EP0739435B1 - Impregnated paper sheet as decorative overlay - Google Patents
Impregnated paper sheet as decorative overlay Download PDFInfo
- Publication number
- EP0739435B1 EP0739435B1 EP94902840A EP94902840A EP0739435B1 EP 0739435 B1 EP0739435 B1 EP 0739435B1 EP 94902840 A EP94902840 A EP 94902840A EP 94902840 A EP94902840 A EP 94902840A EP 0739435 B1 EP0739435 B1 EP 0739435B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sheet
- decorative
- impregnated
- parts
- poly
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
-
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/35—Polyalkenes, e.g. polystyrene
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/22—Structures being applied on the surface by special manufacturing processes, e.g. in presses
- D21H27/24—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the surface to be covered being phenolic-resin paper laminates, vulcan fibre or similar cellulosic fibreboards
-
- 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]
- Y10T428/31971—Of carbohydrate
- Y10T428/31975—Of cellulosic next to another carbohydrate
- Y10T428/31978—Cellulosic next to another 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]
- Y10T428/31971—Of carbohydrate
- Y10T428/31975—Of cellulosic next to another carbohydrate
- Y10T428/31978—Cellulosic next to another cellulosic
- Y10T428/31982—Wood or paper
-
- 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]
- Y10T428/31971—Of carbohydrate
- Y10T428/31993—Of paper
Definitions
- the invention relates to a paper sheet impregnated with a composition in aqueous medium used as coating decorative in the manufacture of panels or profiles decorative.
- the invention also relates to decorative panels or profiles comprising this sheet as well as the methods of manufacturing such sheets and panels or sections comprising such sheets.
- Decorative panels have been used for many years as materials in homes and business premises and industrial. A typical application of such panels is the surface coating of furniture, table tops, walls and others.
- the so-called high pressure panels are produced from a core consisting of sheets, generally made of kraft paper, impregnated with thermosetting resin and more particularly with a phenolic resin.
- a decorative sheet is placed on the stack of sheets constituting the core, which is generally a sheet of paper bearing a printed or colored pattern or comprising decorative particles, impregnated with a thermosetting resin which does not yellow with heat.
- a protective covering sheet called an "overlay", without pattern and transparent in the final laminate, is placed above the decorative sheet.
- the stack of impregnated sheets is then placed in a press fitted with a sheet giving the surface condition. Then, the stack is densified by heating and pressing to obtain a unitary structure. This structure is then fixed on a basic support, for example it is glued to a particle board.
- So-called low pressure panels are produced using only a decorative sheet impregnated with resin thermosetting (and possibly an overlay sheet) that laminate directly on the base support.
- the third kind of decorative panels is constituted by the panels composed of a basic support, in general a panel of particles of wood or agglomerated fibers, and a sheet of decorative paper impregnated with a composition, fixed on the support by means of an adhesive.
- the sheet of paper is a decorative sheet of uniform color or with decorative patterns. The patterns are generally applied by printing on the sheet, before or after impregnation. We also apply a varnish or lacquer which aims to protect the surface of the sheet.
- These sheets are most often impregnated using a sizing press or other impregnation device on a paper machine or outside of a paper machine, with compositions comprising aqueous dispersions based on styrene-acrylate copolymer ethyl butyl acrylate and an aqueous solution of resins comprising formaldehyde such as melamine-formaldehyde or urea-formaldehyde resins.
- the sheets impregnated online on a paper machine are said to be prepregs and those impregnated offline are said to be post-impregnated.
- the invention relates to these two types of impregnated sheets.
- the problem to solve is therefore to provide sheets impregnated with no formaldehyde while having the characteristics required for its application, in particular a high internal cohesion combined with good deformability.
- Sheets must also have good printability and have good aptitude for lacquering or varnishing.
- the Applicant has found that the problems are solved by using as an impregnation composition, a composition free from formaldehyde and which comprises a crosslinkable polymer and having a glass transition temperature of between ⁇ 10 and 35 ° C., used in the form of a stable aqueous dispersion other than a styrene-ethyl acrylate-butyl acrylate copolymer, and a water-soluble binder in certain proportions.
- a polymer in the form of microdroplets in stable aqueous dispersion is also called latex.
- the glass transition temperature (denoted Tg) is between 0 and 20 ° C. The lower limit of the Tg is justified in particular by the fact that if the Tg is very low, the composition can cause problems of fouling on the machine.
- the invention provides an impregnated sheet for coating decorative as defined in claim 1.
- the polymer can be self-crosslinkable or crosslinkable by action from an outside agent.
- the crosslinkable polymer used in the form of a stable aqueous dispersion is preferably chosen from styrene-butadiene copolymers, styrene-butadiene carboxylated copolymers, polymers of acetate of vinyl including poly (ethylene / vinyl acetate), acrylic polymers and derivatives other than a styrene-ethyl acrylate-butyl acrylate copolymer, urethane polymers and mixtures thereof.
- polymer it is necessary to understand homopolymer or copolymer.
- the invention is characterized in that the water-soluble binder is preferably chosen from polyvinyl alcohol, gelatin, starches, cellulose derivatives, alginates and their mixtures.
- cellulose derivatives carboxymethylcellulose can be used in particular.
- the sheet according to the invention is characterized by the fact that it is impregnated with a composition comprising 95 to 50 parts by dry weight of crosslinkable polymer and 5 to 50 parts by dry weight of water-soluble binder, the sum of the respective parts being equal to 100.
- the water-soluble binder is a polyvinyl alcohol having a degree of hydrolysis of 98-99 and a viscosity of 4 mPa.s, [determined at 20 ° C according to standard DIN 53015 for a 4% solution].
- the degree of hydrolysis is expressed as usual in% of moles of hydrolyzed acetate.
- the sheet is impregnated of a composition comprising 70 to 90 parts by dry weight of poly (ethylene / vinyl acetate) and 30 to 10 parts by dry weight poly (vinyl alcohol) defined above, the sum of the parts being 100.
- the invention also relates to decorative panels or profiles comprising such a sheet as a decorative sheet (claim 1), as well as a method of manufacturing the decorative sheet (claim 2) and a method of manufacturing a decorative panel or profile comprising said decorative sheet (claim 8).
- the impregnating composition used to impregnate the sheet used base to decorative coatings is substantially free of formaldehyde and contains a stable aqueous dispersion as a mixture of a crosslinkable polymer, having a transition temperature glassy between -10 and 35 ° C, other than a copolymer styrene-ethyl acrylate-butyl acrylate, and a binder water-soluble, in the relative proportions indicated in claim 1.
- the water-soluble binder is chosen from poly (vinyl alcohol), gelatin, starches, cellulose derivatives, alginates and their mixtures.
- the composition crosslinkable polymer in stable aqueous dispersion is chosen among the styrene-butadiene copolymers, the copolymers of carboxylated styrene-butadiene, polymers of acetate vinyl including poly (ethylene / vinyl acetate), polymers acrylics and derivatives other than a styrene-acrylate copolymer ethyl butyl acrylate, urethane polymers and their mixtures.
- composition comprises 95 to 50 parts by dry weight crosslinkable polymer, used in the form of an aqueous dispersion stable and 5 to 50 parts by dry weight of water-soluble binder, the sum of the respective shares being equal to 100.
- the water-soluble binder is a poly (vinyl alcohol) having a hydrolysis degree of 98-99 and a viscosity of 4 mPa.s [determined at 20 ° C according to DIN 53015 for a solution to 4%].
- the composition comprises 70 to 90 parts in dry weight of poly (ethylene / vinyl acetate) and 30 to 10 parts by dry weight of poly (vinyl alcohol), the sum of the parts being 100.
- the impregnating composition has a viscosity BROOKFIELD less than 200 mPa.s, measured at 100 revolutions per minute so that the sheet can be well impregnated.
- the impregnating composition may also include adjuvants free of formaldehyde commonly used in stationery for facilitate the impregnation and drying of the sheet such as wetting agents, coalescing agents, lubricants like calcium stearate, insolubilizers.
- a sheet of paper is conventionally formed from a composition of cellulose fibers, a binder and other papermaking adjuvants.
- the leaf is wrung and then dried; the sheet obtained has a grammage of 45 g / m 2 .
- the sheet is impregnated in a size press with a composition containing 80 parts by dry weight of a latex of a styrene-ethyl acrylate-butyl acrylate copolymer and 20 parts by dry weight of urea-formaldehyde resin, added in the form aqueous solution.
- the BROOKFIELD viscosity measured with a mobile at 100 rpm is 40 mPa.s.
- the sheet is dried at around 120 ° C. A sheet having a grammage of 60 g / m 2 is obtained.
- the quantity of formaldehyde released from the sheet is measured according to DIN 52368; it is expressed in mg of formaldehyde released per hour and per square meter of sheet. In this example, the amount of formaldehyde is 1.5.
- the internal cohesion of the lacquered sheet is measured to estimate its resistance to delamination and peeling, by a peeling test with an adhesive tape according to the following method: a strip of the sheet previously cut is fixed either in the direction machine, either crosswise on a glass plate using double-sided tape. A piece of adhesive tape is pressed on one side (TESA reference 4204 from the company) on the paper strip, one end of the piece of adhesive tape being kept free by application on an easel 80 mm high. After a period of 7 days, the adhesive tape is torn from the sheet by its free end. To see with the naked eye if the sample has been torn off, the adhesive tape is applied to a white or black background depending on the color of the test. In the case of the example, we check the ribbon on a white background.
- the resistance to deformability of the lacquered sheet is tested. by a wrinkle resistance test described in the article "WARING QUALITY OF EXPERIMENTAL CURRENCY-TYPE PAPERS, Journal of Research of the National Bureau of Standards, Volume 36, pages 249 to 268, March 1946.
- the number of creases is determined necessary to observe the first cracking of the lacquer. In this case, the number of creases is 1, which is very low.
- a sheet is produced as in Example 1 but it is impregnated with a composition containing 80 parts by dry weight of a poly (ethylene / vinyl acetate) latex - called EVA - which is self-crosslinking and whose glass transition temperature Tg is 6 ° C, and 20 parts by dry weight of polyvinyl alcohol having a degree of hydrolysis of 98-99 and a viscosity of 4 mPa.s [determined at 20 ° C according to standard DIN 53015 for a solution at 4%], added in the form of a 10% aqueous solution.
- the dry extract is adjusted so that the composition has a BROOKFIELD viscosity measured with a mobile at 100 rpm of 80 mPa.s.
- Example 1 The sheet thus impregnated is tested as in Example 1.
- the amount of formaldehyde is less than 0.15 mg / (hm 2 ). Its printability and its ability to varnish are of a level as good as that of Example 1. In this case, the number of creases is 8, which represents a very significant gain compared to the sheets according to the prior art.
- Example 2 We make a sheet as in Example 1 but we impregnate it with a composition containing 80 parts by dry weight of a latex polyacrylic, self-crosslinking and having a Tg of 32 ° C, and 20 parts by dry weight of the polyvinyl alcohol used in the example 2.
- the dry extract is adjusted so that the composition has a viscosity BROOKFIELD measured with a mobile at 100 rpm of 80 mPa.s.
- Example 1 The sheet thus impregnated is tested as in Example 1.
- the amount of formaldehyde is less than 0.15 mg / (hm 2 ). Its printability and its ability to varnish are of a level as good as that of Example 1. In this case, the number of creases is 4, which represents a still significant gain compared to the prior art.
- a sheet is produced as in Example 1 but it is impregnated with a composition containing 80 parts by dry weight of a crosslinkable poly (stryrene-butadiene-acrylate) latex and having a Tg of approximately 16 ° C, and 20 parts by dry weight of the polyvinyl alcohol used in Example 2.
- the dry extract is adjusted so that the composition has a BROOKFIELD viscosity measured with a mobile at 100 rpm of 75 mPa.s.
- Example 1 The sheet thus impregnated is tested as in Example 1.
- the amount of formaldehyde is less than 0.15 mg / (hm 2 ). Its printability and its ability to varnish are of a level as good as that of Example 1. In this case, the number of creases is 8.
- a sheet is produced as in Example 1 but it is impregnated with a composition containing 80 parts by dry weight of a latex of a crosslinkable styrene-acrylate copolymer and having a Tg of approximately 50 ° C., and 20 parts by dry weight of the poly (vinyl alcohol) used in Example 2.
- the dry extract is adjusted so that the composition has a BROOKFIELD viscosity measured with a mobile at 100 rpm of 75 mPa.s.
- Example 1 The sheet thus impregnated is tested as in Example 1.
- the amount of formaldehyde is less than 0.15 mg / (hm 2 ). Its printability and its ability to varnish are of a level as good as that of Example 1. However, the number of creases is 2, which is low.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Laminated Bodies (AREA)
- Paper (AREA)
Abstract
Description
L'invention concerne une feuille papetière imprégnée d'une composition en milieu aqueux utilisée comme revêtement décoratif dans la fabrication des panneaux ou profilés décoratifs. L'invention concerne aussi les panneaux ou profilés décoratifs comportant cette feuille ainsi que les procédés de fabrication de telles feuilles et des panneaux ou profilés comportant de telles feuilles.The invention relates to a paper sheet impregnated with a composition in aqueous medium used as coating decorative in the manufacture of panels or profiles decorative. The invention also relates to decorative panels or profiles comprising this sheet as well as the methods of manufacturing such sheets and panels or sections comprising such sheets.
Depuis de nombreuses années, on emploie des panneaux décoratifs comme matériaux dans les habitations et les locaux commerciaux et industriels. Une application typique de tels panneaux est le revêtement superficiel des meubles, des dessus de table, des murs et autres.Decorative panels have been used for many years as materials in homes and business premises and industrial. A typical application of such panels is the surface coating of furniture, table tops, walls and others.
Il existe plusieurs sortes de panneaux décoratifs : les panneaux dits haute pression, les panneaux dits basse pression et les panneaux recouverts d'une feuille adhésive.There are several kinds of decorative panels: panels so-called high pressure, so-called low pressure panels and panels covered with an adhesive sheet.
On produit les panneaux dits haute pression à partir d'une âme
constituée de feuilles, généralement en papier kraft, imprégnées
de résine thermodurcissable et plus particulièrement d'une résine
phénolique.
On place sur la pile de feuilles constituant l'âme, une feuille
décorative qui est en général une feuille de papier portant un
motif imprimé ou de couleur ou comportant des particules
décoratives, imprégnée d'une résine thermodurcissable ne
jaunissant pas à la chaleur. En général, on place au-dessus de
la feuille décorative, une feuille protectrice de recouvrement,
appelée "overlay", dépourvue de motif et transparente dans le
stratifié final. On place ensuite la pile de feuilles imprégnées
dans une presse munie d'une tôle conférant l'état de surface.
Puis, on densifie la pile par chauffage et pressage pour obtenir
une structure unitaire.
On fixe ensuite cette structure sur un support de base, par
exemple on la colle sur un panneau de particules.The so-called high pressure panels are produced from a core consisting of sheets, generally made of kraft paper, impregnated with thermosetting resin and more particularly with a phenolic resin.
A decorative sheet is placed on the stack of sheets constituting the core, which is generally a sheet of paper bearing a printed or colored pattern or comprising decorative particles, impregnated with a thermosetting resin which does not yellow with heat. In general, a protective covering sheet, called an "overlay", without pattern and transparent in the final laminate, is placed above the decorative sheet. The stack of impregnated sheets is then placed in a press fitted with a sheet giving the surface condition. Then, the stack is densified by heating and pressing to obtain a unitary structure.
This structure is then fixed on a basic support, for example it is glued to a particle board.
On produit des panneaux dits basse pression en utilisant uniquement une feuille décorative imprégnée de résine thermodurcissable (et éventuellement une feuille "overlay") que l'on stratifie directement sur le support de base.So-called low pressure panels are produced using only a decorative sheet impregnated with resin thermosetting (and possibly an overlay sheet) that laminate directly on the base support.
La troisième sorte de panneaux décoratifs est constituée par les
panneaux composés d'un support de base, en général un panneau de
particules de bois ou de fibres agglomérées, et d'une feuille de
papier décorative imprégnée d'une composition, fixée sur le
support au moyen d'un adhésif.
La feuille de papier est une feuille décorative de couleur
uniforme ou comportant des motifs décoratifs. Les motifs sont
généralement appliqués par impression sur la feuille, avant ou
après imprégnation. On applique en plus un vernis ou une laque
qui a pour but de protéger la surface de la feuille.The third kind of decorative panels is constituted by the panels composed of a basic support, in general a panel of particles of wood or agglomerated fibers, and a sheet of decorative paper impregnated with a composition, fixed on the support by means of an adhesive.
The sheet of paper is a decorative sheet of uniform color or with decorative patterns. The patterns are generally applied by printing on the sheet, before or after impregnation. We also apply a varnish or lacquer which aims to protect the surface of the sheet.
Ces feuilles sont le plus souvent imprégnées à l'aide d'une
presse encolleuse ou d'un autre dispositif d'imprégnation sur une
machine à papier ou hors machine à papier, avec des compositions
comportant des dispersions aqueuses à base de copolymère styrène-acrylate
d'éthyle-acrylate de butyle et d'une solution aqueuse
de résines comportant du formaldéhyde comme les résines mélamine-formaldéhyde
ou urée-formaldéhyde.
Les feuilles imprégnées en ligne sur machine à papier sont dites
préimprégnées et celles imprégnées hors ligne sont dites post-imprégnées.
L'invention concerne ces deux types de feuilles imprégnées.These sheets are most often impregnated using a sizing press or other impregnation device on a paper machine or outside of a paper machine, with compositions comprising aqueous dispersions based on styrene-acrylate copolymer ethyl butyl acrylate and an aqueous solution of resins comprising formaldehyde such as melamine-formaldehyde or urea-formaldehyde resins.
The sheets impregnated online on a paper machine are said to be prepregs and those impregnated offline are said to be post-impregnated.
The invention relates to these two types of impregnated sheets.
Un inconvénient majeur de ces feuilles ainsi imprégnées est
qu'elles contiennent du formaldéhyde qui est néfaste à la santé;
le taux de ce composé étant soumis à une législation de plus en
plus limitative.
Un autre inconvénient important est que leur flexibilité ou
aptitude à être déformée est un peu insuffisante, elles sont
fragiles à la manipulation, on observe donc des cassures ou
craquèlements de la feuille lorsqu'on l'applique sur une surface
non plane c'est-à-dire en relief ou en creux ou qui présente des
arêtes.A major drawback of these sheets thus impregnated is that they contain formaldehyde which is harmful to health; the level of this compound being subject to increasingly restrictive legislation.
Another important disadvantage is that their flexibility or aptitude to be deformed is a little insufficient, they are fragile with the handling, one thus observes cracks or cracking of the sheet when it is applied on a non planar surface that is ie in relief or in hollow or which has edges.
Par ailleurs elles doivent avoir une bonne résistance à la délamination, donc une bonne cohésion interne, afin qu'elles ne se désolidarisent pas du support sur lequel elles sont collées ni qu'il n'y ait de problèmes d'arrachage ou de détérioration de ces feuilles lors de l'usinage des panneaux.Furthermore, they must have good resistance to delamination, therefore good internal cohesion, so that they do not not dissociate from the support on which they are stuck nor that there are any problems with tearing off or deterioration of these sheets when machining the panels.
Ainsi les feuilles doivent être à la fois suffisamment souples et déformables pour permettre leur utilisation comme revêtement des surfaces non planes et avoir une cohésion interne élevée, or l'homme du métier sait qu'il est difficile d'obtenir simultanément ces deux caractéristiques pour une feuille.So the leaves must be both flexible enough and deformable to allow their use as a coating non-planar surfaces and have high internal cohesion, or those skilled in the art know that it is difficult to obtain these two characteristics simultaneously for a sheet.
Le problème à résoudre est donc de fournir des feuilles imprégnées ne comportant pas de formaldéhyde tout en ayant les caractéristiques requises à son application, en particulier une cohésion interne élevée alliée à une bonne déformabilité.The problem to solve is therefore to provide sheets impregnated with no formaldehyde while having the characteristics required for its application, in particular a high internal cohesion combined with good deformability.
Les feuilles doivent avoir aussi une bonne imprimabilité et avoir une bonne aptitude au laquage ou vernissage.Sheets must also have good printability and have good aptitude for lacquering or varnishing.
Dans la demande WO-A- 94/00523, (priorité 22.06.92, dépot 17.06.93, publication 06.01.94) on décrit une composition d'imprégnation d'une feuille pour revêtement décoratif qui est exempte de formaldéhyde et qui comporte un copolymère styrène-acrylate d'éthyle-acrylate de butyle et un liant.In application WO-A- 94/00523, (priority 22.06.92, deposit 17.06.93, publication 06.01.94) we describe a composition for impregnating a sheet for decorative coating which is free of formaldehyde and which contains a styrene-ethyl acrylate-acrylate copolymer butyl and a binder.
La demanderesse a trouvé que les problèmes sont résolus en
utilisant comme composition d'imprégnation, une composition
exempte de formaldéhyde et qui comporte un polymère réticulable
et ayant une température de transition vitreuse comprise entre -
10 et 35°C, utilisé sous forme d'une dispersion aqueuse stable
autre qu'un copolymère styrène-acrylate d'éthyle-acrylate de
butyle, et un liant hydrosoluble dans certaines proportions.
Un polymère sous forme de microgoutelettes en dispersion aqueuse
stable est aussi appelé latex.
De préférence, la température de transition vitreuse (notée Tg)
est comprise entre 0 et 20°C.
La limite inférieure de la Tg est justifiée notamment par le fait
que si la Tg est très basse, la composition peut poser des
problèmes d'encrassement sur machine. The Applicant has found that the problems are solved by using as an impregnation composition, a composition free from formaldehyde and which comprises a crosslinkable polymer and having a glass transition temperature of between −10 and 35 ° C., used in the form of a stable aqueous dispersion other than a styrene-ethyl acrylate-butyl acrylate copolymer, and a water-soluble binder in certain proportions. A polymer in the form of microdroplets in stable aqueous dispersion is also called latex.
Preferably, the glass transition temperature (denoted Tg) is between 0 and 20 ° C.
The lower limit of the Tg is justified in particular by the fact that if the Tg is very low, the composition can cause problems of fouling on the machine.
D'après les exemples décrits plus loin, si la Tg est trop élevée (supérieure à 40°C environ), l'aptitude de la feuille à se déformer est faible.From the examples described below, if the Tg is too high (greater than about 40 ° C), the ability of the sheet to distort is weak.
Ainsi l'invention fournit une feuille imprégnée pour revêtement décoratif telle que définie dans la revendication 1.Thus the invention provides an impregnated sheet for coating decorative as defined in claim 1.
Le polymère peut être autoréticulable ou réticulable par action d'un agent extérieur.The polymer can be self-crosslinkable or crosslinkable by action from an outside agent.
Plus particulièrement l'invention se caractérise par le fait que
le polymère réticulable utilisé sous forme d'une dispersion
aqueuse stable est de préférence choisi parmi les copolymères de styrène-butadiène,
les copolymères de styrène-butadiène carboxylés, les
polymères de l'acétate de vinyle dont le poly(éthylène/acétate
de vinyle), les polymères acryliques et dérivés autre qu'un
copolymère styrène-acrylate d'éthyle-acrylate de butyle, les
polymères uréthanes et leurs mélanges.
Par polymère, il faut comprendre homopolymère ou copolymère.More particularly the invention is characterized in that the crosslinkable polymer used in the form of a stable aqueous dispersion is preferably chosen from styrene-butadiene copolymers, styrene-butadiene carboxylated copolymers, polymers of acetate of vinyl including poly (ethylene / vinyl acetate), acrylic polymers and derivatives other than a styrene-ethyl acrylate-butyl acrylate copolymer, urethane polymers and mixtures thereof.
By polymer, it is necessary to understand homopolymer or copolymer.
Plus particulièrement l'invention se caractérise par le fait que
le liant hydrosoluble est de préférence choisi parmi les poly(alcool de
vinyle), la gélatine, les amidons, les dérivés de cellulose, les
alginates et leurs mélanges.
Comme dérivés de cellulose on peut utiliser notamment la
carboxyméthylcellulose.More particularly, the invention is characterized in that the water-soluble binder is preferably chosen from polyvinyl alcohol, gelatin, starches, cellulose derivatives, alginates and their mixtures.
As cellulose derivatives, carboxymethylcellulose can be used in particular.
La feuille selon l'invention se caractérise par le fait qu'elle est imprégnée d'une composition comportant 95 à 50 parts en poids sec de polymère réticulable et 5 à 50 parts en poids sec de liant hydrosoluble, la somme des parts respectives étant égale à 100.The sheet according to the invention is characterized by the fact that it is impregnated with a composition comprising 95 to 50 parts by dry weight of crosslinkable polymer and 5 to 50 parts by dry weight of water-soluble binder, the sum of the respective parts being equal to 100.
Selon un cas particulier de l'invention, le liant hydrosoluble
est un poly(alcool de vinyle) ayant un degré d'hydrolyse de 98-99
et une viscosité de 4 mPa.s,[déterminée à 20°C selon la norme
DIN 53015 pour une solution à 4%].
Le degré d'hydrolyse est exprimé comme habituellement en % de
moles d'acétate hydrolysées.According to a particular case of the invention, the water-soluble binder is a polyvinyl alcohol having a degree of hydrolysis of 98-99 and a viscosity of 4 mPa.s, [determined at 20 ° C according to standard DIN 53015 for a 4% solution].
The degree of hydrolysis is expressed as usual in% of moles of hydrolyzed acetate.
Selon un cas préféré de l'invention, la feuille est imprégnée d'une composition comportant 70 à 90 parts en poids sec de poly(éthylène/acétate de vinyle) et 30 à 10 parts en poids sec du poly(alcool de vinyle) défini ci-dessus, la somme des parts respectives étant égale à 100.According to a preferred case of the invention, the sheet is impregnated of a composition comprising 70 to 90 parts by dry weight of poly (ethylene / vinyl acetate) and 30 to 10 parts by dry weight poly (vinyl alcohol) defined above, the sum of the parts being 100.
L'invention concerne aussi les panneaux ou profilés décoratifs comportant une telle feuille comme feuille décorative (revendication 1), ainsi qu'un procédé de fabrication de la feuille décorative (revendication 2) et un procédé de fabrication d'un panneau ou profilé décoratif comprenant ladite feuille décorative (revendication 8).The invention also relates to decorative panels or profiles comprising such a sheet as a decorative sheet (claim 1), as well as a method of manufacturing the decorative sheet (claim 2) and a method of manufacturing a decorative panel or profile comprising said decorative sheet (claim 8).
La composition d'imprégnation utilisée pour imprégner la feuille servant de base aux revêtements décoratifs est substantiellement exempte de formaldéhyde et comporte en mélange une dispersion aqueuse stable d'un polymère réticulable, ayant une température de transition vitreuse comprise entre -10 et 35°C, autre qu'un copolymère styrène-acrylate d'éthyle-acrylate de butyle, et un liant hydrosoluble, dans les proportions relatives indiquées dans la revendication 1.The impregnating composition used to impregnate the sheet used base to decorative coatings is substantially free of formaldehyde and contains a stable aqueous dispersion as a mixture of a crosslinkable polymer, having a transition temperature glassy between -10 and 35 ° C, other than a copolymer styrene-ethyl acrylate-butyl acrylate, and a binder water-soluble, in the relative proportions indicated in claim 1.
De préférence, le liant hydrosoluble est choisi parmi les poly(alcool de vinyle), la gélatine, les amidons, les dérivés de cellulose, les alginates et leurs mélanges.Preferably, the water-soluble binder is chosen from poly (vinyl alcohol), gelatin, starches, cellulose derivatives, alginates and their mixtures.
De préférence, la composition le polymère réticulable en dispersion aqueuse stable est choisi parmi les copolymères de styrène-butadiène, les copolymères de styrène-butadiène carboxylés, les polymères de l'acétate de vinyle dont le poly(éthylène/acétate de vinyle), les polymères acryliques et dérivés autre qu'un copolymère styrène-acrylate d'éthyle-acrylate de butyle, les polymères uréthanes et leurs mélanges. Preferably, the composition crosslinkable polymer in stable aqueous dispersion is chosen among the styrene-butadiene copolymers, the copolymers of carboxylated styrene-butadiene, polymers of acetate vinyl including poly (ethylene / vinyl acetate), polymers acrylics and derivatives other than a styrene-acrylate copolymer ethyl butyl acrylate, urethane polymers and their mixtures.
La composition comporte 95 à 50 parts en poids sec de polymère réticulable, utilisé sous forme de dispersion aqueuse stable et 5 à 50 parts en poids sec de liant hydrosoluble, la somme des parts respectives étant égale à 100.The composition comprises 95 to 50 parts by dry weight crosslinkable polymer, used in the form of an aqueous dispersion stable and 5 to 50 parts by dry weight of water-soluble binder, the sum of the respective shares being equal to 100.
De préférence le liant hydrosoluble est un poly(alcool de vinyle) ayant un degré d'hydrolyse de 98-99 et une viscosité de 4 mPa.s [déterminée à 20°C selon la norme DIN 53015 pour une solution à 4%].Preferably the water-soluble binder is a poly (vinyl alcohol) having a hydrolysis degree of 98-99 and a viscosity of 4 mPa.s [determined at 20 ° C according to DIN 53015 for a solution to 4%].
Plus préférentiellement la composition comporte 70 à 90 parts en poids sec de poly(éthylène/acétate de vinyle) et 30 à 10 parts en poids sec du poly(alcool de vinyle), la somme des parts respectives étant égale à 100.More preferably, the composition comprises 70 to 90 parts in dry weight of poly (ethylene / vinyl acetate) and 30 to 10 parts by dry weight of poly (vinyl alcohol), the sum of the parts being 100.
De préférence la composition d'imprégnation a une viscosité BROOKFIELD inférieure à 200 mPa.s, mesurée à 100 tours par minute afin que la feuille puisse être bien imprégnée.Preferably the impregnating composition has a viscosity BROOKFIELD less than 200 mPa.s, measured at 100 revolutions per minute so that the sheet can be well impregnated.
La composition d'imprégnation peut comporter aussi des adjuvants exempts de formaldéhyde utilisés habituellement en papeterie pour faciliter l'imprégnation et le séchage de la feuille tels que des agents mouillants, des agents de coalescence, des lubrifiants comme le stéarate de calcium, des insolubilisants.The impregnating composition may also include adjuvants free of formaldehyde commonly used in stationery for facilitate the impregnation and drying of the sheet such as wetting agents, coalescing agents, lubricants like calcium stearate, insolubilizers.
L'invention sera mieux comprise à l'aide des exemples non limitatifs suivants :The invention will be better understood using the examples not following limitations:
On forme une feuille de papier classiquement à partir d'une
composition de fibres de cellulose, d'un liant et d'autres
adjuvants papetiers. On essore puis sèche la feuille; la feuille
obtenue a un grammage de 45 g/m2.
On imprègne la feuille en presse encolleuse d'une composition
contenant 80 parts en poids sec d'un latex d'un copolymère
styrène-acrylate d'éthyle-acrylate de butyle et 20 parts en poids
sec de résine urée-formaldéhyde, ajoutée sous forme de solution
aqueuse.
La viscosité BROOKFIELD mesurée avec un mobile à 100 tours/mn est
de 40 mPa.s .
On sèche la feuille vers 120 °C. On obtient une feuille ayant un
grammage de 60 g/m2.A sheet of paper is conventionally formed from a composition of cellulose fibers, a binder and other papermaking adjuvants. The leaf is wrung and then dried; the sheet obtained has a grammage of 45 g / m 2 .
The sheet is impregnated in a size press with a composition containing 80 parts by dry weight of a latex of a styrene-ethyl acrylate-butyl acrylate copolymer and 20 parts by dry weight of urea-formaldehyde resin, added in the form aqueous solution.
The BROOKFIELD viscosity measured with a mobile at 100 rpm is 40 mPa.s.
The sheet is dried at around 120 ° C. A sheet having a grammage of 60 g / m 2 is obtained.
On mesure la quantité de formaldéhyde qui se dégage de la feuille
selon la norme DIN 52368; on l'exprime en mg de formaldéhyde
dégagé par heure et par mètre carré de feuille.
Dans cet exemple la quantité de formaldéhyde est de 1,5.The quantity of formaldehyde released from the sheet is measured according to DIN 52368; it is expressed in mg of formaldehyde released per hour and per square meter of sheet.
In this example, the amount of formaldehyde is 1.5.
On mesure la cohésion interne de la feuille laquée pour estimer
sa résistance à la délamination et à l'arrachage, par un test
d'arrachage avec un ruban adhésif selon la méthode suivante :
on fixe une bande de la feuille préalablement découpée soit dans
le sens machine du papier, soit dans le sens travers sur une
plaque de verre à l'aide d'un ruban adhésif double face. On
presse un morceau de ruban adhésif une face (Référence TESA 4204
de la société ) sur la bande de papier, une extrémité du morceau
de ruban adhésif étant conservée libre par application sur un
chevalet de 80 mm de hauteur.
Après un temps de 7 jours, on arrache le ruban adhésif de la
feuille par son extrémité libre.
Pour voir à l'oeil nu si l'échantillon a été arraché, on applique
le ruban adhésif sur un fond blanc ou noir selon la teinte de
l'épreuve.
Dans le cas de l'exemple, on vérifie le ruban sur fond blanc.The internal cohesion of the lacquered sheet is measured to estimate its resistance to delamination and peeling, by a peeling test with an adhesive tape according to the following method: a strip of the sheet previously cut is fixed either in the direction machine, either crosswise on a glass plate using double-sided tape. A piece of adhesive tape is pressed on one side (TESA reference 4204 from the company) on the paper strip, one end of the piece of adhesive tape being kept free by application on an easel 80 mm high.
After a period of 7 days, the adhesive tape is torn from the sheet by its free end.
To see with the naked eye if the sample has been torn off, the adhesive tape is applied to a white or black background depending on the color of the test.
In the case of the example, we check the ribbon on a white background.
On vérifie que la feuille s'imprime bien.
On vérifie aussi que la feuille a une bonne aptitude au laquage,
on utilise une laque à base de polyester.We check that the sheet prints well.
We also check that the sheet has a good ability to lacquering, we use a polyester-based lacquer.
On teste la résistance à la déformabilité de la feuille laquée par un test de résistance au froissement décrit dans l'article "WARING QUALITY OF EXPERIMENTAL CURRENCY-TYPE PAPERS, Journal of Research of the National Bureau of Standards, Volume 36, pages 249 à 268, mars 1946. On détermine le nombre de froissements nécessaires pour observer la première craquelure de la laque. Dans ce cas, le nombre de froissement est de 1, ce qui est très faible. The resistance to deformability of the lacquered sheet is tested. by a wrinkle resistance test described in the article "WARING QUALITY OF EXPERIMENTAL CURRENCY-TYPE PAPERS, Journal of Research of the National Bureau of Standards, Volume 36, pages 249 to 268, March 1946. The number of creases is determined necessary to observe the first cracking of the lacquer. In this case, the number of creases is 1, which is very low.
On réalise une feuille comme dans l'exemple 1 mais on l'imprègne
avec une composition contenant 80 parts en poids sec d'un latex
de poly(éthylène/acétate de vinyle) - appelé EVA -
autoréticulable et dont la température de transition vitreuse Tg
est de 6°C, et 20 parts en poids sec de poly(alcool vinylique)
ayant un degré d'hydrolyse de 98-99 et une viscosité de 4 mPa.s
[déterminée à 20°C selon la norme DIN 53015 pour une solution à
4%], ajouté sous forme d'une solution aqueuse à 10%.
L'extrait sec est réglé pour que la composition ait une viscosité
BROOKFIELD mesurée avec un mobile à 100 tours/mn de 80 mPa.s .A sheet is produced as in Example 1 but it is impregnated with a composition containing 80 parts by dry weight of a poly (ethylene / vinyl acetate) latex - called EVA - which is self-crosslinking and whose glass transition temperature Tg is 6 ° C, and 20 parts by dry weight of polyvinyl alcohol having a degree of hydrolysis of 98-99 and a viscosity of 4 mPa.s [determined at 20 ° C according to standard DIN 53015 for a solution at 4%], added in the form of a 10% aqueous solution.
The dry extract is adjusted so that the composition has a BROOKFIELD viscosity measured with a mobile at 100 rpm of 80 mPa.s.
On teste la feuille ainsi imprégnée comme dans l'exemple 1.
La quantité de formaldéhyde est inférieure à 0,15mg/(h.m2).
Son imprimabilité et son aptitude au vernissage sont d'un niveau
aussi bon que celles de l'exemple 1.
Dans ce cas, le nombre de froissements est de 8, ce qui
représente un gain très important par rapport aux feuilles selon
l'art antérieur.The sheet thus impregnated is tested as in Example 1. The amount of formaldehyde is less than 0.15 mg / (hm 2 ). Its printability and its ability to varnish are of a level as good as that of Example 1.
In this case, the number of creases is 8, which represents a very significant gain compared to the sheets according to the prior art.
On réalise une feuille comme dans l'exemple 1 mais on l'imprègne avec une composition contenant 80 parts en poids sec d'un latex de polyacrylique, autoréticulable et ayant une Tg de 32°C, et 20 parts en poids sec du poly(alcool vinylique) utilisé à l'exemple 2.We make a sheet as in Example 1 but we impregnate it with a composition containing 80 parts by dry weight of a latex polyacrylic, self-crosslinking and having a Tg of 32 ° C, and 20 parts by dry weight of the polyvinyl alcohol used in the example 2.
L'extrait sec est réglé pour que la composition ait une viscosité BROOKFIELD mesurée avec un mobile à 100 tours/mn de 80 mPa.s .The dry extract is adjusted so that the composition has a viscosity BROOKFIELD measured with a mobile at 100 rpm of 80 mPa.s.
On teste la feuille ainsi imprégnée comme dans l'exemple 1.
La quantité de formaldéhyde est inférieure à 0,15mg/(h.m2).
Son imprimabilité et son aptitude au vernissage sont d'un niveau
aussi bon que celles de l'exemple 1.
Dans ce cas, le nombre de froissements est de 4, ce qui
représente un gain encore important par rapport à l'art
antérieur.The sheet thus impregnated is tested as in Example 1. The amount of formaldehyde is less than 0.15 mg / (hm 2 ). Its printability and its ability to varnish are of a level as good as that of Example 1.
In this case, the number of creases is 4, which represents a still significant gain compared to the prior art.
On réalise une feuille comme dans l'exemple 1 mais on l'imprègne
avec une composition contenant 80 parts en poids sec d'un latex
de poly(stryrène-butadiène-acrylate) réticulable et ayant une Tg
d'environ 16°C, et 20 parts en poids sec du poly(alcool
vinylique) utilisé à l'exemple 2.
L'extrait sec est réglé pour que la composition ait une viscosité
BROOKFIELD mesurée avec un mobile à 100 tours/mn de 75 mPa.s .A sheet is produced as in Example 1 but it is impregnated with a composition containing 80 parts by dry weight of a crosslinkable poly (stryrene-butadiene-acrylate) latex and having a Tg of approximately 16 ° C, and 20 parts by dry weight of the polyvinyl alcohol used in Example 2.
The dry extract is adjusted so that the composition has a BROOKFIELD viscosity measured with a mobile at 100 rpm of 75 mPa.s.
On teste la feuille ainsi imprégnée comme dans l'exemple 1.
La quantité de formaldéhyde est inférieure à 0,15mg/(h.m2).
Son imprimabilité et son aptitude au vernissage sont d'un niveau
aussi bon que celles de l'exemple 1.
Dans ce cas, le nombre de froissements est de 8.The sheet thus impregnated is tested as in Example 1. The amount of formaldehyde is less than 0.15 mg / (hm 2 ). Its printability and its ability to varnish are of a level as good as that of Example 1.
In this case, the number of creases is 8.
On réalise une feuille comme dans l'exemple 1 mais on l'imprègne
avec une composition contenant 80 parts en poids sec d'un latex
d'un copolymère styrène-acrylate réticulable et ayant une Tg
d'environ 50°C, et 20 parts en poids sec du poly(alcool
vinylique) utilisé à l'exemple 2.
L'extrait sec est réglé pour que la composition ait une viscosité
BROOKFIELD mesurée avec un mobile à 100 tours/mn de 75 mPa.s .A sheet is produced as in Example 1 but it is impregnated with a composition containing 80 parts by dry weight of a latex of a crosslinkable styrene-acrylate copolymer and having a Tg of approximately 50 ° C., and 20 parts by dry weight of the poly (vinyl alcohol) used in Example 2.
The dry extract is adjusted so that the composition has a BROOKFIELD viscosity measured with a mobile at 100 rpm of 75 mPa.s.
On teste la feuille ainsi imprégnée comme dans l'exemple 1.
La quantité de formaldéhyde est inférieure à 0,15mg/(h.m2).
Son imprimabilité et son aptitude au vernissage sont d'un niveau
aussi bon que celles de l'exemple 1.
Cependant le nombre de froissements est de 2, ce qui est faible.The sheet thus impregnated is tested as in Example 1. The amount of formaldehyde is less than 0.15 mg / (hm 2 ). Its printability and its ability to varnish are of a level as good as that of Example 1.
However, the number of creases is 2, which is low.
Les résultats du test à l'arrachage sont bons dans tous les cas.The results of the grub test are good in all cases.
Claims (11)
- Impregnated decorative paper sheet, intended to be applied to a base support by means of an adhesive in order to form a decorative panel or moulded section, characterized in that the said sheet is impregnated with an impregnating composition substantially devoid of formaldehyde and comprising, as a mixture, a water-soluble binder and a crosslinkable polymer, other than a styrene-ethyl acrylate-butyl acrylate copolymer, the said crosslinkable polymer exhibiting a glass transition temperature of between -10 and 35°C and being used in the form of a stable aqueous dispersion, the said impregnating composition comprising 95 to 50 parts by weight on a dry basis of crosslinkable polymer and 5 to 50 parts by weight on a dry basis of water-soluble binder, the sum of the respective parts being equal to 100.
- Sheet according to Claim 1, characterized in that the water-soluble binder is chosen from poly(vinyl alcohol)s, gelatin, starches, cellulose derivatives, alginates and their mixtures.
- Sheet according to either of Claims 1 and 2, characterized in that the crosslinkable polymer used in the form of a stable aqueous dispersion is chosen from styrene-butadiene copolymers, styrene-butadiene copolymers which are carboxylated, vinyl acetate copolymers, including poly(ethylene/vinyl acetate), acrylic polymers and derivatives, other than a styrene-ethyl acrylate-butyl acrylate copolymer, urethane polymers and their mixtures.
- Sheet according to one of Claims 1 to 3, characterized in that the water-soluble binder is a poly(vinyl alcohol) having a degree of hydrolysis of 98-99 and a viscosity of 4 mPa·s [determined at 20°C according to DIN Standard 53015 for a 4% solution].
- Sheet according to Claim 4, characterized in that the said impregnating composition comprises 70 to 90 parts by weight on a dry basis of poly(ethylene/vinyl acetate) and 30 to 10 parts by weight on a dry basis of the poly(vinyl alcohol), the sum of the respective parts being equal to 100.
- Sheet according to one of Claims 1 to 5, characterized in that the said impregnating composition has a Brookfield viscosity, measured at 100 revolutions/min, of less than 200 mPa·s.
- Decorative panel or moulded section, characterized in that it comprises, as decorative sheet, a sheet as defined in one of Claims 1 to 6.
- Process for the manufacture of a decorative panel or moulded section according to Claim 7, characterized in that a decorative sheet as defined in one of Claims 1 to 6 is attached using an adhesive to a base support, in particular a panel made of agglomerated particles or fibres.
- Process for the manufacture of a decorative sheet, characterized in that a paper sheet is impregnated with an impregnating composition as defined in one of Claims 1 to 6.
- Process for the manufacture of a decorative sheet according to Claim 9, characterized in that the paper sheet is printed after having been impregnated with the impregnating composition.
- Process for the manufacture of a decorative sheet according to Claim 9, characterized in that the paper sheet is printed before impregnating it with the impregnating composition.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES94902840T ES2125433T3 (en) | 1993-12-21 | 1993-12-21 | PAPER SHEET IMPREGNATED AS DECORATIVE COATING. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/FR1993/001275 WO1995017551A1 (en) | 1993-12-21 | 1993-12-21 | Impregnated sheet used as a basis for a decorative coating |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0739435A1 EP0739435A1 (en) | 1996-10-30 |
EP0739435B1 true EP0739435B1 (en) | 1998-10-28 |
Family
ID=9443761
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94902840A Expired - Lifetime EP0739435B1 (en) | 1993-12-21 | 1993-12-21 | Impregnated paper sheet as decorative overlay |
Country Status (9)
Country | Link |
---|---|
US (1) | US5885719A (en) |
EP (1) | EP0739435B1 (en) |
AT (1) | ATE172766T1 (en) |
CA (1) | CA2179541C (en) |
DE (1) | DE69321853T2 (en) |
ES (1) | ES2125433T3 (en) |
HU (1) | HU220243B (en) |
PL (1) | PL173782B1 (en) |
WO (1) | WO1995017551A1 (en) |
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WO2004074577A1 (en) * | 2003-02-24 | 2004-09-02 | AHLSTROM OSNABRÜCK GmbH | Prepreg |
WO2009000769A1 (en) | 2007-06-28 | 2008-12-31 | Technocell Dekor Gmbh & Co. Kg | Pre-impregnated product |
DE102013114420A1 (en) | 2012-12-23 | 2014-06-26 | Michael Jokiel | Impregnated paper comprises base paper which is impregnated on one side with water-based impregnating solution comprising e.g. aqueous dispersion of styrene-ethyl-butyl acrylate copolymer and aqueous dispersion of styrene-acrylate copolymer |
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ES2153243B1 (en) * | 1997-03-03 | 2001-08-16 | Planchas De Goma Ind S A | PROCEDURE TO PROVIDE A COATING ON A SMOOTH SURFACE. |
BR0011744A (en) * | 1999-06-11 | 2002-11-26 | Unidur Gmbh | Composition for impregnating paper, method for producing it, impregnated and laminated paper comprising said impregnated paper |
DE60026882T2 (en) | 1999-12-21 | 2006-11-16 | Omnova Solutions Inc., Fairlawn | POLYVINYLALKOHOLCOPOLYMERZUSAMMENSETZUNG |
DE10134302C1 (en) * | 2001-07-14 | 2002-12-12 | Technocell Dekor Gmbh & Co Kg | Pre-impregnate obtained by impregnation of crude paper with a thermally hardenable formaldehyde-free resin useful in the production of decorative impregnates or coatings, and surface treatment of printed and unprinted papers |
DE10334008A1 (en) * | 2003-07-25 | 2005-02-24 | Bausch Gmbh | Process for coating carrier materials with different degrees of gloss and subsequently produced carrier material |
US7732057B2 (en) * | 2006-07-20 | 2010-06-08 | Neenah Paper, Inc. | Formaldehyde-free paper backed veneer products and methods of making the same |
ES2641738T5 (en) | 2007-12-17 | 2021-08-02 | Schoeller Technocell Gmbh & Co Kg | Decorative paper impregnation that can be compressed and printable using an inkjet process |
JP2011506794A (en) † | 2007-12-21 | 2011-03-03 | テクノチェル デコール ゲー エム ベー ハー ウント コンパニー コマンディートゲゼルシャフト | Base paper for decorative coating materials |
DE102011105676B4 (en) | 2011-06-22 | 2018-05-09 | Schoeller Technocell Gmbh & Co. Kg | Prepreg and decorative paper or decorative coating material therefrom |
DE202013009496U1 (en) | 2013-10-24 | 2013-11-14 | Samtastic Products GmbH | Multilayer decorative plastic sheet or plate |
CA3092809A1 (en) * | 2018-03-01 | 2019-09-06 | Arclin Usa Llc | Formaldehyde-free highly water and abrasion resistant overlay for building products |
EP3754109B1 (en) | 2019-06-18 | 2022-09-28 | Schoeller Technocell GmbH & Co. KG | Pre-impregnate with improved flatness |
EP3896953B1 (en) | 2020-04-17 | 2024-05-01 | Felix Schoeller GmbH & Co. KG | Method for controlling a decorative printing process |
CN111501416B (en) * | 2020-05-09 | 2022-05-27 | 中国林业科学研究院生态保护与修复研究所 | Formaldehyde-free impregnation adhesive for decorative paper and preparation method thereof |
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GB1010339A (en) * | 1962-11-21 | 1965-11-17 | Monsanto Chemicals | Process for treating fibrous materials |
GB1250056A (en) * | 1968-04-16 | 1971-10-20 | Formica Corp | Decorative laminate having adherable coating thereon |
JPS5375308A (en) * | 1976-12-15 | 1978-07-04 | Matsushita Electric Works Ltd | Production of decorative plate comprising natural wood |
US4587141A (en) * | 1983-12-15 | 1986-05-06 | U.S. Plywood Corporation | Laminated panel and process |
US5171627A (en) * | 1990-09-27 | 1992-12-15 | The Lincoln Group, Inc. | Process for fabricating a precursor sheet, particularly as book cover stock and product produced thereby |
JPH0931890A (en) * | 1995-07-18 | 1997-02-04 | Mitsubishi Paper Mills Ltd | Decorative paper |
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1993
- 1993-12-21 WO PCT/FR1993/001275 patent/WO1995017551A1/en active IP Right Grant
- 1993-12-21 HU HU9601718A patent/HU220243B/en not_active IP Right Cessation
- 1993-12-21 EP EP94902840A patent/EP0739435B1/en not_active Expired - Lifetime
- 1993-12-21 CA CA002179541A patent/CA2179541C/en not_active Expired - Fee Related
- 1993-12-21 PL PL93315115A patent/PL173782B1/en not_active IP Right Cessation
- 1993-12-21 AT AT94902840T patent/ATE172766T1/en active
- 1993-12-21 US US08/652,482 patent/US5885719A/en not_active Expired - Lifetime
- 1993-12-21 ES ES94902840T patent/ES2125433T3/en not_active Expired - Lifetime
- 1993-12-21 DE DE69321853T patent/DE69321853T2/en not_active Expired - Lifetime
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JPS54154428A (en) * | 1978-05-26 | 1979-12-05 | Nitto Electric Ind Co Ltd | Strippable coating composition |
WO1994000523A1 (en) * | 1992-06-22 | 1994-01-06 | Gebrueder Buhl Papierfabriken Gmbh | Aqueous impregnating composition |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004074577A1 (en) * | 2003-02-24 | 2004-09-02 | AHLSTROM OSNABRÜCK GmbH | Prepreg |
WO2009000769A1 (en) | 2007-06-28 | 2008-12-31 | Technocell Dekor Gmbh & Co. Kg | Pre-impregnated product |
DE102013114420A1 (en) | 2012-12-23 | 2014-06-26 | Michael Jokiel | Impregnated paper comprises base paper which is impregnated on one side with water-based impregnating solution comprising e.g. aqueous dispersion of styrene-ethyl-butyl acrylate copolymer and aqueous dispersion of styrene-acrylate copolymer |
Also Published As
Publication number | Publication date |
---|---|
CA2179541C (en) | 2001-07-10 |
DE69321853T2 (en) | 1999-05-27 |
WO1995017551A1 (en) | 1995-06-29 |
PL315115A1 (en) | 1996-10-14 |
HUT77902A (en) | 1998-09-28 |
HU9601718D0 (en) | 1996-08-28 |
HU220243B (en) | 2001-11-28 |
ES2125433T3 (en) | 1999-03-01 |
US5885719A (en) | 1999-03-23 |
ATE172766T1 (en) | 1998-11-15 |
DE69321853D1 (en) | 1998-12-03 |
EP0739435A1 (en) | 1996-10-30 |
CA2179541A1 (en) | 1995-06-29 |
PL173782B1 (en) | 1998-04-30 |
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