WO1999035335A1 - Feuille papetiere decorative comprenant une composition de dioxyde de titane et stratifie decoratif - Google Patents
Feuille papetiere decorative comprenant une composition de dioxyde de titane et stratifie decoratif Download PDFInfo
- Publication number
- WO1999035335A1 WO1999035335A1 PCT/FR1998/002875 FR9802875W WO9935335A1 WO 1999035335 A1 WO1999035335 A1 WO 1999035335A1 FR 9802875 W FR9802875 W FR 9802875W WO 9935335 A1 WO9935335 A1 WO 9935335A1
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- WO
- WIPO (PCT)
- Prior art keywords
- sheet
- decorative
- paper
- impregnated
- fibers
- Prior art date
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Classifications
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- 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
- D21H27/26—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures
- D21H27/28—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures treated to obtain specific resistance properties, e.g. against wear or weather
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C7/00—Paperhanging
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
- C09C1/0084—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound containing titanium dioxide
- C09C1/0087—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound containing titanium dioxide only containing titanium dioxide and silica or silicate
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
Definitions
- the invention relates to decorative paper sheets used in the manufacture of decorative laminated panels or profiles
- the invention relates in particular to decorative sheets impregnated with a thermosetting resin as well as the impregnated sheets obtained, called “decorative films” It also relates to so-called decorative sheets finished sheets It also relates to the manufacturing processes of the sheets as well as the laminated decorative panels or profiles comprising them
- laminated panels or profiles also called “laminates”
- laminates For many years, decorative laminated panels or profiles (also called “laminates”) have been used as materials in dwellings and commercial and industrial premises Typical applications of such laminates are furniture coverings, table tops, chairs and others or floor coverings such as floor coverings
- Decorative rings or profiles are made up of panels composed of a basic support, in general a panel of wood particles or agglomerated fibers, and a sheet of decorative paper impregnated with a composition, called finished sheet, fixed on the support by means of an adhesive
- the sheet of paper is a decorative sheet comprising between 40 to 90% of short cellulosic fibers and 10 to 60% of long cellulosic fibers, the sum making 100 by weight, between 0.2 and 1%. by dry weight of the impregnated paper, of a wet resistance agent, between 0J and 20%. by dry weight of the impregnated paper, of mineral and / or organic opacifying and / or coloring fillers
- the sheet is of uniform color or has decorative patterns
- opacifying fillers titanium dioxide is used in particular and preferably at a rate of 10 to 20 %
- decorative patterns can be applied by printing on the sheet, before or after impregnation.
- a venus or a lacquer is applied which aims to protect the surface of the sheet.
- These sheets are most often impregnated using a size press or other impregnation device on a paper machine or outside of a paper machine, at a rate of 15 to 30% by dry weight of the impregnated paper, with compositions comprising aqueous dispersions based on copolymer styrene-allyl acrylate and an aqueous solution of thermosetting resins containing formaldehyde such as melamine-form dehyde or urea-foimaldehyde resins t it has been proposed to impregnate the sheet with a composition free of foaldehyde, this composition preferably comprises 95 to 50 paits by dry weight, of a crosslinkable polymer and having a glass transition temperature between -10 and 35 ° C.
- styrene-ethyl acrylate copolymer- butyl acrylate and a binder preferably chosen from poly (vinyl alcohol), gelatin, starches, cellulose fibers, algmas at a rate of preferably 5 to 50 parts by dry weight, the sum of respective shares being equal to 100
- Such sheets are deentents in patent applications WO 93/01549 and WO 93/01275.
- the sheets impregnated online on a paper machine are said to be prepregs and those impregnated offline are said to be post-impregnated
- the sheet obtained is very opaque so that the support cannot be seen through. It is also necessary that the light fastness, due to their exposure, be high, it is preferably greater than or equal to 6 on the blue scale according to ISO standard 4586-2 16
- the titanium dioxide pigments used are in fact pigments whose surface has been treated with oxides of silicon or aluminum or phosphorus or even cenum, .zinc or .zirconium, possibly mixed, at a rate of about 5 to 10% by weight More precisely, these are silica, alumina and phosphate particles Ce treatment also makes it possible to adjust the ionicity of the pigments
- a surface treatment of this type has for example been dec ⁇ t in the patent US 4461810 In the patent application GB 2234990, there has also been the surface treatment of an anatase titanium dioxide and a .kaolin to improve their light fastness ière
- the so-called high pressure decorative laminates are produced from a core consisting of sheets impregnated with resin
- These sheets are generally made of kraft paper and have been impregnated with a thermosetting resin, most often a phenolic resin
- the number of sheets in the pile depends on apphcations and vane between 3 and 9, but can be superior
- a decorative sheet is then placed on the stack of sheets constituting the core.
- a protective covering sheet called "overlay”, without pattern and transparent in the final laminate, is placed above the decorative sheet, to improve the abrasion resistance of the laminate.
- the stack of impregnated sheets is then placed in a laminating press, the plates of which are provided with a sheet, the state of the laminate surface. Then, the stack is densified by heating, at a temperature of the order of 110 ° C to 170 ° C. and by pressing, at a pressure of the order of 5.5 MPa to 11 MPa, for approximately 25 to 60 minutes, to obtain a unitary structure.
- This structure is then fixed on a basic support, for example by bonding it to said base.
- support such as a panel of agglomerated particles, in particular of agglomerated wood particles
- the so-called low pressure decorative laminates are produced using only a decorative sheet impregnated with theirnosetting resin, and optionally an overlay sheet, which is laminated directly onto the base support such as a panel during a short cycle, the temperature being around 160 to 175 ° C and pressure from 1.25 MPa to 3 MPa
- the impregnable decorative sheet used for the manufacture of these two kinds of laminates, low and high pressure is generally a sheet of paper produced on a paper machine and which comprises cellulose fibers and possibly synthetic fibers, the cellulose fibers dividing, by weight, between 40 to 100%, preferably 80 to 100%, in short fibers and between 0 to 60%, preferably 0 to 20%, in long fibers, 0.2 to 1% by dry weight relative to the sheet, preferably 0.4 to 0.5%.
- opacifying fillers such as dioxide of titanium, in particular of the rutile type, said opacifying filler such as titanium dioxide being in amounts preferably at least 15%, in general, between about 15 to 40% relative to the weight of the sheet
- thermosetting resin but thermally stable (not yellowing), most often with melamine-formaldehyde resins or urea-formaldehyde resins, or sometimes benzoguanamine-formaldehyde resins, unsaturated polyester resins
- the impregnated sheet is heated and the resin is partially crosslinked (their hardening) so that the resin is no longer in a sticky state and that the sheet can be handled
- Such a decorative sheet impregnated with partially crosslinked resin is called, in terms of profession, "decor film” or “decorative film or even” melamine film "
- This second step is generally carried out by bringing the sheet to temperatures of about 110 to 140 ° C. and is controlled, so that the resme during the final lamination of the decor film flowed correctly into the sheet, by measuring the rate of volatiles remaining in the decor film
- this decor film then comprises a certain percentage, of the order of 5 to 8%, of volatile products (water solvent for the resin, water resulting from the chemical condensation of the resin, the residual formaldehyde, the other residual products)
- volatiles represent the compounds which will be eliminated during the total crosslinking of the resin, during the lamination of the decor film
- the resin once completely their hardened, after lamination, will bring surface resistance to the laminate final (abrasion resistance, resistance to sanding, water vapor and chemical agents such as solvents, acids and bases, etc.)
- this sheet once laminated, must have a very high light fastness because it is exposed almost quasi-manence to light radiation by its use of surface covering, the compounds which constitute it must therefore be selected so to obtain this light outfit, preferably greater than or equal to 6 on the blue scale according to ISO standard 4586-2 16
- the pigments of titanium dioxide used are in fact of the same type as those used in the case of the finished sheet
- this sheet must allow '' obtaining an opaque decoration film after lamination II is indeed important, as in the case of the finished sheet, that we do not see the basic support and / or the sheets of kiaft paper on which we have laminated the decorative sheet impregnated, through said sheet, so that there is no interference with the decoration of the sheet. It is therefore necessary to have a decorative sheet giving the most opacity possible
- One of the parameters which intern in the opacifying power of a pigment is its diffusion power
- One of the characteristics of the pigment which is linked to this diffusion is the particle size and the form of the opacifying pigment
- the particle size and the form of the opacifying pigment In the case of dioxide pigments of titanium, their particle size is approximately 0.2 to 0.3 ⁇ m
- the other characteristic which influences the scattering of light is the refractive index
- Titanium dioxide of the rutile type is preferred to that of the anatase type because its refractive index is the highest, that of the anatase not being only 2.55 to improve the power ir opacifier of a pigment, it has been found that it is preferable that said pigments are separated, this is why it is customary to add to it particles, called extenders
- the extenders of titanium dioxide are chosen from sihcoaluminates, silica, 1alc or kaolins in particular calcined kaolin These extenders are generally in the form of aggregates and have a particle size greater than that of titanium dioxide, they are between approximately 1 and 10 ⁇ m in diameter
- extender of the titanium dioxide is deente in the article "A companson of structured pigments for ùtanium dioxide dioxide extension", APPI JOURNAL, Avnl 1993, pages 70-76 More specifically in the field of decorative laminated panels, we were disappointed in the patent application WO 89/08739, the use of a peculiar precipitated
- the invention aims to solve these problems and therefore aims to provide a decorative paper sheet usable in decorative laminates, said sheet leading to high opacity of the final decorative laminate while retaining good light fastness.
- the Applicant has found that the object of the invention is achieved if the paper sheet comprises as opacifying pigments pigments of a composition of titanium dioxide and silica in the form of ripe mixed mineral flocs
- the invention provides a decorative paper sheet usable in the manufacture of decorative panels or profiles, comprising from 5 to 50%, by dry weight relative to the sheet, of a composition of titanium dioxide T ⁇ 0 and silica S ⁇ 0 2 in the form of mixed mineral flocs in which particles of T ⁇ 0 2 are spaced from each other by aggregates of S ⁇ 0 2 .
- the decorative sheet according to the invention is characterized in that the said flocs have been matured at a temperature between 60 and 100 ° C for at least thirty minutes
- floc is intended to denote mixed agglomerates of the two mineral species T1O 2 and S ⁇ 0 2 These agglomerates result from the association between particles of T ⁇ 0 and particles or aggregates of particles SI0 2 that come between the particles of T ⁇ 0 2
- the internal cohesion of the mixed mineral flocs, resulting from the association with T ⁇ 0 2 of an inorganic spacer agent such as silica is based on the solidity of ionic bonds established between T ⁇ 0 2 and the spacer agent
- This cohesion results directly from the process for preparing said mixed flocs More precisely, these flocs are obtained under operating conditions such as T ⁇ 0 2 and the spacing agent S ⁇ 0 2 have opposite and significantly different surface charges.
- the T ⁇ 0 2 and the spacing agent consider must be have sufficiently different isoelectric points for there to be a pH range in which these two mineral species have opposite charges.
- the process for the preparation of a said composition based on T ⁇ 0 2 and silica according to the invention comprises the steps according to which a) an aqueous dispersion of T1O2 is mixed with an aqueous dispersion of silica S ⁇ 0 2 .
- the mixing of the two dispersions being carried out with stirring and at pH compns between the respective isoelectric points of said T1O 2 and S ⁇ 0 2 and chosen in such a way that said T ⁇ 0 2 and S ⁇ 0 2 have opposite and sufficiently different surface charges to conduct, under the effect of electrostatic forces, in their arrangement in mixed mineral flocs in which the particles of T1O2 are globally spaced from one another by aggregates of S ⁇ 0 2 , in particular between 4.5 and 6.5, preferably of the order 5.5 b) the pH is regulated, where appropriate, at the value fixed in step 1, in particular at approximately 5.5 c) the resulting aqueous dispersion of mixed mineral flocs is matured at a temperature sufficient to reinforce the solidity of the bonds established between the particles of T ⁇ 0 and the particles and / or aggregates of S ⁇ 0 2 , in particular at a temperature between 60 ° C and 100 ° C for at least 30 minutes. d) said composition is recovered in the form of an aqueous dispersion of mixed mineral floc
- Said flocs obtained can then be micronized, that is to say that said flocs after having been made as previously and dried, are deagglomerated by an air jet grinding step (micronization) in order to be able to be suitably dispersed during their incorporation into a paper composition
- the mixed mineral flocs making up the expected composition therefore form with stirring of said dispersions, generally at room temperature and at a pH as defined above.
- the attraction is immediate However, it is preferable to maintain the aeration for about 15 minutes so as to stabilize the system before the ripening stage
- the aqueous dispersion of T ⁇ 0 2 used in the process comprises approximately 5 to 80% by weight of T ⁇ 0 and preferably approximately 5 to 40%
- the limiting point is the viscosity of the suspension which must remain at a reasonable value to be easy to handle
- the silica can be introduced either in the form of an aqueous dispersion of slurry-type silica particles or can be generated in situ by acidification of a solution of silicates.
- the pH of the reaction medium is adjusted after the precipitation step, to a value conducive to the manifestation of electrostatic forces between T ⁇ 0 2 and the silica thus generated and which are therefore necessary for their heterocoagulation
- the operating conditions conducive to the manifestation of the heterocoagulation phenomenon between the inorganic spacer agent S ⁇ 0 2 and T1O2 are in particular the choice of 'A pH in a range defined by their respective isoelectric points It is advisable to choose this pH in such a way that the two compounds have opposite and sufficiently different surface charges.
- it is desirable that the isoelectric points of the spacer agent and T ⁇ 0 are spaces at least one pH unit
- silica as a spacing agent in accordance with the present invention is advantageous for several reasons First of all, it has an isoelectric point at around 2, a value sufficiently different from that of the isoelectric point of the cationic form. T ⁇ 0 2 (6.5 to 7) Furthermore, silica has the advantage of not significantly absorbing visible light which is favorable in terms of whiteness of the sheet
- the titanium dioxide has a high light fastness. It is in particular a titanium dioxide of rutile type.
- the particles of T ⁇ 0 2 have a size of 0J to 1 ⁇ m
- the titanium dioxide T ⁇ 0 2 is coated with a mineral surface treatment and optionally the mixed mineral flocs are also coated with a surface treatment.
- the surface trimer comprises a component chosen from alumina, silica,.
- the surface treatment represents approximately 5 to 20% relative to the total weight of the mixed mineral flocs
- the silica S1O2 is used for 1 to 20%, preferably 5 to 15%, by weight relative to the weight of T1O 2 More particularly, the silica S1O 2 is used at a rate of approximately 10% to 15% by weight relative to the weight of T1O 2
- T1O 2 is a cationic rutile T1O 2
- the silica has a specific surface of between 20 and 300 m 2 / g.
- silica is used which is in the form of aggregates of size between 0.5 and 10 ⁇ , preferably between 0.5 and 2 ⁇ m
- the grammage of the sheet is from 40 to 150 g / m 2 , preferably from 60 to 100 g / m 2
- the opacifying fillers based on said composition of said titanium dioxide and of silica are present at a rate of 8 to 45% by dry weight of the sheet.
- Other white fillers such as kaolin or talc and / or segmental dyes can be used in addition with said titanium dioxide.
- the sheet of paper according to the invention comprises cellulose fibers and possibly synthetic fibers. , the cellulose fibers being distributed by weight between 40 to 100%.
- the present invention also relates to a wet manufacturing process of said decorative Bairlle which is characterized in that it comprises the following stages
- a sheet is formed from an aqueous suspension of cellulose fibers and optionally synthetic fibers, and 5 to 50% by dry weight relative to the sheet of the titanium dioxide composition and silica and possibly other additives usually used for these sheets,
- the process includes the following steps
- a sheet is formed, from an aqueous suspensron of cellulose fibers and optionally synthetic fibers, these fibers being distributed between 40 to 100%, preferably 60 to 100%. in short fibers and between 0 to 60%, preferably 0 to 20%, in long fibers, 0.2 to 1%, preferably 0.4 to 0.6%, of a wet strength agent by dry weight per compared to the flower. and 5 to 50%. in dry form with respect to the flower, of said composition of titanium dioxide and silica and possibly other additives usually used for these sheets, - the sheet is drained and dried
- said flocs have been micronized, that is to say that said flocs, after having been manufactured as previously and have been dried, have been deagglomerated by an air jet grinding step. (mrcronrsation) in order to be able to be appropriately dispersed during their incorporation in a paper composter
- the composter of the flocs of titanium dioxide and srhce is introduced as obtained in an aqueous medium
- the invention also provides a method of manufacturing a decorative sheet filled with a partially crosslinked thermosetting resin (decorative film) which is characterized in that a paper sheet as previously deentized is used, which the '.impregnates said sheet with a resin the hardener and that is partially crosslinked, the rate of volatile compounds being between 5 and 8% by weight of the flower
- thermosetting resin is chosen from melamine-formaldehyde resins, urea-formaldehyde resins or from benzoguana ⁇ une-formaldehyde resins, unsaturated polyester resins or their mixtures
- the invention also relates to an impregnated decorative sheet known as a finished sheet as its manufacturing process.
- the impregnated decorative sheet comprises a basic paper sheet comprising between 40 to 90% of short cellulose fibers and 10 to 60% of fibers. long, the sum being 100 by weight, between 0.2 and 1%, by dry weight of the impregnated paper, of a wet-strength agent, between 5 and 25% by dry weight of the impregnated paper, of said composition of dioxide titanium and silica according to the invention, and said paper sheet being impregnated, at a rate of 15 to 30% by dry weight of paprer rmpregne.
- the composition of pregnatron comprises in mixture 5 to 50 parts in dry pords d '' a binder chosen from poly (vinyl alcohol), gelatin, starches, cellulose fibers, alginates and their mixtures and 95 to 50 parts by dry weight of a crosslinkable polymer having a glass transition temperature between -10 and 35 ° C and used in the form of a stable aqueous dispersion or of a styrene-ethyl acrylate-butyl acrylate copolymer, the sum of the parts making 100
- the invention also relates to a decorative panel or profile laminate which is characterized by the wax that lr includes as decorative sheet one of the sheets as previously decnt More particularly, the decorative panel or profile according to the invention comprises a suppor t basic as a panel of particles or agglomerated
- Step 1 A sheet of control paper for decorative use according to the prior art is produced on a Foudnnier type paper machine.
- a sheet of paper is produced by mixing in mass with a suspension of cellulose fibers in an aqueous medium, 0.5% by dry weight relative to the strength of a r e wet resistance (résme a polyamide-polyamine- whochlorhydnne), titanium dioxide of prgments in amounts such that they are present at about 38% by weight in the paper Titanium dioxide rate is determined by the ash rate at 800 ° C, titanium dioxide being the only mineral compound therefore incombustible in the paprer, apart from the residues in the pulp (in very small quantities) Titanium dioxide is of rutrle type laminated grade that is- that is to say that it comprises a surface treatment with approximately 8% phosphate-alumina (P 2 0, s / .Al 2 ⁇ 3 ) with a positive Zeta potential at pH 6, in order to obtain good light-fastness of the pigment and regulate the surface
- thermosetting resin sheet (melamine-formaldehyde) is impregnated in aqueous solution. Then the resin is dried to obtain a resin with a volatile content of 6.5% in pords. volatiles rate is determined by heating the flower impregnated with resin at 160 ° C. for five minutes, it corresponds to the ratio of the difference in weight of the sheet on leaving the oven and its weight before entering the oven on the weight before entering the oven
- Stage 3 A plate of laminated paprers of the high pressron type is produced in the laboratory by borrowing five sheets of kraft paper already impregnated with a thermosetting phenolic resin and the sheet obtained which is placed on the top of the stack. the assembly at a temperature of 150 ° C for 40 minutes under a pressure of 10 MPa
- Step 1 A sheet of control paper for decorative use according to the prior art is produced using a titanium dioxide extending agent.
- a sheet of paper is produced by mixing in a mass, with a suspension of cellulose fibers in an aqueous medium, 0.5% by dry weight relative to the sheet of a wet resistance agent.
- a polyamide-polyanune-epichlorhydne resin titanium dioxide pigments grade laminated in quantities such that they are present in an amount of approximately 36% by weight in the paprer mixed with an extender in quantities such that they are released present in an amount of about 2% by weight in the paper
- the titanium dioxide is the same as that used in Example 1
- the extending agent is calcined kaolrn
- the sheet is dried We proceed to steps 2 and 3 as in 'example 1
- Step 1 We make a flower of decorative paper according to the invention
- a sheet of paper is produced by mass mixing, with a suspensron of cellulose fibers in an aqueous medium, 0.5% by weight relative to the sheet of a wet resistance agent (a polyamide-polyamme-epichlorhydne resin), a composition of flocs of the pigments of titanium dioxide laminated grade and of silica in quantities such that they are present at a rate of approximately 38% by weight in the paper
- a wet resistance agent a polyamide-polyamme-epichlorhydne resin
- the mixed general flocs Tr0 2 / Sr0 are produced by heterofloculatron of Tr0 2 particles with aggregates of srlrce
- the heterocoagulatron process therefore consists in adding the regulated slurry of srhce to a regulated pH in a stirred tank pred containing the suspensron of Tr0 2 (aqueous suspension of RL 62 pigments titrating at 40 g ⁇ )
- the final suspension contains 10% by mass of silica relative to the content of pigment T ⁇ 0 2 and the overall dry extract (Tr0 2 + Sr0 2 ) is around 11%
- the suspension After a contact of 16 minutes at a regulated pH of 5.5, the suspension, still agitated, is brought to a temperature between 60 ° C. and the boiling temperature for 1 to 3 hours then cooled to room temperature.
- the paprer furrlle obtained is treated according to step 2 of impregnation with thermosetting resin and step 3 of lamination as in Example 1
- Tr0 2 level in Table 1 expresses the Tr0 2 rate without the surface treatment giving the laminated grade and without the flock silrce if necessary -
- the grammage of the sheets is determined according to ISO 536 after packaging according to ISO 187
- the measurements of the colon coordinates L *, a *, b * in the CIELAB system were measured to define the whiteness of the sheet after stratification on an ELREPHO 2000 spectrocolonmetre in the CIE system under D65 illuminant (daylight and without UV) and under an observation angle of 10 degrees -
- the opacity is determined on the visible face of the decorative film as a surplus on an ELREPHO 2000 spectrophotometer, under C illuminator and under an observation angle of 10 degrees, the coefficient of reflection of the decorative laminated film on a kraft background Ro and the reflection coefficient R b of the laminated film on a white background
- the opacity of the sample is given by the ratio between these two coefficients) / R b and is expressed in percent -
- the light resistance is carried out according to ISO standard 4586-2 16 according to the blue scale. This rnventron provides decorative sheets which, when laminated, present a superior light resistance. ure or equal to 6 on the blue scale
- the abrasion resistance of the laminates according to the invention is not altered or very little altered. There are no cracks on their surface and they have good resistance to tearing off.
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- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Organic Chemistry (AREA)
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- Silicon Compounds (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU18837/99A AU1883799A (en) | 1997-12-30 | 1998-12-24 | Decorative paper sheet comprising a titanium dioxide composition and decorative laminate |
DE69808517T DE69808517T2 (de) | 1997-12-30 | 1998-12-24 | Titandioxidzusammensetzung enthaltendes dekorationspapier und dekorative schichtstoffplatte |
AT98963633T ATE225439T1 (de) | 1997-12-30 | 1998-12-24 | Titandioxidzusammensetzung enthaltendes dekorationspapier und dekorative schichtstoffplatte |
EP98963633A EP1044304B1 (fr) | 1997-12-30 | 1998-12-24 | Feuille papetiere decorative comprenant une composition de dioxyde de titane et stratifie decoratif |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9716656A FR2773180B1 (fr) | 1997-12-30 | 1997-12-30 | Feuille papetiere decorative comprenant une composition de dioxyde de titane et stratifie decoratif la comportant |
FR97/16656 | 1997-12-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999035335A1 true WO1999035335A1 (fr) | 1999-07-15 |
Family
ID=9515259
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1998/002875 WO1999035335A1 (fr) | 1997-12-30 | 1998-12-24 | Feuille papetiere decorative comprenant une composition de dioxyde de titane et stratifie decoratif |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP1044304B1 (fr) |
AT (1) | ATE225439T1 (fr) |
AU (1) | AU1883799A (fr) |
DE (1) | DE69808517T2 (fr) |
ES (1) | ES2185243T3 (fr) |
FR (1) | FR2773180B1 (fr) |
WO (1) | WO1999035335A1 (fr) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10115570A1 (de) * | 2001-03-28 | 2002-10-10 | Technocell Dekor Gmbh & Co Kg | Dekorrohpapier mit verbesserter Opazität |
US9023179B2 (en) | 2012-01-16 | 2015-05-05 | E I Du Pont De Nemours And Company | Dispersions made from treated inorganic particles for making decor paper having improved optical performance |
US9321278B2 (en) | 2012-08-06 | 2016-04-26 | Unilin, Bvba | Method for manufacturing panels having a decorative surface |
US9546450B2 (en) | 2012-11-13 | 2017-01-17 | The Chemours Company Tt, Llc | Laminates prepared from decor paper comprising self-dispersing pigments |
US9551112B2 (en) | 2012-11-13 | 2017-01-24 | The Chemours Company Tt, Llc | Decor paper comprising self-dispersing pigments |
US9701842B2 (en) | 2012-11-13 | 2017-07-11 | The Chemours Company Tt, Llc | Process for preparing self-dispersing pigments |
US9920486B2 (en) | 2013-01-09 | 2018-03-20 | The Chemours Company Fc, Llc | Décor paper having improved optical performance comprising treated inorganic particles |
US9975318B2 (en) | 2012-01-16 | 2018-05-22 | The Chemours Company Fc, Llc | Paper laminates made from decor paper having improved optical performance comprising treated inorganic particles |
US10124603B2 (en) | 2014-02-06 | 2018-11-13 | Unilin, Bvba | Methods for manufacturing panels having a decorative surface |
US10316209B2 (en) | 2012-11-13 | 2019-06-11 | The Chemours Company Fc, Llc | Self-dispersing pigments |
US10906349B2 (en) | 2014-01-10 | 2021-02-02 | Unilin Bv | Method for manufacturing panels having a decorative surface |
US11794460B2 (en) | 2018-01-04 | 2023-10-24 | Flooring Industries Limited, Sarl | Methods for manufacturing panels |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10057294C5 (de) * | 2000-11-17 | 2005-06-30 | Technocell Dekor Gmbh & Co. Kg | Dekorrohpapier mit hoher Opazität, sowie Dekorpapier oder Dekorfolie |
JP3935012B2 (ja) * | 2002-07-18 | 2007-06-20 | 日本化学工業株式会社 | 改質赤燐、その製造方法、消色化赤燐組成物及び難燃性高分子組成物 |
FI121119B (fi) | 2003-04-15 | 2010-07-15 | Kemira Oyj | Menetelmä paperin valmistamiseksi |
DE10334008A1 (de) * | 2003-07-25 | 2005-02-24 | Bausch Gmbh | Verfahren zum Lackieren von Trägerwerkstoffen mit unterschiedlichen Glanzgradzonen und danach hergestellter Trägerwerkstoff |
AU2012275788B2 (en) | 2011-06-28 | 2017-04-13 | E. I. Du Pont De Nemours And Company | Treated inorganic pigments having reduced photoactivity and anti-microbial properties and their use in paper slurries |
US9120074B2 (en) * | 2011-10-28 | 2015-09-01 | The Chemours Company Tt, Llc | Laminate paper treated with inorganic pigments having improved dispersability |
US10094069B2 (en) | 2013-01-09 | 2018-10-09 | The Chemours Company Fc, Llc | Process for making a décor paper having improved optical performance |
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US2943013A (en) * | 1956-07-27 | 1960-06-28 | Hurlbut Paper Company | High ash content absorbent paper for the decorative laminating industry and a process for preparing the same |
US4461810A (en) * | 1983-04-04 | 1984-07-24 | E. I. Du Pont De Nemours And Company | TiO2 Pigment bearing a coating with cerium cations and sulfate-, phosphate- or silicate anions and laminate and coating containing same |
WO1989008739A1 (fr) * | 1988-03-18 | 1989-09-21 | Ppg Industries, Inc. | Papier de qualite saturation |
GB2234990A (en) * | 1989-08-18 | 1991-02-20 | Tioxide Group Plc | Fibrous sheet material |
EP0573150A2 (fr) * | 1992-06-04 | 1993-12-08 | Tioxide Group Services Limited | Matériau pigmentaire composite |
-
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- 1997-12-30 FR FR9716656A patent/FR2773180B1/fr not_active Expired - Fee Related
-
1998
- 1998-12-24 DE DE69808517T patent/DE69808517T2/de not_active Expired - Lifetime
- 1998-12-24 AT AT98963633T patent/ATE225439T1/de not_active IP Right Cessation
- 1998-12-24 ES ES98963633T patent/ES2185243T3/es not_active Expired - Lifetime
- 1998-12-24 WO PCT/FR1998/002875 patent/WO1999035335A1/fr active IP Right Grant
- 1998-12-24 AU AU18837/99A patent/AU1883799A/en not_active Abandoned
- 1998-12-24 EP EP98963633A patent/EP1044304B1/fr not_active Expired - Lifetime
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US2943013A (en) * | 1956-07-27 | 1960-06-28 | Hurlbut Paper Company | High ash content absorbent paper for the decorative laminating industry and a process for preparing the same |
US4461810A (en) * | 1983-04-04 | 1984-07-24 | E. I. Du Pont De Nemours And Company | TiO2 Pigment bearing a coating with cerium cations and sulfate-, phosphate- or silicate anions and laminate and coating containing same |
WO1989008739A1 (fr) * | 1988-03-18 | 1989-09-21 | Ppg Industries, Inc. | Papier de qualite saturation |
GB2234990A (en) * | 1989-08-18 | 1991-02-20 | Tioxide Group Plc | Fibrous sheet material |
EP0573150A2 (fr) * | 1992-06-04 | 1993-12-08 | Tioxide Group Services Limited | Matériau pigmentaire composite |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10115570B4 (de) * | 2001-03-28 | 2005-09-08 | Technocell Dekor Gmbh & Co. Kg | Dekorrohpapier mit verbesserter Opazität |
DE10115570A1 (de) * | 2001-03-28 | 2002-10-10 | Technocell Dekor Gmbh & Co Kg | Dekorrohpapier mit verbesserter Opazität |
US9975318B2 (en) | 2012-01-16 | 2018-05-22 | The Chemours Company Fc, Llc | Paper laminates made from decor paper having improved optical performance comprising treated inorganic particles |
US9023179B2 (en) | 2012-01-16 | 2015-05-05 | E I Du Pont De Nemours And Company | Dispersions made from treated inorganic particles for making decor paper having improved optical performance |
US11446938B2 (en) | 2012-08-06 | 2022-09-20 | Flooring Industries Limited, Sarl | Method for manufacturing panels having a decorative surface |
US10549550B2 (en) | 2012-08-06 | 2020-02-04 | Unilin, Bvba | Method for manufacturing panels having a decorative surface |
US9566823B2 (en) | 2012-08-06 | 2017-02-14 | Unilin, Bvba | Method for manufacturing panels having a decorative surface |
US11987044B2 (en) | 2012-08-06 | 2024-05-21 | Unilin, Bv | Method for manufacturing panels having a decorative surface |
US9321278B2 (en) | 2012-08-06 | 2016-04-26 | Unilin, Bvba | Method for manufacturing panels having a decorative surface |
US10814648B1 (en) | 2012-08-06 | 2020-10-27 | Unilin, Bvba | Method for manufacturing panels having a decorative surface |
US10807385B2 (en) | 2012-08-06 | 2020-10-20 | Unilin, Bvba | Method for manufacturing panels having a decorative surface |
US10214028B2 (en) | 2012-08-06 | 2019-02-26 | Unilin, Bvba | Method for manufacturing panels having a decorative surface |
US9546450B2 (en) | 2012-11-13 | 2017-01-17 | The Chemours Company Tt, Llc | Laminates prepared from decor paper comprising self-dispersing pigments |
US10316209B2 (en) | 2012-11-13 | 2019-06-11 | The Chemours Company Fc, Llc | Self-dispersing pigments |
US9551112B2 (en) | 2012-11-13 | 2017-01-24 | The Chemours Company Tt, Llc | Decor paper comprising self-dispersing pigments |
US9701842B2 (en) | 2012-11-13 | 2017-07-11 | The Chemours Company Tt, Llc | Process for preparing self-dispersing pigments |
US9920486B2 (en) | 2013-01-09 | 2018-03-20 | The Chemours Company Fc, Llc | Décor paper having improved optical performance comprising treated inorganic particles |
US10906349B2 (en) | 2014-01-10 | 2021-02-02 | Unilin Bv | Method for manufacturing panels having a decorative surface |
US11465439B2 (en) | 2014-01-10 | 2022-10-11 | Flooring Industries Limited, Sarl | Method for manufacturing panels having a decorative surface |
US11878548B2 (en) | 2014-01-10 | 2024-01-23 | Flooring Industries Limited, Sarl | Method for manufacturing panels having a decorative surface |
US10124603B2 (en) | 2014-02-06 | 2018-11-13 | Unilin, Bvba | Methods for manufacturing panels having a decorative surface |
US10994555B2 (en) | 2014-02-06 | 2021-05-04 | Unilin Bv | Methods for manufacturing panels having a decorative surface |
US11613133B2 (en) | 2014-02-06 | 2023-03-28 | Unilin Bv | Methods for manufacturing panels having a decorative surface |
US11794460B2 (en) | 2018-01-04 | 2023-10-24 | Flooring Industries Limited, Sarl | Methods for manufacturing panels |
Also Published As
Publication number | Publication date |
---|---|
ES2185243T3 (es) | 2003-04-16 |
DE69808517T2 (de) | 2003-06-26 |
AU1883799A (en) | 1999-07-26 |
FR2773180B1 (fr) | 2000-02-04 |
ATE225439T1 (de) | 2002-10-15 |
EP1044304A1 (fr) | 2000-10-18 |
EP1044304B1 (fr) | 2002-10-02 |
DE69808517D1 (de) | 2002-11-07 |
FR2773180A1 (fr) | 1999-07-02 |
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