comprising a propagation site.
Des composés particulièrement préférés sont le diméthacrylate de 1,4-butylèneglycol et et le triméthacrylate de triméthylolpropane.Particularly preferred compounds are 1,4-butylene glycol dimethacrylate and and trimethylolpropane trimethacrylate.
A titre d'exemple et selon un mode d'exécution particulièrement avantageux, la couche d'usure qui constitue la deuxième zone est déposée à raison de 300 g par m2 et est constituée d'un mélange de 100 parties d'un vernis de base qui contient :
- - 100 parties de PVC obtenu par émulsion,
- - 42 parties de plastifiants (phtalate)
- - 3 parties de stabilisants (baryum-zinc) et
- - 15 parties de white spirit,
de 12,4 parties d'un monomère acrylique (ROCRYL®980 - ROHM & HAAS) et de 0,1 à 0,3 partie d'une solution à 80 % d'hydroperoxyde de cumyle (initiateur thermique), dans le cumène.By way of example and according to a particularly advantageous embodiment, the wear layer which constitutes the second zone is deposited at the rate of 300 g per m 2 and consists of a mixture of 100 parts of a varnish of base which contains:
- - 100 parts of PVC obtained by emulsion,
- - 42 parts of plasticizers (phthalate)
- - 3 parts of stabilizers (barium-zinc) and
- - 15 parts of white spirit,
12.4 parts of an acrylic monomer (ROCRYL®980 - ROHM & HAAS) and 0.1 to 0.3 part of an 80% solution of cumyl hydroperoxide (thermal initiator) in cumene.
On peut encore citer, à titre d'exemple, mais sans vouloir être limitatif, les initiateurs thermiques suivants :
- peroxyde de benzoyle,
- peroxyde de diisobutyryle,
- peroxyde de 2,4-dichlorobenzoyle,
- peroxyde de diisononanoyle
- peroxyde de décanoyle,
- peroxyde de lauroyle,
- peroxyde d'acétyle,
- peroxyde de l'acide succinique,
- peroxyde de bis-p-chlorobenzoyle,
- 2,5-dihydroperoxy-2,5-diméthylhexane,
- hydroperoxyde de cumyle,
- hydroperoxyde de t-butyle,
- hydroperoxyde de p-menthane,
- hydroperoxyde de diisopropylbenzène,
- hydroperoxyde de 1,1,3,3-tétraméthylbutyle,
- peroxydicarbonate de di(n-propyle),
- peroxydicarbonate de diisopropyle,
- peroxydicarbonate de di(sec-butyle)
- peroxydicarbonate de di(2-éthylhexyle)
- peroxydicarbonate de dicyclohexyle,
- peroxydicarbonate de dicétyle,
- peroxydicarbonate de bis(4-t-butylcyclohexyle),
- monocarbonate de t-butylperoxyisopropyle,
- 1,1-bis(t-butylperoxy)-3,3,5-triméthylcyclohexane,
- peroxyacétate de t-butyle,
- peroxyisobutyrate de t-butyle,
- peroxy-2-éthylhexanoate de t-butyle,
- peroxypivalate de t-butyle,
- peroxynéodécanoate de t-butyle,
- hydroperoxyde de t-butyle,
- acide t-butyle peroxymaléique,
- diperoxyphtalate de di-t-butyle,
- 2,5-diméthyl-2,5-bis(peroxybenzoyle)hexane,
- 2,3-diméthyl-2,5-bis-octanoylperoxy)hexane,
- peroctoate de t-butyle,
- perbenzoate de t-butyle,
- peroxyde d'acétylcyclohexyl sulfonyle,
- peroxyde d'acétylsec-heptyl sulfonyle,
- peroxyde de méthyléthylcétone,
- peroxyde de 2,4-pentanedione,
- peroxyde de cyclohexanone.
- benzoyl peroxide,
- diisobutyryl peroxide,
- 2,4-dichlorobenzoyl peroxide,
- diisononanoyl peroxide
- decanoyl peroxide,
- lauroyl peroxide,
- acetyl peroxide,
- succinic acid peroxide,
- bis-p peroxide - chlorobenzoyl,
- 2,5-dihydroperoxy-2,5-dimethylhexane,
- cumyl hydroperoxide,
- t-butyl hydroperoxide,
- p-menthane hydroperoxide,
- diisopropylbenzene hydroperoxide,
- 1,1,3,3-tetramethylbutyl hydroperoxide,
- di (n-propyl) peroxydicarbonate,
- diisopropyl peroxydicarbonate,
- di (sec-butyl) peroxydicarbonate
- di (2-ethylhexyl) peroxydicarbonate
- dicyclohexyl peroxydicarbonate,
- diketyl peroxydicarbonate,
- bis (4-t-butylcyclohexyl) peroxydicarbonate,
- t-butylperoxyisopropyl monocarbonate,
- 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane,
- t-butyl peroxyacetate,
- t-butyl peroxyisobutyrate,
- t-butyl peroxy-2-ethylhexanoate,
- t-butyl peroxypivalate,
- t-butyl peroxynodeodecanoate,
- t-butyl hydroperoxide,
- peroxymaleic t-butyl acid,
- di-t-butyl diperoxyphthalate,
- 2,5-dimethyl-2,5-bis (peroxybenzoyl) hexane,
- 2,3-dimethyl-2,5-bis-octanoylperoxy) hexane,
- t-butyl peroctoate,
- t-butyl perbenzoate,
- acetylcyclohexyl sulfonyl peroxide,
- acetylsec-heptyl sulfonyl peroxide,
- methyl ethyl ketone peroxide,
- 2,4-pentanedione peroxide,
- cyclohexanone peroxide.
Parmi ceux-ci, on préfère l'hydroperoxyde de 1,1,3,3-tétraméthylbutyle, l'hydroperoxyde de cumyle, le 2,5-dihydroperoxyde de 2,5-diméthylhexane, l'hydroperoxyde de t-butyle et le peroxyde de 2,4-pentanedione, tout particulièrement l'hydroperoxyde de cumyle à des taux d'au moins 0,0001 %.Among these, 1,1,3,3-tetramethylbutyl hydroperoxide, cumyl hydroperoxide, 2,5-
Du fait qu'un grand nombre de ces peroxydes présentent une décomposition trop importante à la température de travail habituelle, il peut être intéressant d'y ajouter des inhibiteurs de décomposition de l'initiateur thermique du type (énumération non limitative) :
- acide benzoïque,
- pyridine,
- phénol,
- alcool benzylique,
- résorcine,
- éthylamine,
- benzylamine,
- hydroquinone,
- pyrocatéchol,
- pyrogallol.
- benzoic acid,
- pyridine,
- phenol,
- benzyl alcohol,
- resorcin,
- ethylamine,
- benzylamine,
- hydroquinone,
- pyrocatechol,
- pyrogallol.
On peut également utiliser comme initiateurs des composés azoiques du type AIBN (azo-bisisobutyronitrile) ou des composés inorganiques comportant la liaison peroxyde.It is also possible to use, as initiators, azo compounds of the AIBN (azo-bisisobutyronitrile) type or inorganic compounds comprising the peroxide bond.
Ces produits sont choisis en fonction des conditions de température et de pression de mise en oeuvre et en fonction de la vitesse de production, en tenant compte de leur cinétique.These products are chosen according to the conditions of temperature and pressure of implementation and according to the speed of production, taking into account their kinetics.
A titre d'initiateur de polymérisation U.V., on utilise de préférence les produits Merck DAROCUR ® 1173 ou DAROCUR ® ll16 à raison de 1 à 50 %, de préférence 20 % en poids, de l'encre ou de la coupure.As a UV polymerization initiator, preferably use Merck products DAROCUR ® 1173 or DAROCUR ® ll16 at a rate of 1 to 50%, preferably 20% by weight, of the ink or the cut.
D'autres composés tels que les suivants conviennent également (énumération non limitative) :
- benzophénone,
- 2-chloro-thioxanthone,
- 2-méthyl-thioxanthone,
- 2-isopropyl-thioxanthone, benzoïne,
- 4,4'-diméthyoxybenzoine,
- benzoïne-éthyl-éther,
- benzoïne-isopropyl-éther,
- benzyldiméthylcétal,
- 1,1,1,-trichloro-acétophénone,
- 1-phényl-1,2-propanedione-2-(éthoxycarbonyl)-oxime, diéthoxyacétophénone,
- dibenzosubérone,
- Darocur ® 1398
- Darocur ® 1174
- Darocur ® 1020.
- benzophenone,
- 2-chloro-thioxanthone,
- 2-methyl-thioxanthone,
- 2-isopropyl-thioxanthone, benzoin,
- 4,4'-dimethyoxybenzoine,
- benzoin-ethyl ether,
- benzoin-isopropyl-ether,
- benzyldimethylketal,
- 1,1,1, -trichloroacetophenone,
- 1-phenyl-1,2-propanedione-2- (ethoxycarbonyl) -oxime, diethoxyacetophenone,
- dibenzosuberone,
- Darocur ® 1398
- Darocur ® 1174
- Darocur ® 1020.
On peut également utiliser les inhibiteurs d'expansion classiques, de préférence l'anhydride trimellitique (TMA) pour un moussage différentiel.Conventional expansion inhibitors can also be used, preferably trimellitic anhydride (TMA) for differential foaming.
L'enduction contenant le monomère réticulable ainsi que l'initiateur de la deuxième zone, dans le cas particulier l'initiateur thermique, contient 1 à 50 %, de préférence 11 % en poids de monomère comportant au moins deux sites de propagation de chaîne, éventuellement en mélange avec des monomères possédant un site de propagation de chaîne.The coating containing the crosslinkable monomer as well as the initiator of the second zone, in the particular case the thermal initiator, contains 1 to 50%, preferably 11% by weight of monomer comprising at least two chain propagation sites, optionally mixed with monomers having a chain propagation site.
L'invention sera décrite plus en détail à l'appui des figures annexées dans lesquelles :
- la figure 1 représente le support utilisé pour le procédé de l'invention,
- la figure 2 représente la première étape du procédé,
- la figure 3 représente le revêtement après l'enduction de la deuxième zone,
- la figure 4 représente l'étape de grainage,
- la figure 5 représente la première initiation de polymérisation et
- la figure 6 représente le produit fini.
- FIG. 1 represents the support used for the method of the invention,
- FIG. 2 represents the first step of the process,
- Figure 3 shows the coating after the duction of the second zone,
- FIG. 4 represents the graining step,
- FIG. 5 represents the first initiation of polymerization and
- Figure 6 shows the finished product.
Il faut noter que la description à l'aide de modes d'exécution particulièrement préférés de l'invention est uniquement données à titre d'exemple et qu'elle ne vise nullement à limiter la portée de la présente invention. Des variantes opératoires, telles que la réalisation d'un relief par des techniques sérigraphiques, relèvent aussi de l'invention, ainsi que l'impression de motifs par technique sérigraphique.It should be noted that the description using particularly preferred embodiments of the invention is only given by way of example and that it in no way aims to limit the scope of the present invention. Operational variants, such as the production of a relief by screen printing techniques, also fall within the scope of the invention, as well as the printing of patterns by screen printing technique.
Selon une variante de l'invention, il est aussi possible de compléter le lissage par tension superficielle se produisant lors de la gélification, soit par un traitement de lissage mécanique par rouleau, soit par un grainage, de préférence léger, à chaud.According to a variant of the invention, it is also possible to complete the smoothing by surface tension occurring during gelation, either by a mechanical smoothing treatment by roller, or by a graining, preferably light, hot.
Il relève également de l'invention de prévoir une exposition à des rayonnements infra-rouges en fin de traitement, par exemple à la sortie d'un four d'expansion afin d'assister l'opération de lissage de la surface du produit.It is also a matter of the invention to provide exposure to infrared radiation at the end of treatment, for example at the outlet of an expansion furnace in order to assist the smoothing operation of the surface of the product.
Selon une forme d'exécution complémentaire, afin de faciliter les opérations de production du revêtement de sols ou de murs et pouvoir initier différentiellement les étapes de réticulation, il est prévu que ladite deuxième zone peut être initiée directement ou par l'intermédiaire d'un agent de transfert énergétique par voie radiative, de manière que chacune des initiations puisse être déclenchée par un effet physico-chimique qui lui est propre. De cette manière, il devient possible de séparer les initiations de polymérisation dans les zones en question en fonction des initiateurs et/ou des effets physico-chimiques d'initiation utilisés de telle sorte que l'énergie d'initiation de polymérisation apportée par voie radiative dans une première zone ne puisse initier la polymérisation de l'autre zone.According to an additional embodiment, in order to facilitate the production operations of the covering of floors or walls and to be able to initiate the crosslinking steps differently, it is provided that said second zone can be initiated directly or by means of a radiative energy transfer agent, so that each of the initiations can be triggered by its own physicochemical effect. In this way, it becomes possible to separate the polymerization initiations in the zones in question as a function of the initiators and / or of the physicochemical initiation effects used so that the polymerization initiation energy supplied by the radiative route in a first zone cannot initiate the polymerization of the other zone.
Cette séparation des effets permet donc de polymériser une zone et de fixer son aspect puis de polymériser la deuxième zone sans altérer l'aspect de la première zone.This separation of effects therefore allows poly merit an area and fix its appearance then polymerize the second area without altering the appearance of the first area.
Avantageusement, l'initiation de polymérisation de la deuxième zone par voie radiative directe ou par l'intermédiaire d'un agent de transfert énergétique peut être effectuée par un-rayonnement X, un faisceau d'électrons ou par un rayonnement t.Advantageously, the initiation of polymerization of the second zone by direct radiative route or by means of an energy transfer agent can be carried out by X-ray, an electron beam or by t-radiation.
Afin que l'agent de transfert énergétique puisse exercer pleinement son effet, celui-ci doit agir sur un produit pour lequel une mobilité suffisante du monomère réticulable est assurée.In order for the energy transfer agent to be able to fully exert its effect, it must act on a product for which sufficient mobility of the crosslinkable monomer is ensured.
Cette condition est la mieux réalisée du point de vue industriel à chaud en soumettant le produit dans un four, de préférence le four dans lequel on réalise de manière classique la gélification et/ou l'expansion éventuelle ou immédiatement à la sortie de ce four quand le produit est encore à une température suffisante.This condition is best achieved from the hot industrial point of view by subjecting the product to an oven, preferably the oven in which gelation and / or possible expansion is carried out in a conventional manner or immediately upon leaving this oven when the product is still at a sufficient temperature.
De cette manière, on peut provoquer la polymérisation dans la première zone par les techniques décrites ci-dessus, et ensuite la polymérisation dans la deuxième zone par les moyens physico-chimiques adéquats, et ceci sans modifications importantes des lignes de production de revêtement de sol existantes.In this way, the polymerization can be brought about in the first zone by the techniques described above, and then the polymerization in the second zone by the appropriate physicochemical means, and this without significant modifications to the production lines of flooring. existing.
On choisira bien entendu les différents effets d'initiation utilisés dans les zones respectives de manière à pouvoir disposer d'effets initiatifs suffisamment différents pour obtenir l'effet souhaité. A titre d'exemple, il pourrait être difficile de maîtriser une opération dans laquelle deux initiateurs U.V. différents, c'est-à-dire déclenchés par des plages de radiations U.V. différentes, seraient utilisés car la séparation des effets dans le spectre U.V. serait difficile à réaliser.The different initiation effects used in the respective zones will of course be chosen so as to have sufficiently different initial effects to obtain the desired effect. For example, it might be difficult to master an operation in which two different UV initiators, i.e. triggered by different UV radiation ranges, would be used because the separation of the effects in the UV spectrum would be difficult to achieve.
Les monomères utilisés, les techniques d'application localisées dans les différentes zones et, de manière générale, l'ensemble du processus technologique est identique, mutatis mutandis à ce qui a été décrit ci-dessus.The monomers used, the application techniques located in the different zones and, in general, the whole technological process is identical, mutatis mutandis to what has been described above.
La technique à mettre en oeuvre pour réaliser l'initiation dans ladite deuxième zone par voie radiative en utilisant comme monomère le triméthylacrylate de triméthylolpropane peut être celle décrite par exemple par Salmon et Loan J. Appl. Polym. Sci., 16, 671 (1972).The technique to be used to carry out initiation in said second zone by radiative means using trimethylolpropane trimethylacrylate as monomer can be that described for example by Salmon and Loan J. Appl. Polym. Sci., 16, 671 (1972).
Pour la mise en pratique des techniques impliquant le recours aux faisceaux d'électrons, on peut notamment recourir à l'appareillage "ELECTROCURTAIN" fabriqué par Ateliers de Charmilles (Energy Sciences International) de Genève (Suisse) en appliquant une énergie suffisante pour pénétrer en profondeur la couche à réticuler, par exemple de l'ordre de 175 KV pour des doses de 2 Mrad.For the implementation of techniques involving the use of electron beams, one can in particular use the "ELECTROCURTAIN" apparatus manufactured by Ateliers de Charmilles (Energy Sciences International) of Geneva (Switzerland) by applying sufficient energy to penetrate into depth of the layer to be crosslinked, for example of the order of 175 KV for doses of 2 Mrad.
De préférence, le support est constitué d'un subjectile 1 et d'une enduction à raison de 50D g/m2 d'un plastisol moussable 2. Sur cette enduction de plastisol moussable, on dépose (figure 2), en une ou plusieurs étapes, dans une première zone, selon un décor imitant le dessin d'un joint de carrelage 3, une encre classique contenant un inhibiteur d'expansion et environ 20 % d'un initiateur U.V. DAROCUR @ 1173 ou 1116 et, selon un motif décoratif quelconque 4, une encre contenant un initiateur U.V. Il est bien évident que l'encre peut être remplacée par une coupure, c'est-à-dire une solution sans colorant ou pigment, selon les effets décoratifs que l'on désire obtenir. Ce dépôt se fait avantageusement par une technique d'impression par héliogravure.Preferably, the support consists of a
Ensuite, on dépose (figure 3) sur toute la surface une enduction de plastisol transparent, à titre de couche d'usure 5, contenant un monomère acrylique (ROCRYL ®980) et l'initiateur thermique, de préférence l'hydroperoxyde de cumyle; puis on effectue une prégélification à une température telle que la décomposition de l'initiateur thermique soit nulle ou négligeable, c'est-à-dire entre 100 et 160 degrés.Is then deposited (Figure 3) over the entire surface a transparent plastisol coating, as a
La figure 4 représente l'étape de grainage au moyen d'un cylindre de grainage, sur toute la surface, à une température ne permettant pas la polymérisation du plastisol, c'est-à-dire à une température supérieure à 100° C, sous une pression dépendant du degré de matite désiré. Les étapes de prégélification et de grainage peuvent être effectuées en une seule étape, au moyen d'un cylindre de grainage chauffé de manière adéquate.FIG. 4 represents the graining step by means of a graining cylinder, over the entire surface, at a temperature which does not allow the polymerization of the plastisol, that is to say at a temperature higher than 100 ° C, under a pressure depending on the degree of matte desired. The pre-gelation and graining steps can be carried out in a single step, using an adequately heated graining cylinder.
Le passage sous une lampe U.V. 7 (figure 5) permet de réticuler la zone contenant l'initiateur U.V. de manière à ce que l'état (grainé) de cette zone soit fixé par la réticulation.Passage under a UV lamp 7 (FIG. 5) makes it possible to crosslink the area containing the U.V. initiator so that the (grained) state of this area is fixed by the crosslinking.
Ensuite, on fait passer le produit obtenu, pendant une minute à deux minutes trente secondes, dans un four à environ 200° C, destiné à expanser l'enduction moussable 2 aux endroits qui ne contiennent pas d'inhibiteur d'expansion et à polymériser la zone contenant l'initiateur thermique. Lors de cette polymérisation, la zone qui n'a pas été polymérisée lors de l'initiation U.V. subit lors de la gélification, une fluidification qui a pour effet de lisser la surface grainée, tandis que la zone grainée et réticulée lors de l'initiation U.V. maintient son état grainé (mat). On obtient le produit représenté à la figure 6.Then, the product obtained is passed, for one minute to two minutes and thirty seconds, in an oven at approximately 200 ° C., intended to expand the
On procède comme dans l'exemple 1, à la différence cependant que l'encre utilisée contientl à 20 % de peroxyde de benzoyle solubilisé dans le minimum d'éther ou de méthyl-éthyl-cétone.The procedure is as in Example 1, with the difference however that the ink used contains 1 to 20% of benzoyl peroxide dissolved in the minimum amount of ether or methyl ethyl ketone.
L'enduction déposée sur toute la surface contient comme dans l'exemple 1, l'autre initiateur thermique : hydroperoxyde de cumyle et l'effet souhaité sera dans ce cas provoqué en jouant sur les températures d'initiation différentes des initiateurs utilisés.The coating deposited on the entire surface contains, as in Example 1, the other thermal initiator: cumyl hydroperoxide and the desired effect will in this case be caused by varying the initiation temperatures different from the initiators used.
Un premier traitement thermique (pré-gélification) est en effet effectué à 120° C, suivi d'un grainage et finalement d'une étape de gélification et d'expansion à 180-200° C pouvant s'accompagner d'un lissage mécanique.A first heat treatment (pre-gelling) is indeed carried out at 120 ° C, followed by graining and finally a gelling and expansion step at 180-200 ° C which can be accompanied by mechanical smoothing .
On procède comme dans l'exemple 2 en utilisant 1 à 20 % d'azoisobutyronitrile (AIBN) solubilisé dans le minimum de méthyl-éthyl-cétone et ajouté à l'encre.The procedure is as in Example 2, using 1 to 20% of azoisobutyronitrile (AIBN) dissolved in the minimum amount of methyl ethyl ketone and added to the ink.
On procède comme dans l'exemple 1, en remplaçant le PVC par un copolymère de PVC (95 %) et d'acétate de polyvinyle (5 %), toutes les autres parties restant égales.The procedure is as in Example 1, replacing the PVC with a copolymer of PVC (95%) and polyvinyl acetate (5%), all the other parts remaining equal.
La composition suivante a été utilisée :
La prégélification est avantageusement effectuée sur cylindre à 130° C, cette température pouvant être même dépassée en fonction de la vitesse de défilement du produit.The pregelling is advantageously carried out on a cylinder at 130 ° C., this temperature can even be exceeded as a function of the running speed of the product.
On constate que cette composition permet de réaliser une meilleure gélification et un meilleur lissage.It is found that this composition makes it possible to achieve better gelation and better smoothing.
Claims (24)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT84104555T ATE28761T1 (en) | 1983-04-25 | 1984-04-21 | PROCESSES FOR LOCAL MATTING OF SYNTHETIC COATINGS AND THE PRODUCTS OBTAINED IN THE WAY. |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
LU84765 | 1983-04-25 | ||
LU84765A LU84765A1 (en) | 1983-04-25 | 1983-04-25 | METHOD FOR LOCAL MATIFICATION OF SYNTHETIC COATINGS AND PRODUCTS OBTAINED |
LU84957 | 1983-08-11 | ||
LU84957A LU84957A1 (en) | 1983-08-11 | 1983-08-11 | PVC floor covering material - with smooth and matt zones formed using polymerisation initiators with differential curing conditions |
Publications (2)
Publication Number | Publication Date |
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EP0123308A1 true EP0123308A1 (en) | 1984-10-31 |
EP0123308B1 EP0123308B1 (en) | 1987-08-05 |
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EP84104555A Expired EP0123308B1 (en) | 1983-04-25 | 1984-04-21 | Process for locally matting synthetic coatings, and products obtained |
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US (1) | US4608294A (en) |
EP (1) | EP0123308B1 (en) |
CA (1) | CA1251764A (en) |
DE (1) | DE3465208D1 (en) |
DK (1) | DK168743B1 (en) |
ES (1) | ES532397A0 (en) |
FR (1) | FR2544635B1 (en) |
GR (1) | GR81939B (en) |
IE (1) | IE55251B1 (en) |
IT (1) | IT1209533B (en) |
NO (1) | NO164646C (en) |
PT (1) | PT78481B (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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US5153047A (en) * | 1989-06-06 | 1992-10-06 | Armstrong World Industries, Inc. | Release carrier with spherulite formations |
US5080954A (en) * | 1989-06-06 | 1992-01-14 | Armstrong World Industries, Inc. | Surface covering with inverse spherulite patterns |
US20020009554A1 (en) * | 1997-06-26 | 2002-01-24 | Weder Donald E. | Preformed pot cover formed of polymeric materials having a texture or appearance simulating the texture or appearance of paper |
US7081291B2 (en) * | 2002-01-11 | 2006-07-25 | Domco Tarkett Inc. | Selectively embossed surface coverings and processes of manufacture |
CA2473028A1 (en) * | 2002-01-11 | 2003-07-17 | Tarkett Inc. | Selectively embossed surface coverings and processes of manufacture |
EP1493861A1 (en) * | 2003-07-02 | 2005-01-05 | Tarkett SAS | Selectively embossed surface coverings and processes of manufacture |
US8801887B2 (en) * | 2005-12-23 | 2014-08-12 | The Boeing Company | Textured structure and method of making the textured structure |
JP5373272B2 (en) * | 2007-06-18 | 2013-12-18 | ニチハ株式会社 | Exterior wall plate and coating method thereof |
CN109789661A (en) * | 2016-07-18 | 2019-05-21 | 博优国际集团公众有限公司 | Show the multi-layer sheet for being suitable as floor or wall covering of three-dimensional embossment and decorative picture |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1061259A (en) * | 1952-08-05 | 1954-04-12 | Blanchiment Et Apprets De Tara | Process and device for the manufacture of polyvinyl chloride floor and floor coverings and resulting product |
US3310422A (en) * | 1965-07-16 | 1967-03-21 | Congoleum Nairn Inc | Smooth wear-resistant resilient floor covering and method of making same |
FR1538506A (en) * | 1966-07-25 | 1968-09-06 | Ici Ltd | Production of a pigmented and embossed thermoplastic sheet |
GB1159645A (en) * | 1966-07-06 | 1969-07-30 | Gaf Corp | Foamed Decorative Covering Material and Method of Manufacture |
FR2235796A1 (en) * | 1973-07-06 | 1975-01-31 | Marley Tile Ag | |
US4068030A (en) * | 1972-07-18 | 1978-01-10 | Armstrong Cork Company | Multilevel embossing by printing with a reactive monomer |
US4273819A (en) * | 1980-07-10 | 1981-06-16 | Congoleum Corporation | Differential gloss products and methods of making the same |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4029831A (en) * | 1975-06-19 | 1977-06-14 | Masonite Corporation | Method of making a multi-gloss panel |
US4172169A (en) * | 1976-10-01 | 1979-10-23 | Nairn Floors Limited | Floor or wall coverings |
US4187131A (en) * | 1978-02-21 | 1980-02-05 | Congoleum Corporation | Resinous polymer sheet materials having selective, surface decorative effects and methods of making the same |
US4491616A (en) * | 1982-05-28 | 1985-01-01 | Congoleum Corporation | Resinous polymer sheet material having surface decorative effects of contrasting gloss and method of making the same |
-
1984
- 1984-04-18 IE IE967/84A patent/IE55251B1/en not_active IP Right Cessation
- 1984-04-18 NO NO841604A patent/NO164646C/en not_active IP Right Cessation
- 1984-04-20 IT IT8420662A patent/IT1209533B/en active
- 1984-04-21 DE DE8484104555T patent/DE3465208D1/en not_active Expired
- 1984-04-21 EP EP84104555A patent/EP0123308B1/en not_active Expired
- 1984-04-24 PT PT78481A patent/PT78481B/en not_active IP Right Cessation
- 1984-04-24 FR FR8406411A patent/FR2544635B1/en not_active Expired
- 1984-04-24 GR GR74484A patent/GR81939B/el unknown
- 1984-04-24 CA CA000452584A patent/CA1251764A/en not_active Expired
- 1984-04-25 US US06/603,843 patent/US4608294A/en not_active Ceased
- 1984-04-25 DK DK206884A patent/DK168743B1/en active IP Right Grant
- 1984-04-25 ES ES532397A patent/ES532397A0/en active Granted
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1061259A (en) * | 1952-08-05 | 1954-04-12 | Blanchiment Et Apprets De Tara | Process and device for the manufacture of polyvinyl chloride floor and floor coverings and resulting product |
US3310422A (en) * | 1965-07-16 | 1967-03-21 | Congoleum Nairn Inc | Smooth wear-resistant resilient floor covering and method of making same |
GB1159645A (en) * | 1966-07-06 | 1969-07-30 | Gaf Corp | Foamed Decorative Covering Material and Method of Manufacture |
FR1538506A (en) * | 1966-07-25 | 1968-09-06 | Ici Ltd | Production of a pigmented and embossed thermoplastic sheet |
US4068030A (en) * | 1972-07-18 | 1978-01-10 | Armstrong Cork Company | Multilevel embossing by printing with a reactive monomer |
FR2235796A1 (en) * | 1973-07-06 | 1975-01-31 | Marley Tile Ag | |
US4273819A (en) * | 1980-07-10 | 1981-06-16 | Congoleum Corporation | Differential gloss products and methods of making the same |
Also Published As
Publication number | Publication date |
---|---|
EP0123308B1 (en) | 1987-08-05 |
IE840967L (en) | 1984-10-25 |
DK206884A (en) | 1984-10-26 |
DK168743B1 (en) | 1994-05-30 |
PT78481A (en) | 1984-05-01 |
PT78481B (en) | 1986-05-22 |
ES8503574A1 (en) | 1985-03-16 |
FR2544635A1 (en) | 1984-10-26 |
IE55251B1 (en) | 1990-07-18 |
NO164646C (en) | 1990-10-31 |
ES532397A0 (en) | 1985-03-16 |
DE3465208D1 (en) | 1987-09-10 |
FR2544635B1 (en) | 1986-10-03 |
GR81939B (en) | 1984-12-12 |
NO164646B (en) | 1990-07-23 |
US4608294A (en) | 1986-08-26 |
IT1209533B (en) | 1989-08-30 |
CA1251764A (en) | 1989-03-28 |
IT8420662A0 (en) | 1984-04-20 |
NO841604L (en) | 1984-10-26 |
DK206884D0 (en) | 1984-04-25 |
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