EP1570023A1 - Light transforming material comprising as additive a barium and magnesium silicate - Google Patents

Light transforming material comprising as additive a barium and magnesium silicate

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Publication number
EP1570023A1
EP1570023A1 EP03767895A EP03767895A EP1570023A1 EP 1570023 A1 EP1570023 A1 EP 1570023A1 EP 03767895 A EP03767895 A EP 03767895A EP 03767895 A EP03767895 A EP 03767895A EP 1570023 A1 EP1570023 A1 EP 1570023A1
Authority
EP
European Patent Office
Prior art keywords
additive
matrix
compound
material according
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.)
Withdrawn
Application number
EP03767895A
Other languages
German (de)
French (fr)
Inventor
Wilfried Blanc
Claude Ceintrey
Claude Fouassier
Thierry Le Mercier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Electronics and Catalysis SAS
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Rhodia Electronics and Catalysis SAS
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Filing date
Publication date
Application filed by Rhodia Electronics and Catalysis SAS filed Critical Rhodia Electronics and Catalysis SAS
Publication of EP1570023A1 publication Critical patent/EP1570023A1/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77342Silicates
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/20Forcing-frames; Lights, i.e. glass panels covering the forcing-frames
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/12Technologies relating to agriculture, livestock or agroalimentary industries using renewable energies, e.g. solar water pumping

Definitions

  • the present invention relates to a light-transforming material, in particular for greenhouse walls, comprising as an additive a barium and magnesium silicate.
  • light-transforming material is meant in the sense of the present description a material which is in particular capable of transforming UV radiation into red light. The need for such a material exists in several technical fields.
  • polymers and mineral glasses are widely used for the manufacture of walls for greenhouses for agriculture. These polymers or mineral glasses must meet specific technical characteristics to allow optimal protection and development of crops.
  • the object of the present invention is to provide a material which is capable of transforming UV radiation and in particular solar energy of the UV range, into a red light, in particular into a light which is more easily assimilated or usable for plants.
  • the light-transforming material according to the invention is of the type comprising a matrix and an additive and it is characterized in that it comprises, as an additive, a compound of formula:
  • FIG. 1 is a graph which represents the emission spectra of two additives according to the invention for an excitation wavelength of 370 nm;
  • FIG. 2 is a graph which represents the excitation spectrum of an additive according to the invention for an emission wavelength of 623nm;
  • FIG. 3 is a graph which represents the variation in intensity of absorption (1-R, R denoting the intensity of diffuse reflection) as a function of the wavelength for an additive of the invention, measured in synchronous mode using a spectrophotometer equipped with a front monochromator and a rear monochromator.
  • the invention applies to any type of material based on a matrix and an additive and which, by virtue of its mechanical and / or optical properties, is used or capable of being used in an application in which it is sought to transform UV radiation into red light in particular or else to transform UV radiation, and in particular UV radiation from sunlight, into less energetic radiation.
  • This matrix can be a fiber, natural or not, such as silk, wool, cotton, hemp or even viscose, nylon, polyamides, polyester and their copolymers.
  • the matrix can also be a mineral (silicate) or organic glass.
  • the matrix may also be based on a polymer, in particular of the thermoplastic type.
  • thermoplastic polymers suitable for the invention mention may be made of: polycarbonates such as poly [methane bis (4-phenyl) carbonate], poly [1,1-ether bis (4-phenyl) carbonate], poly [diphenyl methane bis (4-phenyl) carbonate], poly [1,1-cyclohexane bis (4-phenyl) carbonate] and polymers of the same family; polyamides such as poly (4-amino butyric acid), poly (hexamethylene adipamide), poly (6-aminohexanoic acid), poly (m-xylylene adipamide), poly (p- xylylene sebacamide), poly ( 2,2,2-trimethylhexamethylene terephthalamide), poly (metaphenylene isophthalamide), poly (p-phenylene terephthalamide), and polymers of the
  • comonomers used can be cyclic olefins such as 1,4-hexadiene, cyclopentadiene and ethylidenenorbornene.
  • the copolymers can also be a carboxylic acid such as acrylic acid or methacrylic acid.
  • polyethylenes are particularly preferred, including PEBD (low density polyethylenes), LLDPE (linear low density polyethylenes), polyethylenes obtained by metallocene synthesis, PVC (polyvinyl chloride), PET (polyethylene terephthalate) , polymethylmethacrylate, copolyolefins such as EVA (polyethylene of vinyl alcohol or ethylene vinyl acetate), mixtures and copolymers based on these (co) polymers, polycarbonate
  • the polymer may be in a rigid form and a sheet or plate a few millimeters thick, for example in the case of polyvinyl chloride, methyl methacrylate or polycarbonate.
  • the material of the invention can be deposited on, or associated with another substrate, such as the thermoplastics described above. This deposition or this association can be done by known methods of coextrusion, lamination, coating.
  • Multilayer structures can be formed from one or more layers of material according to the invention, associated by layers of coextrusion binder with one or more other layers of one or more thermoplastic polymers (for example polyethylene, polychloride vinyl) which can constitute a support element, majority in the constitution of the film.
  • the films thus obtained can be mono-stretched, bi-stretched according to known techniques for processing thermoplastics.
  • the sheets or plates can be cut, thermoformed, stamped to give them the desired shape.
  • the material of the invention can also be in the form of a matrix based on a paint or varnish or on a latex, this matrix being able to be deposited as a coating on an organic or mineral substrate such as a glass.
  • paint or varnish is meant the formulations or compositions usually designated by this term in the technical field of paints and which are for example based on the following emulsion resins: alkyd resins, the most common of which is called glycerophthalic; long or short oil modified resins; acrylic resins derived from acrylic (methyl or ethyl) and methacrylic acid esters optionally copolymerized with ethyl acrylate, 2-ethylhexyl or butyl acrylate as well as acrylic-isocyanate resins; vinyl resins such as, for example, polyvinyl acetate, polyvinyl chloride, butyralpolyvinyl, formalpolyvinyl, and the copolymers of vinyl chloride and vinyl acetate or vinyliden
  • latex is understood to mean the aqueous dispersions of polymer particles resulting from conventional emulsion (co) polymerization processes of polymerizable organic monomers.
  • organic monomers can be chosen, for example, from alkyl (meth) acrylates, alpha, beta-ethylenically unsaturated esters; esters and hemi-esters of alpha, beta-polycarboxylic acids ethylenically unsaturated; vinyl halides; aromatic vinyls; conjugated aliphatic dienes; alpha, beta-ethylenically unsaturated nitriles; polyvinyl acetate latexes, isocyanates, polyols.
  • the material as described above contains, as an additive, a barium and magnesium silicate, doped with europium, which can be considered as a partial substitution for barium, and with manganese, which can be considered as a partial substitution for magnesium, this silicate corresponding to formula (1) which has been given above.
  • this additive When it is subjected to UV or near UV (UVA) excitation, that is to say radiation in a wavelength range between about 250 nm and about 390 nm, this additive has the property of emitting especially in red and also in blue, that is to say in a wavelength range between about 370 nm and about 400 nm (between 400 nm and 500 nm for blue and between 550 nm and 700 nm for red) with good yield.
  • UV or near UV (UVA) excitation that is to say radiation in a wavelength range between about 250 nm and about 390 nm
  • UVA near UV
  • the compound corresponds to the above formula (1) in which 0.0001 ⁇ x ⁇ 0.25 and 0.0001 ⁇ y ⁇ 0.25.
  • the compound corresponds to the above formula (1) in which 0.01 ⁇ x ⁇ 0.25 and 0.01 ⁇ y ⁇ 0.25. It may be noted that it is advantageous to have a concentration of europium in the compound of at least 0.01% in order to obtain a better intensity emission. It is also advantageous to have a concentration of europium and manganese of at most 25% in order to limit as much as possible annoying self-extinction phenomena.
  • the percentages indicated above correspond to the substitution rates by mole of the doping ions Eu 2+ and Mn 2 respectively for the ions Ba 2+ and Mg 2+ .
  • the compound of formula (1) checks the following values of x and y: 0.01 ⁇ x ⁇ 0.03 and 0.04 ⁇ y ⁇ 0.06. For these values of x and y the emission intensity is the most important.
  • barium, magnesium and silicon may be partially substituted by elements other than those which have been described above.
  • the barium can be partially substituted by calcium and / or strontium in a proportion which can go up to approximately 30%, this proportion being expressed by the atomic substituent / (susbtituant + barium) ratio.
  • the magnesium can be partially substituted by zinc in a proportion which can go up to approximately 30%, this proportion being also expressed by the atomic ratio Zn / (Zn + Mg).
  • silicon can be partially substituted by germanium, of aluminum and / or phosphorus in a proportion which can go up to approximately 10%, this proportion being expressed by the atomic ratio substituent / (susbtituant + silicon).
  • the amount of silicate in the material can be in particular between 0.01% and 10% by mass relative to the total mass of the material, more particularly between 0.1% and 1%. These values are given by way of example only and they may vary depending on the nature of the matrix.
  • the low value is fixed according to the intensity of the desired effect which one wishes to obtain.
  • the high value is not critical, generally one does not exceed the value beyond which an additional quantity does not bring an advantage or additional effect compared to other constraints for example cost constraints.
  • the additive of the invention has a UV absorption capacity which also enables it to provide an anti-UV function and therefore to protect against the UV the materials in which it is incorporated.
  • the silicate used for the invention is generally prepared by a reaction in the solid state at high temperature.
  • the oxides of the required metals or organic or inorganic compounds capable of forming these oxides by heating such as the carbonates, oxalates, hydroxides, acetates, nitrates, borates of said metals.
  • the mixture of starting materials is then heated at least once for a period of between one hour and one hundred hours approximately, to a temperature between approximately 500 ° C and approximately 1600 ° C; it is preferable to carry out the heating at least in part under a reducing atmosphere (hydrogen in argon for example) to bring the europium completely to the divalent state.
  • a reducing atmosphere hydrogen in argon for example
  • silicates there is no limitation to the shape, the morphology, the average particle size or the particle size distribution of the silicates thus obtained.
  • These products can be ground, micronized, sieved and surface treated, in particular with organic additives, to facilitate compatibility or dispersion in the application medium.
  • the material of the invention in addition to the matrix based on the elements described above such as fiber, polymer, paint or varnish or latex, and the compound based on barium silicate and magnesium mentioned above, can also comprise, in a known manner, other additives, such as for example stabilizers, plasticizers, flame retardants, dyes, optical brighteners, lubricants, anti-sticking agents, matting agents, processing, elastomers or compositions of elastomers (for example acrylic copolymers or copolymers of methacrylate butadiene styrene) making it possible to improve the flexibility or the mechanical resistance of films or sheets, adhesion agents (for example polyolefins grafted with maleic anhydride allowing adhesion to polyamide), dispersing agents allowing a better distribution of the silicate in the material or t any other additive necessary for the production of multilayer thermoplastic film structures, in particular those known and often used for the production of greenhouse films (for example anti-drip, anti-fogging)
  • a first method consists in mixing the silicate and the other aforementioned additives in a thermoplastic compound in molten form and optionally subjecting the mixture to significant shearing, for example in a twin-screw extrusion device, in order to achieve good dispersion.
  • Another method consists in mixing the additive (s) to be dispersed with the monomers in the polymerization medium, then in carrying out the polymerization.
  • Another method consists in mixing with a thermoplastic polymer in molten form, a concentrated mixture of a thermoplastic polymer and dispersed additives, prepared for example according to one of the methods described above.
  • the silicate can be introduced into the synthesis medium of the macromolecular compound, or into a molten thermoplastic polymer in any form. It can for example be introduced in the form of a solid powder or in the form of a dispersion in water or in an organic dispersant.
  • a process suitable for paints or varnishes or latexes consists in directly dispersing the silicate compound in the form of powder in the latex or in the paint or varnish, for example by stirring, or else in preparing a powder concentrate in a liquid or pasty medium which is then added to paints or varnishes or latex.
  • the concentrate can be prepared in an aqueous or solvent medium, optionally with surfactants, water-soluble or hydrophobic polymers or alternatively comprising hydrophilic and hydrophobic ends, polar or not, necessary for the stabilization of the mixture to avoid decantation.
  • surfactants water-soluble or hydrophobic polymers or alternatively comprising hydrophilic and hydrophobic ends, polar or not, necessary for the stabilization of the mixture to avoid decantation.
  • additives which may enter into the composition of the concentrate.
  • the material of the invention can be very particularly used in the manufacture or in the construction of greenhouse walls.
  • the term "greenhouse” should be understood here broadly as covering any type of shelter used in agriculture for the protection and development of crops.
  • it can be greenhouses and large plastic tunnels, glass greenhouses, large shelters, semi-forcings, flat tarpaulins, mulches etc. as described in the brochure published by CIPA (International Congress of Plastic in Agriculture) 65 rue de Prony, Paris, "The evolution of plasticulture in the World” by Jean-Pierre Jouet.
  • the invention therefore relates to walls for greenhouses which comprise a material as described above.
  • the material of the invention can also be used in the field of cosmetics, in particular in the preparation of nail varnishes and styling gels.
  • Nail polishes generally contain:
  • plasticizer for example, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, tricresylphosphate, n-butyl stearate, resorcin diacetate or a mixture thereof,
  • a solvent such as ethyl, isopropyl, butyl, isobutyl alcohol, ethyl acetate, butyl acetate or most often the mixture of these solvents, - a diluent, in particular toluene or xylene,
  • perfume or pearlescent product mica flakes coated with bismuth oxychloride or titanium dioxide.
  • plasticizer (s) from 3 to 5% by weight of plasticizer (s),
  • the varnish constitutes the matrix and the compound of formula (1) is present as an additive in this matrix.
  • the compound is generally ground in a plastic mass consisting of nitrocellulose and plasticizer (s) which is then dissolved in the solvent (s).
  • the amount of compound used is usually 1% to 5% by mass relative to the varnish. It should be noted that these values are given as an indication and that they are not critical. They can be modified as a function of the intensity of the desired effect, ie the luminescence in the red, and cost constraints.
  • the invention therefore also relates to nail varnishes which comprise a compound of formula (1) as described above.
  • Styling gels generally contain:
  • a gelling agent which can be, for example, hydroxyethyl cellulose, an ethylene-maleic anhydride copolymer or a carbomer (homopolymer of acrylic acid crosslinked with an allyl ether of pentaerythritol, an allyl ether of sucrose or an allyl ether of propylene);
  • a fixing polymer which can in particular be polyvinyl pyrrolidone (PVP), a polyvinyl pyrrolidone / vinyl acetate mixture, terpolymers;
  • a conditioning agent such as polyquaternium-11, polyquatemium-4 or polyquatemium-7, a PVP / dimethylaminoethylmethacrylate copolymer mixture, a guar;
  • a plasticizing agent such as dimethicone copolyol.
  • the gel constitutes the matrix and the compound of formula (1) is present as an additive in this matrix.
  • the amount of compound used is usually 0.5% to 4% by mass relative to the gel.
  • the material of the invention can also be used in the manufacture of fabrics for clothing, in the construction of buildings or shelters, in automobile industry. Thus, it can be used in the manufacture of luminescent films for non-agricultural applications, for luminescent paints or glasses with luminescent coatings for buildings or automobiles.
  • the material of the invention can also be used in light-emitting diodes (LEDs). Finally, it can be used in the manufacture of materials usable in bio-technologies. Examples will now be given.
  • EXAMPLE 1 This example relates to the preparation of a compound corresponding to the composition Ba 3 MgSi 2 O 8 : 2% Eu 2+ , 5% Mn 2+ and corresponding to the formula Ba2, 94 Euo, o6Mgo, 95 Mno, o 5 If 2 ⁇ 8 (the percentages indicated for the doping ions correspond to the rates of substitution by mole of the Eu 2+ and Mn 2+ ions respectively to the Ba 2+ and Mg 2+ ions).
  • Per channel is carried by mixing the solid BaC0 3 oxide, Eu 2 O 3, (MgCO 3) 4 Mg (OH) 2 .5H 2 O, MnCO 3 and SiO 2 in stoichiometric proportions. 0.4 mole of NH 4 CI is added to the mixture as a stream.
  • This example concerns the preparation of a compound corresponding to the composition Ba 3 MgSi 2 O 8 : 2% Eu 2+ , 20% Mn 2+ and corresponding to the formula Ba2.94Euo, o6Mgo, 8Mno, 2 Si 2 ⁇ 8 .
  • the procedure is as in Example 1, by solid route, by mixing the oxides BaC0 3 , Eu 2 0 3 , (MgCO 3 ) 4 Mg (OH) 2 .5H 2 ⁇ , MnCO 3 and Si ⁇ 2 in stoichiometric proportions. 0.4 mole of NH 4 CI is added to the mixture as a stream.
  • the curves of FIG. 1 give, for the compounds thus obtained, the emission spectrum for an excitation wavelength of 370 nm. We therefore see that in response to an excitation in the UV range, the compounds emit in red (peak around 625nm) and also in blue (peak towards
  • FIG. 3 is a graph, produced in synchronous mode, which represents the variation in intensity of absorption as a function of the wavelength of the compound of Example 1. This graph clearly shows the absorption capacity of the UV of the compound since the reflection intensity is practically zero for a wavelength less than about 425nm.
  • Example 2 illustrates the use in an polymer film of an additive according to the invention.
  • the product obtained in Example 1 is steamed for 12 hours at 90 ° C. It is then mixed in a cube mixer for 10 minutes with LDPE Lacqtène 1020FN24, PEG 400 (sticky agent) and an antioxidant Irganox B225.
  • the formulations used are as follows:
  • the implementation is carried out on a ZSK30 twin screw extruder on which is adapted a flat die of 30cm width and adjustable opening as well as a cast film machine allowing to stretch the film at the extruder outlet in order to l '' bring to the thickness of 100 ⁇ m.
  • the temperature in the extruder and in the film die is 180 ° C.
  • the temperature at the inlet of the film cast machine is 70 ° C.
  • the other conditions are as follows:
  • the film obtained emits a purple color when subjected to lighting with a wavelength of 370nm.
  • Films are prepared in the same manner as in Example 3 with the product of Example 1 which, however, has not undergone oven treatment.
  • HALS is a known anti-UV additive (50% Tinuvin622-50% Chimasorb 944).
  • the films produced have a thickness of between 110 ⁇ m and 130 ⁇ m.
  • the films obtained are placed on a contrast card and the chromaticity coordinates L, a and b are measured on a white background with a Minolta 508d spectrocolorimeter, the specular component being included. These coordinates are given in the CIE 1976 system (L, a and b) as defined by the International Lighting Commission and listed in the Collection of French Standards (AFNOR), colorimetric n ° X08-12, n ° X08- 14 (1983). A Haze measurement is also carried out with an XL-211 Hazegard haze meter from Byk-Garner.
  • the film of test 1 is colorless.
  • the white ⁇ E varies in proportions which are below the measurement uncertainties, which shows that the addition of the compound of the invention does not cause the color of the film to change, there is no yellowing by example.
  • the Haze measurement makes it possible to assess the transparency of the film. There is also no significant variation in transparency.
  • control test 1 in the wavelength range from 250 nm to 750 nm, no significant modification of the transmission spectrum between the film is observed. of control test 1 and the film of test 2 or between that of test 3 and that of control test 4.
  • EXAMPLE 5 This example relates to the use of the product of Example 1 in the preparation of a nail varnish.
  • This varnish is a transparent base marketed by the company GEMEY (3.55 g) and containing:
  • This example relates to the use of the product of Example 1 in the preparation of a styling gel.

Abstract

The invention concerns a light transforming material, in particular for greenhouse walls, comprising as additive a barium and magnesium silicate of formula Ba3(1-x)Eu3xMg1-yMnySi2O8 (1), wherein 0 < x = 0.3 and 0 < y = 0.3. Said material is capable of transforming solar energy of UV range into a red light. Said material can also be used in paints and cosmetics.

Description

MATERIAU TRANSFORMANT LA LUMIERE COMPRENANT COMME ADDITIF UN SILICATE DE BARYUM ET DE MAGNESIUM LIGHT TRANSFORMING MATERIAL INCLUDING BARYUM AND MAGNESIUM SILICATE AS ADDITIVE
La présente invention concerne un matériau transformant la lumière, notamment pour parois de serres, comprenant comme additif un silicate de baryum et de magnésium.The present invention relates to a light-transforming material, in particular for greenhouse walls, comprising as an additive a barium and magnesium silicate.
Par « matériau transformant la lumière », on entend au sens de la présente description un matériau qui est notamment capable de transformer un rayonnement UV en lumière rouge. Le besoin en un tel matériau existe dans plusieurs domaines techniques.By “light-transforming material” is meant in the sense of the present description a material which is in particular capable of transforming UV radiation into red light. The need for such a material exists in several technical fields.
Ainsi, les polymères et les verres minéraux sont largement utilisés pour la fabrication de parois pour serres pour l'agriculture. Ces polymères ou ces verres minéraux doivent répondre à des caractéristiques techniques spécifiques pour permettre une protection et un développement optimaux des cultures.Thus, polymers and mineral glasses are widely used for the manufacture of walls for greenhouses for agriculture. These polymers or mineral glasses must meet specific technical characteristics to allow optimal protection and development of crops.
On recherche en particulier des matériaux qui permettent une utilisation la plus efficace possible des radiations solaires. On sait notamment que les radiations dans le domaine du rouge-orange c'est dire pour des longueurs d'onde entre environ 500nm et environ 700nm sont particulièrement utiles pour le développement des plantes, elles favorisent notamment la photosynthèse, alors que les radiations du domaine de l'ultra-violet ne sont pas absorbées par celles-ci. II existe aussi d'autres domaines, comme le domaine de la cosmétique ou encore celui des peintures, dans lesquels on cherche des matériaux qui peuvent émettre notamment dans le rouge lorsqu'ils sont soumis à un rayonnement UV.We are looking in particular for materials that allow the most efficient use of solar radiation. We know in particular that the radiations in the red-orange domain, that is to say for wavelengths between about 500nm and about 700nm are particularly useful for the development of plants, they promote photosynthesis in particular, while the radiations in the domain of the ultraviolet are not absorbed by them. There are also other fields, such as the field of cosmetics or even that of paints, in which materials are sought which can emit in particular in red when they are subjected to UV radiation.
L'objet de la présente invention est de fournir un matériau qui soit capable de transformer un rayonnement UV et notamment l'énergie solaire de la gamme des UV, en une lumière rouge, en particulier en une lumière qui soit plus facilement assimilable ou utilisable pour les plantes.The object of the present invention is to provide a material which is capable of transforming UV radiation and in particular solar energy of the UV range, into a red light, in particular into a light which is more easily assimilated or usable for plants.
Dans ce but, le matériau transformant la lumière selon l'invention est du type comprenant une matrice et un additif et il est caractérisé en ce qu'il comprend à titre d'additif un composé de formule :For this purpose, the light-transforming material according to the invention is of the type comprising a matrix and an additive and it is characterized in that it comprises, as an additive, a compound of formula:
Ba3(i-χ)Eu3χMg1.yMnySi2θ8 (1) dans laquelle 0 < x < 0,3 et 0 < y < 0,3. D'autres caractéristiques, détails et avantages de l'invention apparaîtront encore plus complètement à la lecture de la description qui va suivre et du dessin annexé dans lequel :Ba 3 ( i-χ ) Eu 3 χMg 1 . y Mn y Si 2 θ 8 (1) in which 0 <x <0.3 and 0 <y <0.3. Other characteristics, details and advantages of the invention will appear even more completely on reading the description which follows and the attached drawing in which:
- la figure 1 est un graphe qui représente les spectres d'émission de deux additifs selon l'invention pour une longueur d'onde d'excitation de 370nm;- Figure 1 is a graph which represents the emission spectra of two additives according to the invention for an excitation wavelength of 370 nm;
- la figure 2 est un graphe qui représente le spectre d'excitation d'un additif selon l'invention pour une longueur d'onde d'émission de 623nm;- Figure 2 is a graph which represents the excitation spectrum of an additive according to the invention for an emission wavelength of 623nm;
- la figure 3 est un graphe qui représente la variation d'intensité de l'absorption (1-R, R désignant l'intensité de reflexion diffuse) en fonction de la longueur d'onde pour un additif de l'invention, mesurée en mode synchrone à l'aide d'un spectrophotomètre équipé d'un monochromateur avant et d'un monochromateur arrière.FIG. 3 is a graph which represents the variation in intensity of absorption (1-R, R denoting the intensity of diffuse reflection) as a function of the wavelength for an additive of the invention, measured in synchronous mode using a spectrophotometer equipped with a front monochromator and a rear monochromator.
L'invention s'applique à tout type de matériau à base d'une matrice et d'un additif et qui, de par ses propriétés mécaniques et/ou optiques, est utilisé ou susceptible d'être utilisé dans une application dans laquelle on cherche à transformer un rayonnement UV en lumière rouge notamment ou bien à transformer les rayonnements UV, et notamment les rayonnements UV de la lumière solaire, en des rayonnements moins énergétiques.The invention applies to any type of material based on a matrix and an additive and which, by virtue of its mechanical and / or optical properties, is used or capable of being used in an application in which it is sought to transform UV radiation into red light in particular or else to transform UV radiation, and in particular UV radiation from sunlight, into less energetic radiation.
Cette matrice peut être une fibre, naturelle ou non, telle que la soie, la laine, le coton, le chanvre ou encore la viscose, le nylon, les polyamides, le polyester et leurs copolymères.This matrix can be a fiber, natural or not, such as silk, wool, cotton, hemp or even viscose, nylon, polyamides, polyester and their copolymers.
La matrice peut être aussi un verre minéral (silicate) ou organique. La matrice peut encore être à base d'un polymère notamment de type thermoplastique. A titre d'exemple de polymères thermoplastiques convenables pour l'invention on peut citer : les polycarbonates comme le poly[méthane bis(4- phényl) carbonate], le poly[1 ,1-éther bis(4-phényl) carbonate], le poly[diphényl méthane bis(4-phényl)carbonate], le poly[1 ,1-cyclohexane bis(4- phényl)carbonate] et les polymères de la même famille; les polyamides comme le poly(acide 4-amino butyrique), le poly(héxaméthylène adipamide), le poly(acide 6-aminohéxanoïque), le poly(m-xylylène adipamide), le poly(p- xylylène sébacamide), le poly(2,2,2-triméthyl héxaméthylène téréphtalamide), le poly(métaphénylène isophtalamide), le poly(p-phénylène téréphtalamide), et les polymères de la même famille; les polyesters comme le poly(éthylène azélate), le poly(éthylène-1 ,5-naphtalate, le poly(1 ,4-cyclohexane diméthylène téréphtalate), le poly(éthylène oxybenzoate), le poly ara-hydroxy benzoate), le poly(1 ,4-cyclohéxylidène diméthylène téréphtalate), le poly(1 ,4- cyclohéxylidène diméthylène téréphtalate), le polyéthylène téréphtalate, le polybutylène téréphtalate et les polymères de la même famille; les polymères vinyliques et leurs copolymères comme l'acétate de polyvinyle, l'alcool polyvinylique, le chlorure de polyvinyle; le polyvinyle butyral, le chlorure de polyvinylidène, les copolymères éthylène- acétate de vinyle, et les polymères de la même famille; les polymères acryliques, les polyacrylates et leurs copolymères comme l'acrylate de polyéthyle, le poly(n-butyl acrylate), le polyméthylméthacrylate, le polyéthyl méthacrylate, le poly(n-butyl méthacrylate), le poly(n-propyl méthacrylate), le polyacrylamide, le polyacrylonitrile, le poly(acide acrylique), les copolymères éthylène- acide acrylique, les copolymères éthylène- alcool vinylique, les copolymères de l'acrylonitrile, les copolymères méthacrylate de méthyle -styrène, les copolymères éthylène-acrylate d'éthyle, les copolymères méthacrylate- butadiène-styrène, l'ABS, et les polymères de la même famille; les polyoléfines comme le poly(éthylène) basse densité, le poly(propylène) ) et en général les alpha oléfines d'éthylènes et de propylène copolymérisées avec d'autres alpha oléfines telles que les 1 -butène, et 1-hexènes qui peuvent être utilisées jusqu'à moins de 1%. D'autres comonomères utilisés peuvent être des oléfines cycliques telles que le 1 ,4-hexadiène, le cyclopentadiène et l'éthylidènenorbornène. Les copolymères peuvent aussi être un acide carboxylique tel que l'acide acrylique ou l'acide méthacrylique. On peut enfin mentionner le poly(éthylène) chloré basse densité, le poly(4-méthyl-1- pentène), le poly(éthylène), le poly(styrène).The matrix can also be a mineral (silicate) or organic glass. The matrix may also be based on a polymer, in particular of the thermoplastic type. By way of example of thermoplastic polymers suitable for the invention, mention may be made of: polycarbonates such as poly [methane bis (4-phenyl) carbonate], poly [1,1-ether bis (4-phenyl) carbonate], poly [diphenyl methane bis (4-phenyl) carbonate], poly [1,1-cyclohexane bis (4-phenyl) carbonate] and polymers of the same family; polyamides such as poly (4-amino butyric acid), poly (hexamethylene adipamide), poly (6-aminohexanoic acid), poly (m-xylylene adipamide), poly (p- xylylene sebacamide), poly ( 2,2,2-trimethylhexamethylene terephthalamide), poly (metaphenylene isophthalamide), poly (p-phenylene terephthalamide), and polymers of the same family; polyesters such as poly (ethylene azelate), poly (ethylene-1,5-naphthalate, poly (1,4-cyclohexane dimethylene terephthalate), poly (ethylene oxybenzoate), poly ara-hydroxy benzoate) (1,4-cyclohexylidene dimethylene terephthalate), poly (1,4-cyclohexylidene dimethylene terephthalate), polyethylene terephthalate, polybutylene terephthalate and polymers of the same family; vinyl polymers and their copolymers such as polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride; polyvinyl butyral, polyvinylidene chloride, ethylene-vinyl acetate copolymers, and polymers of the same family; acrylic polymers, polyacrylates and their copolymers such as polyethyl acrylate, poly (n-butyl acrylate), polymethylmethacrylate, polyethyl methacrylate, poly (n-butyl methacrylate), poly (n-propyl methacrylate), polyacrylamide, polyacrylonitrile, poly (acrylic acid), ethylene-acrylic acid copolymers, ethylene-vinyl alcohol copolymers, acrylonitrile copolymers, methyl methacrylate-styrene copolymers, ethylene-ethyl acrylate copolymers , methacrylate-butadiene-styrene copolymers, ABS, and polymers of the same family; polyolefins such as low density poly (ethylene), poly (propylene)) and in general the alpha olefins of ethylene and propylene copolymerized with other alpha olefins such as 1-butene, and 1-hexenes which may be used up to less than 1%. Other comonomers used can be cyclic olefins such as 1,4-hexadiene, cyclopentadiene and ethylidenenorbornene. The copolymers can also be a carboxylic acid such as acrylic acid or methacrylic acid. Finally, mention may be made of low density chlorinated poly (ethylene), poly (4-methyl-1-pentene), poly (ethylene), poly (styrene).
Parmi ces polymères thermoplastiques, on préfère tout particulièrement les polyéthylenes dont les PEBD (polyéthylenes basse densité), les LLDPE (polyéthylenes basse densité linéaires), les polyéthylenes obtenus par synthèse métallocène, le PVC (polychlorure de vinyle), le PET (polyéthylène téréphtalate), le polyméthylméthacrylate, les copolyoléfines telles que l'EVA (polyéthylène d'alcool vinylique ou éthylène vinyl acétate), les mélanges et copolymères à base de ces (co)polymères, le polycarbonate Le polymère peut se présenter sous une forme rigide et d'une feuille ou d'une plaque de quelques millimètres d'épaisseur par exemple dans le cas du chlorure de polyvinyle, du méthacrylate de méthyle ou du polycarbonate. Il peut aussi se présenter sous forme d'un film de quelques dizaines de microns voire quelques microns à quelques dixièmes de millimètre d'épaisseur par exemple dans le cas des polyuréthanes, des copolymères éthylène-acétate de vinyle, des polyéthylenes à basse densité ou des copolymères éthylène- tétrafluoroéthylène ou du chlorure de polyvinyle. Ces films, ces feuilles ou ces plaques peuvent constituer à eux seuls la matrice du matériau selon l'invention. Mais une constitution plus complexe peut aussi être envisagée. Ainsi, le matériau de l'invention peut être déposé sur, ou associé avec un autre substrat, tel que les thermoplastiques décrits précédemment. Ce dépôt ou cette association peut se faire par les méthodes connues de coextrusion, lamination, enduction. Des structures multicouches peuvent être formées d'une ou de plusieurs couches de matériau selon l'invention, associées par des couches de liant de coextrusion à une ou plusieurs autres couches d'un ou de plusieurs polymères thermoplastiques (par exemple le polyéthylène, le polychlorure de vinyle) le ou lesquels peuvent constituer un élément support, majoritaire dans la constitution du film. Les films ainsi obtenus peuvent être monoétirés, biétirés selon les techniques connues de transformation des thermoplastiques. Les feuilles ou les plaques peuvent être découpées, thermoformées, estampées afin de leur donner la forme voulue.Among these thermoplastic polymers, polyethylenes are particularly preferred, including PEBD (low density polyethylenes), LLDPE (linear low density polyethylenes), polyethylenes obtained by metallocene synthesis, PVC (polyvinyl chloride), PET (polyethylene terephthalate) , polymethylmethacrylate, copolyolefins such as EVA (polyethylene of vinyl alcohol or ethylene vinyl acetate), mixtures and copolymers based on these (co) polymers, polycarbonate The polymer may be in a rigid form and a sheet or plate a few millimeters thick, for example in the case of polyvinyl chloride, methyl methacrylate or polycarbonate. It can also be in the form of a film of a few tens of microns or even a few microns to a few tenths of a millimeter thick, for example in the case of polyurethanes, ethylene-vinyl acetate copolymers, low density polyethylenes or ethylene-tetrafluoroethylene or polyvinyl chloride copolymers. These films, these sheets or these plates can alone constitute the matrix of the material according to the invention. But a more complex constitution can also be envisaged. Thus, the material of the invention can be deposited on, or associated with another substrate, such as the thermoplastics described above. This deposition or this association can be done by known methods of coextrusion, lamination, coating. Multilayer structures can be formed from one or more layers of material according to the invention, associated by layers of coextrusion binder with one or more other layers of one or more thermoplastic polymers (for example polyethylene, polychloride vinyl) which can constitute a support element, majority in the constitution of the film. The films thus obtained can be mono-stretched, bi-stretched according to known techniques for processing thermoplastics. The sheets or plates can be cut, thermoformed, stamped to give them the desired shape.
Le matériau de l'invention peut aussi se présenter sous la forme d'une matrice à base d'une peinture ou vernis ou d'un latex, cette matrice pouvant être déposée en revêtement sur un substrat organique ou minéral comme un verre. Par peinture ou vernis on entend les formulations ou compositions désignées habituellement par ce terme dans le domaine technique des peintures et qui sont par exemple à base des résines en émulsion suivantes : résines alkydes dont la plus courante est dénommée glycérophtalique; les résines modifiées à l'huile longue ou courte; les résines acryliques dérivées des esters de l'acide acrylique (méthylique ou éthylique) et méthacrylique éventuellement copolymérisés avec Pacrylate d'éthyle, d'éthyl-2 hexyle ou de butyle ainsi que les résines acryliques-isocyanates; les résines vinyliques comme par exemple l'acétate de polyvinyle, le chlorure de polyvinyle, le butyralpolyvinylique, le formalpolyvinylique, et les copolymères chlorure de vinyle et acétate de vinyle ou chlorure de vinylidène; les résines aminoplastes ou phénoliques le plus souvent modifiées; les résines polyesters; les résines polyuréthannes; les résines époxy; les résines silicones; les résines cellulosiques ou nitrocellulosiques.The material of the invention can also be in the form of a matrix based on a paint or varnish or on a latex, this matrix being able to be deposited as a coating on an organic or mineral substrate such as a glass. By paint or varnish is meant the formulations or compositions usually designated by this term in the technical field of paints and which are for example based on the following emulsion resins: alkyd resins, the most common of which is called glycerophthalic; long or short oil modified resins; acrylic resins derived from acrylic (methyl or ethyl) and methacrylic acid esters optionally copolymerized with ethyl acrylate, 2-ethylhexyl or butyl acrylate as well as acrylic-isocyanate resins; vinyl resins such as, for example, polyvinyl acetate, polyvinyl chloride, butyralpolyvinyl, formalpolyvinyl, and the copolymers of vinyl chloride and vinyl acetate or vinylidene chloride; the aminoplast or phenolic resins most often modified; polyester resins; polyurethane resins; epoxy resins; silicone resins; cellulosic or nitrocellulosic resins.
On entend par latex les dispersions aqueuses de particules de polymères issu de procédés classiques de (co)polymérisation en émulsion de monomères organiques polymérisables.The term “latex” is understood to mean the aqueous dispersions of polymer particles resulting from conventional emulsion (co) polymerization processes of polymerizable organic monomers.
Ces monomères organiques peuvent être choisis par exemple parmi les (méth)acrylate d'alkyle, les esters alpha, beta-éthylèniquement insaturés; les esters et les hemi-esters d'acides polycarboxyliques alpha, beta- éthyléniquement insaturés; les halogénures vinyliques; les vinyl aromatiques; les diènes aliphatiques conjugués; les nitriles alpha, beta-éthyléniquement insaturés; les latex polyacétate de vinyle, les isocyanates, les polyols.These organic monomers can be chosen, for example, from alkyl (meth) acrylates, alpha, beta-ethylenically unsaturated esters; esters and hemi-esters of alpha, beta-polycarboxylic acids ethylenically unsaturated; vinyl halides; aromatic vinyls; conjugated aliphatic dienes; alpha, beta-ethylenically unsaturated nitriles; polyvinyl acetate latexes, isocyanates, polyols.
Selon l'invention, le matériau tel que décrit ci-dessus contient à titre d'additif un silicate de baryum et de magnésium, dopé avec de l'europium, qui peut être considéré en substitution partielle du baryum, et avec du manganèse, qui peut être considéré en substitution partielle du magnésium, ce silicate répondant à la formule (1) qui a été donnée plus haut.According to the invention, the material as described above contains, as an additive, a barium and magnesium silicate, doped with europium, which can be considered as a partial substitution for barium, and with manganese, which can be considered as a partial substitution for magnesium, this silicate corresponding to formula (1) which has been given above.
Lorsqu'il est soumis à une excitation UV ou proche UV (UVA), c'est à dire à un rayonnement dans une gamme de longueur d'onde comprise entre environ 250 nm et environ 390 nm, cet additif a pour propriété d'émettre notamment dans le rouge et aussi dans le bleu c'est à dire dans une gamme de longueur d'onde comprise entre environ 370 nm et environ 400 nm (entre 400 nm et 500 nm pour le bleu et entre 550 nm et 700 nm pour le rouge) avec un bon rendement.When it is subjected to UV or near UV (UVA) excitation, that is to say radiation in a wavelength range between about 250 nm and about 390 nm, this additive has the property of emitting especially in red and also in blue, that is to say in a wavelength range between about 370 nm and about 400 nm (between 400 nm and 500 nm for blue and between 550 nm and 700 nm for red) with good yield.
Selon un premier mode de réalisation, le composé répond à la formule (1 ) précitée dans laquelle 0,0001 < x < 0,25 et 0,0001 < y < 0,25.According to a first embodiment, the compound corresponds to the above formula (1) in which 0.0001 <x <0.25 and 0.0001 <y <0.25.
Selon un autre mode de réalisation plus particulier, le composé répond à la formule (1) précitée dans laquelle 0,01 < x < 0,25 et 0,01 < y < 0,25. On peut noter qu'il est avantageux d'avoir une concentration en europium dans le composé d'au moins 0,01% pour obtenir une émission de meilleure intensité. Il est aussi avantageux d'avoir une concentration en europium et en manganèse d'au plus 25% afin de limiter au maximum des phénomènes d'auto-extinction gênants. Les pourcentages indiqués ci-dessus correspondent aux taux de substitution en mole des ions dopants Eu2+ et Mn2 respectivement aux ions Ba2+ et Mg2+.According to another more specific embodiment, the compound corresponds to the above formula (1) in which 0.01 <x <0.25 and 0.01 <y <0.25. It may be noted that it is advantageous to have a concentration of europium in the compound of at least 0.01% in order to obtain a better intensity emission. It is also advantageous to have a concentration of europium and manganese of at most 25% in order to limit as much as possible annoying self-extinction phenomena. The percentages indicated above correspond to the substitution rates by mole of the doping ions Eu 2+ and Mn 2 respectively for the ions Ba 2+ and Mg 2+ .
Selon un autre mode de réalisation préféré, le composé de formule (1 ) vérifie les valeurs de x et y suivantes : 0,01 < x < 0,03 et 0,04 < y < 0,06. Pour ces valeurs de x et de y l'intensité d'émission est la plus importante. Enfin, dans le composé de formule (1 ), le baryum, le magnésium et le silicium peuvent être partiellement substitués par d'autres éléments que ceux qui ont été décrits plus haut. Ainsi, le baryum peut être partiellement substitué par du calcium et/ou du strontium dans une proportion qui peut aller jusqu'à environ 30%, cette proportion étant exprimée par le rapport atomique substituant/(susbtituant+baryum). Le magnésium peut être partiellement substitué par du zinc dans une proportion qui peut aller jusqu'à environ 30%, cette proportion étant aussi exprimée par le rapport atomique Zn/(Zn+Mg). Enfin, le silicium peut être partiellement substitué par du germanium, de l'aluminium et/ou du phosphore dans une proportion qui peut aller jusqu'à environ 10%, cette proportion étant exprimée par le rapport atomique substituant/(susbtituant+silicium).According to another preferred embodiment, the compound of formula (1) checks the following values of x and y: 0.01 <x <0.03 and 0.04 <y <0.06. For these values of x and y the emission intensity is the most important. Finally, in the compound of formula (1), barium, magnesium and silicon may be partially substituted by elements other than those which have been described above. Thus, the barium can be partially substituted by calcium and / or strontium in a proportion which can go up to approximately 30%, this proportion being expressed by the atomic substituent / (susbtituant + barium) ratio. The magnesium can be partially substituted by zinc in a proportion which can go up to approximately 30%, this proportion being also expressed by the atomic ratio Zn / (Zn + Mg). Finally, silicon can be partially substituted by germanium, of aluminum and / or phosphorus in a proportion which can go up to approximately 10%, this proportion being expressed by the atomic ratio substituent / (susbtituant + silicon).
La quantité de silicate dans le matériau peut être comprise notamment entre 0,01% et 10% en masse par rapport à la masse totale du matériau, plus particulièrement entre 0,1% et 1%. Ces valeurs sont données à titre d'exemple uniquement et elles peuvent varier en fonction de la nature de la matrice. La valeur basse est fixée en fonction de l'intensité de l'effet recherché que l'on désire obtenir. La valeur haute n'est pas critique, généralement on ne dépasse pas la valeur au delà de laquelle une quantité supplémentaire n'apporte pas d'avantage ou d'effet supplémentaire par rapport à d'autres contraintes par exemple des contraintes de coût.The amount of silicate in the material can be in particular between 0.01% and 10% by mass relative to the total mass of the material, more particularly between 0.1% and 1%. These values are given by way of example only and they may vary depending on the nature of the matrix. The low value is fixed according to the intensity of the desired effect which one wishes to obtain. The high value is not critical, generally one does not exceed the value beyond which an additional quantity does not bring an advantage or additional effect compared to other constraints for example cost constraints.
Alors qu'un silicate de baryum et de magnésium dopé à l'europium émet dans le bleu, la présence de manganèse comme dopant permet d'orienter l'émission de ce composé vers le rouge. Il est possible de régler la colorimétrie de émission de l'additif de l'invention en faisant varier le rapport Eu/Mn.While a barium and magnesium silicate doped with europium emits in blue, the presence of manganese as a dopant makes it possible to direct the emission of this compound towards the red. It is possible to adjust the emission colorimetry of the additive of the invention by varying the Eu / Mn ratio.
Par ailleurs, l'additif de l'invention présente une capacité d'absorption des UV ce qui lui permet d'assurer aussi une fonction anti-UV et donc de protéger contre les UV les matériaux dans lesquels il est incorporé. Le silicate utilisé pour l'invention se prépare généralement par une réaction à l'état solide à haute température.Furthermore, the additive of the invention has a UV absorption capacity which also enables it to provide an anti-UV function and therefore to protect against the UV the materials in which it is incorporated. The silicate used for the invention is generally prepared by a reaction in the solid state at high temperature.
Comme produit de départ, on peut utiliser directement les oxydes des métaux requis ou des composés organiques ou minéraux susceptibles de former ces oxydes par chauffage comme les carbonates, oxalates, hydroxydes, acétates, nitrates, borates desdits métaux.As starting material, it is possible to use directly the oxides of the required metals or organic or inorganic compounds capable of forming these oxides by heating such as the carbonates, oxalates, hydroxides, acetates, nitrates, borates of said metals.
On forme un mélange intime aux concentrations appropriées de tous les produits de départ à l'état finement divisé.An intimate mixture is formed at the appropriate concentrations of all the starting materials in the finely divided state.
On peut également envisager de préparer un mélange de départ par co- précipitation à partir de solutions des précurseurs des oxydes désirés, par exemple en milieu aqueux.It is also possible to envisage preparing a starting mixture by co-precipitation from solutions of the precursors of the desired oxides, for example in an aqueous medium.
Le mélange des produits de départ est ensuite chauffé au moins une fois pendant une période comprise entre une heure et une centaine d'heures environ, à une température située entre environ 500°C et environ 1600°C; il est préférable d'effectuer le chauffage au moins en partie sous une atmosphère réductrice (hydrogène dans l'argon par exemple) pour porter totalement l'europium à l'état divalent.The mixture of starting materials is then heated at least once for a period of between one hour and one hundred hours approximately, to a temperature between approximately 500 ° C and approximately 1600 ° C; it is preferable to carry out the heating at least in part under a reducing atmosphere (hydrogen in argon for example) to bring the europium completely to the divalent state.
Il n'y a pas de limitation à la forme, la morphologie, la granulométrie moyenne ou la répartition de granulométrie des silicates ainsi obtenus. Ces produits peuvent être broyés, micronisés, tamisés et traités en surface, notamment par des additifs organiques, pour en faciliter la compatibilité ou la dispersion dans le milieu d'application.There is no limitation to the shape, the morphology, the average particle size or the particle size distribution of the silicates thus obtained. These products can be ground, micronized, sieved and surface treated, in particular with organic additives, to facilitate compatibility or dispersion in the application medium.
Le matériau de l'invention, outre la matrice à base des éléments décrits précédemment comme la fibre, le polymère, la peinture ou le vernis ou le latex, et le composé à base de silicate de baryum et de magnésium précité, peut également comprendre, de manière connue, d'autres additifs, tels que par exemple des stabilisants, des plastifiants, des ignifugeants, des colorants, des azurants optiques, des lubrifiants, des agents anti-collage (anti-blocking), des agents matifiants, des agents de mise en œuvre, des élastomères ou des composition d'élastomères (par exemple des copolymères acryliques ou des copolymères de méthacrylate butadiène styrène) permettant d'améliorer la souplesse ou la résistance mécanique des films ou des feuilles, des agents d'adhésion (par exemple des polyoléfines greffées par de l'anhydride maléique permettant l'adhésion sur du polyamide), des agents dispersants permettant une meilleure répartition du silicate dans le matériau ou tout autre additif nécessaire à la réalisation de structure de films thermoplastique multicouches notamment ceux connus et souvent utilisés pour la réalisation de film pour serre (par exemple anti-goutte, anti buée) ou bien encore des catalyseurs. Cette liste n'a aucun caractère limitatif.The material of the invention, in addition to the matrix based on the elements described above such as fiber, polymer, paint or varnish or latex, and the compound based on barium silicate and magnesium mentioned above, can also comprise, in a known manner, other additives, such as for example stabilizers, plasticizers, flame retardants, dyes, optical brighteners, lubricants, anti-sticking agents, matting agents, processing, elastomers or compositions of elastomers (for example acrylic copolymers or copolymers of methacrylate butadiene styrene) making it possible to improve the flexibility or the mechanical resistance of films or sheets, adhesion agents (for example polyolefins grafted with maleic anhydride allowing adhesion to polyamide), dispersing agents allowing a better distribution of the silicate in the material or t any other additive necessary for the production of multilayer thermoplastic film structures, in particular those known and often used for the production of greenhouse films (for example anti-drip, anti-fogging) or else catalysts. This list is in no way limiting.
Toute méthode permettant d'obtenir une dispersion du silicate de formule (1) dans une matrice et notamment dans un composé macromoléculaire du type des polymères, latex et peintures ou vernis précités peut être utilisée pour réaliser le matériau de l'invention. Notamment, un premier procédé consiste à mélanger le silicate et les autres additifs précités dans un composé thermoplastique sous forme fondue et à éventuellement soumettre le mélange à un cisaillement important, par exemple dans un dispositif d'extrusion bi-vis, afin de réaliser une bonne dispersion. Un autre procédé consiste à mélanger le ou les additifs à disperser aux monomères dans le milieu de polymérisation, puis à effectuer la polymérisation. Un autre procédé consiste à mélanger à un polymère thermoplastique sous forme fondue, un mélange concentré d'un polymère thermoplastique et d'additifs dispersés, préparé par exemple selon l'un des procédés décrits précédemment.Any method making it possible to obtain a dispersion of the silicate of formula (1) in a matrix and in particular in a macromolecular compound of the type of the aforementioned polymers, latexes and paints or varnishes can be used to produce the material of the invention. In particular, a first method consists in mixing the silicate and the other aforementioned additives in a thermoplastic compound in molten form and optionally subjecting the mixture to significant shearing, for example in a twin-screw extrusion device, in order to achieve good dispersion. Another method consists in mixing the additive (s) to be dispersed with the monomers in the polymerization medium, then in carrying out the polymerization. Another method consists in mixing with a thermoplastic polymer in molten form, a concentrated mixture of a thermoplastic polymer and dispersed additives, prepared for example according to one of the methods described above.
Le silicate peut être introduit dans le milieu de synthèse du composé macromoléculaire, ou dans un polymère thermoplastique fondu sous une forme quelconque. Il peut par exemple être introduit sous forme d'une poudre solide ou sous forme d'une dispersion dans de l'eau ou dans un dispersant organique. Un procédé adapté aux peintures ou vernis ou aux latex consiste à disperser directement le composé silicate sous forme de poudre dans le latex ou la peinture ou le vernis, par exemple par agitation, ou bien à préparer un concentré de poudre en milieu liquide ou pâteux lequel est ensuite ajouté au peintures ou vernis ou au latex. Le concentré peut être préparé dans un milieu aqueux ou solvant, avec éventuellement des tensioactifs, des polymères hydrosolubles ou hydrophobes ou bien encore comportant des extrémités hydrophiles et hydrophobes, polaires ou non, nécessaires à la stabilisation du mélange pour en éviter la décantation. Il n'y a pas de limitation aux additifs qui peuvent entrer dans la composition du concentré.The silicate can be introduced into the synthesis medium of the macromolecular compound, or into a molten thermoplastic polymer in any form. It can for example be introduced in the form of a solid powder or in the form of a dispersion in water or in an organic dispersant. A process suitable for paints or varnishes or latexes consists in directly dispersing the silicate compound in the form of powder in the latex or in the paint or varnish, for example by stirring, or else in preparing a powder concentrate in a liquid or pasty medium which is then added to paints or varnishes or latex. The concentrate can be prepared in an aqueous or solvent medium, optionally with surfactants, water-soluble or hydrophobic polymers or alternatively comprising hydrophilic and hydrophobic ends, polar or not, necessary for the stabilization of the mixture to avoid decantation. There is no limitation to the additives which may enter into the composition of the concentrate.
Le matériau de l'invention peut être tout particulièrement utilisé dans la fabrication ou dans la construction des parois de serres. Le terme « serre » doit être compris ici au sens large comme couvrant tout type d'abris utilisé dans l'agriculture pour la protection et le développement des cultures. Par exemple, il peut s'agir des serres et grand tunnels plastiques, des serres en verre, des grands abris, des semi forçages, des bâches à plat, des paillages etc tels que décrits dans la brochure éditée par le CIPA (Congrès International du Plastique dans l'Agriculture) 65 rue de Prony, Paris, « L'évolution de la plasticulture dans le Monde » par Jean-Pierre Jouet. L'invention concerne donc des parois pour serres qui comprennent un matériau tel que décrit ci-dessus.The material of the invention can be very particularly used in the manufacture or in the construction of greenhouse walls. The term "greenhouse" should be understood here broadly as covering any type of shelter used in agriculture for the protection and development of crops. For example, it can be greenhouses and large plastic tunnels, glass greenhouses, large shelters, semi-forcings, flat tarpaulins, mulches etc. as described in the brochure published by CIPA (International Congress of Plastic in Agriculture) 65 rue de Prony, Paris, "The evolution of plasticulture in the World" by Jean-Pierre Jouet. The invention therefore relates to walls for greenhouses which comprise a material as described above.
Le matériau de l'invention peut aussi être utilisé dans le domaine de la cosmétique, en particulier dans la préparation des vernis à ongles et des gels coiffants. Les vernis à ongles contiennent généralement :The material of the invention can also be used in the field of cosmetics, in particular in the preparation of nail varnishes and styling gels. Nail polishes generally contain:
- un agent filmogène à bas de nitrocellulose,- a film-forming agent based on nitrocellulose,
- une résine, résine dammer naturelle ou résine synthétique du type formaldéhyde-sulfamide, résine polystyrène, résine polyvinylique etc.,- a resin, natural dammer resin or synthetic resin of the formaldehyde-sulfonamide type, polystyrene resin, polyvinyl resin etc.,
- un plastifiant par exemple, le phtalate de diéthyle, le phtalate de dibutyle, le phtalate de dioctyle, le tricrésylphosphate, le stéarate de n-butyle, le diacétate de résorcine ou leur mélange,a plasticizer, for example, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, tricresylphosphate, n-butyl stearate, resorcin diacetate or a mixture thereof,
- un dissolvant tel que l'alcool éthylique, isopropylique, butylique, isobutylique, l'acétate d'éthyle, l'acétate de butyle ou le plus souvent le mélange de ces solvants, - un diluant, notamment le toluène ou le xylène,- a solvent such as ethyl, isopropyl, butyl, isobutyl alcohol, ethyl acetate, butyl acetate or most often the mixture of these solvents, - a diluent, in particular toluene or xylene,
- éventuellement d'autres additifs, parfum ou produit nacrant (flocons de mica enrobés d'oxychlorure de bismuth ou de bioxyde de titane).- possibly other additives, perfume or pearlescent product (mica flakes coated with bismuth oxychloride or titanium dioxide).
On donne ci-après un exemple de composition-type : - de 10 à 15% en poids de nitrocellulose,An example of a typical composition is given below: - from 10 to 15% by weight of nitrocellulose,
- de 10 à 15% en poids de résine,- from 10 to 15% by weight of resin,
- de 3 à 5% en poids de plastifiant(s),- from 3 to 5% by weight of plasticizer (s),
- q.s.p. 100% en poids de solvant(s). Dans la mise en œuvre de l'invention visée ici, le vernis constitue la matrice et le composé de formule (1) est présent comme additif dans cette matrice. Pour la préparation de ce vernis, le composé est généralement broyé dans une masse plastique constituée de nitrocellulose et de plastifiant(s) qui est ensuite mise en solution dans le(s) solvant(s). La quantité de composé utilisée est habituellement de 1% à 5% en masse par rapport au vernis. Il est à noter que ces valeurs sont données à titre indicatif et qu'elles ne sont pas critiques. Elles peuvent être modifiées en fonction de l'intensité de l'effet recherché, c'est à dire la luminescence dans le rouge, et des contraintes de coûts. L'invention concerne donc aussi des vernis à ongles qui comprennent un composé de formule (1 ) tel que décrit ci-dessus.- q.s.p. 100% by weight of solvent (s). In the implementation of the invention referred to here, the varnish constitutes the matrix and the compound of formula (1) is present as an additive in this matrix. For the preparation of this varnish, the compound is generally ground in a plastic mass consisting of nitrocellulose and plasticizer (s) which is then dissolved in the solvent (s). The amount of compound used is usually 1% to 5% by mass relative to the varnish. It should be noted that these values are given as an indication and that they are not critical. They can be modified as a function of the intensity of the desired effect, ie the luminescence in the red, and cost constraints. The invention therefore also relates to nail varnishes which comprise a compound of formula (1) as described above.
Les gels coiffants contiennent généralement :Styling gels generally contain:
- de l'eau à titre de solvant;- water as solvent;
- un gélifiant qui peut être par exemple l'hydroxyéthyle cellulose, un copolymère éthylène-anhydride maléique ou un carbomère (homopolymère de l'acide acrylique réticulé avec un allyle éther de pentaérythritol, un allyle éther de sucrose ou un allyle éther de propylène);- A gelling agent which can be, for example, hydroxyethyl cellulose, an ethylene-maleic anhydride copolymer or a carbomer (homopolymer of acrylic acid crosslinked with an allyl ether of pentaerythritol, an allyl ether of sucrose or an allyl ether of propylene);
- un polymère fixant qui peut être notamment la polyvinyle pyrrolidone (PVP), un mélange polyvinyle pyrrolidone/acétate de vinyle, des terpolymères;- A fixing polymer which can in particular be polyvinyl pyrrolidone (PVP), a polyvinyl pyrrolidone / vinyl acetate mixture, terpolymers;
- un agent conditionnant comme le polyquaternium-11 , le polyquatemium-4 ou le polyquatemium-7, un mélange PVP/copolymère de diméthylaminoéthylméthacrylate, un guar;- a conditioning agent such as polyquaternium-11, polyquatemium-4 or polyquatemium-7, a PVP / dimethylaminoethylmethacrylate copolymer mixture, a guar;
- un agent plastifiant comme le diméthicone copolyol.- a plasticizing agent such as dimethicone copolyol.
Pour la mise en œuvre de l'invention dans ce type de gels, le gel constitue la matrice et le composé de formule (1) est présent comme additif dans cette matrice. La quantité de composé utilisée est habituellement de 0,5% à 4% en masse par rapport au gel. On notera là encore que ces valeurs sont données à titre indicatif, qu'elles ne sont pas critiques et qu'elles peuvent être modifiées, là aussi, en fonction de l'intensité de l'effet recherché et des contraintes de coûts. L'invention concerne donc aussi des gels coiffants qui comprennent un composé de formule (1) tel que décrit ci-dessus.For the implementation of the invention in this type of gels, the gel constitutes the matrix and the compound of formula (1) is present as an additive in this matrix. The amount of compound used is usually 0.5% to 4% by mass relative to the gel. Again, it should be noted that these values are given for information only, that they are not critical and that they can be modified, there too, according to the intensity of the desired effect and cost constraints. The invention therefore also relates to styling gels which comprise a compound of formula (1) as described above.
Le matériau de l'invention peut aussi être utilisé dans la fabrication de tissus pour vêtements, dans la construction de bâtiments ou abris, dans l'industrie automobile. Ainsi, il peut être utilisé dans la fabrication de films luminescents pour des applications non agricoles, pour des peintures luminescentes ou des verres à revêtements luminescents pour les bâtiments ou les automobiles. Le matériau de l'invention peut être utilisé aussi dans des diodes électroluminescentes (LED). Enfin, il peut être employé dans la fabrication de matériaux utilisables dans les bio-technologies. Des exemples vont maintenant être donnés.The material of the invention can also be used in the manufacture of fabrics for clothing, in the construction of buildings or shelters, in automobile industry. Thus, it can be used in the manufacture of luminescent films for non-agricultural applications, for luminescent paints or glasses with luminescent coatings for buildings or automobiles. The material of the invention can also be used in light-emitting diodes (LEDs). Finally, it can be used in the manufacture of materials usable in bio-technologies. Examples will now be given.
EXEMPLE 1 Cet exemple concerne la préparation d'un composé répondant à la composition Ba3MgSi2O8 : 2% Eu2+, 5% Mn2+ et correspondant à la formule Ba2,94Euo,o6Mgo,95Mno,o5Si2θ8 (les pourcentages indiqués pour les ions dopants correspondent aux taux de substitution en mole des ions Eu2+ et Mn2+ respectivement aux ions Ba2+ et Mg2+). On procède par voie solide en mélangeant les oxydes BaC03, Eu2O3, (MgCO3)4Mg(OH)2.5H2O, MnCO3 et SiO2 dans des proportions stœchiométriques. 0,4 mole de NH4CI est ajoutée au mélange en tant que flux.EXAMPLE 1 This example relates to the preparation of a compound corresponding to the composition Ba 3 MgSi 2 O 8 : 2% Eu 2+ , 5% Mn 2+ and corresponding to the formula Ba2, 94 Euo, o6Mgo, 95 Mno, o 5 If 2 θ8 (the percentages indicated for the doping ions correspond to the rates of substitution by mole of the Eu 2+ and Mn 2+ ions respectively to the Ba 2+ and Mg 2+ ions). Per channel is carried by mixing the solid BaC0 3 oxide, Eu 2 O 3, (MgCO 3) 4 Mg (OH) 2 .5H 2 O, MnCO 3 and SiO 2 in stoichiometric proportions. 0.4 mole of NH 4 CI is added to the mixture as a stream.
Produits de départ Quantités mises en œuyreStarting materials Quantities used
BaC03 1 ,8629 gBaC0 3 1, 8629 g
Eu2O3 0,0339 gEu 2 O 3 0.0339 g
(MgC03)4Mg(OH)2.5H2O 0,2963 g(MgC0 3) 4 Mg (OH) 2 .5H 2 O 0.2963 g
MnC03 0,0185 gMnC0 3 0.0185 g
SiO2 0,3858 gSiO 2 0.3858 g
NH4CI 0,0687 gNH 4 CI 0.0687 g
Ces produits de départ sont mélangés de façon homogène par broyage; le mélange, placé dans un creuset en alumine, est introduit dans un four où il subit deux traitements thermiques. Un premier traitement thermique est effectué à 600 °C pendant 4 heures à l'air. Le mélange, de couleur grise, est alors broyé puis replacé au four dans un creuset en alumine. Après une purge de 4 heures du four avec un mélange Ar/H2 10 %, le mélange est chauffé 4 heures à 1200 °C dans cette atmosphère réductrice. Une rampe de montée et de descente en température de 360 °C/h est employée. Le produit obtenu se présente sous la forme d'une poudre blanche. EXEMPLE 2These starting materials are mixed homogeneously by grinding; the mixture, placed in an alumina crucible, is introduced into an oven where it undergoes two heat treatments. A first heat treatment is carried out at 600 ° C for 4 hours in air. The gray mixture is then ground and then returned to the oven in an alumina crucible. After a 4 hour purge from the oven with a 10% Ar / H 2 mixture, the mixture is heated for 4 hours at 1200 ° C. in this reducing atmosphere. A ramp up and down in temperature of 360 ° C / h is used. The product obtained is in the form of a white powder. EXAMPLE 2
Cet exemple concerne la préparation d'un composé répondant à la composition Ba3MgSi2O8 : 2% Eu2+, 20% Mn2+ et correspondant à la formule Ba2,94Euo,o6Mgo,8Mno,2Si2θ8. On procède comme dans l'exemple 1 , par voie solide, en mélangeant les oxydes BaC03, Eu203, (MgCO3)4Mg(OH)2.5H2θ, MnCO3 et Siθ2 dans des proportions stœchiométriques. 0,4 mole de NH4CI est ajoutée au mélange en tant que flux.This example concerns the preparation of a compound corresponding to the composition Ba 3 MgSi 2 O 8 : 2% Eu 2+ , 20% Mn 2+ and corresponding to the formula Ba2.94Euo, o6Mgo, 8Mno, 2 Si 2 θ 8 . The procedure is as in Example 1, by solid route, by mixing the oxides BaC0 3 , Eu 2 0 3 , (MgCO 3 ) 4 Mg (OH) 2 .5H 2 θ, MnCO 3 and Siθ2 in stoichiometric proportions. 0.4 mole of NH 4 CI is added to the mixture as a stream.
Produits de départ Quantités mises en œuyreStarting materials Quantities used
BaCO3 1 ,8629 gBaCO 3 1, 8629 g
Eu2O3 0,0339 gEu 2 O 3 0.0339 g
(MgCO3)4Mg(OH)2.5H2O 0,2492 g(MgCO 3) 4 Mg (OH) 2 .5H 2 O 0.2492 g
MnCO3 0,0740 gMnCO 3 0.0740 g
SiO2 0,3858 gSiO 2 0.3858 g
NH4CI 0,0687 g Le mode opératoire est ensuite identique à celui de l'exemple 1.NH 4 CI 0.0687 g The procedure is then identical to that of Example 1.
Les courbes de la figure 1 donnent, pour les composés ainsi obtenus, le spectre d'émission pour une longueur d'onde d'excitation de 370nm. On voit donc qu'en réponse à une excitation dans le domaine des UV, les composés émettent dans le rouge (pic vers 625nm) et aussi dans le bleu (pic versThe curves of FIG. 1 give, for the compounds thus obtained, the emission spectrum for an excitation wavelength of 370 nm. We therefore see that in response to an excitation in the UV range, the compounds emit in red (peak around 625nm) and also in blue (peak towards
440nm).440nm).
Le spectre d'excitation du composé de l'exemple 1 , pour la longueur d'onde d'émission 623 nm, est représenté à la figure 2. Il apparaît de cette figure que le rendement maximum est atteint pour une longueur d'onde de 350nm. Entre 350nm et 400nm le rendement relatif varie entre 100% et 78%.The excitation spectrum of the compound of Example 1, for the emission wavelength 623 nm, is shown in Figure 2. It appears from this figure that the maximum efficiency is reached for a wavelength of 350nm. Between 350nm and 400nm the relative efficiency varies between 100% and 78%.
La figure 3 est un graphe, réalisé en mode synchrone, qui représente la variation d'intensité de l'absorption en fonction de la longueur d'onde du composé de l'exemple 1. Ce graphe fait bien apparaître la capacité d'absorption des UV du composé puisque l'intensité de réflexion est pratiquement nulle pour une longueur d'onde inférieure à environ 425nm.FIG. 3 is a graph, produced in synchronous mode, which represents the variation in intensity of absorption as a function of the wavelength of the compound of Example 1. This graph clearly shows the absorption capacity of the UV of the compound since the reflection intensity is practically zero for a wavelength less than about 425nm.
EXEMPLE 3EXAMPLE 3
Cet exemple illustre l'utilisation dans un film polymère d'un additif selon l'invention. Le produit obtenu à l'exemple 1 est étuvé pendant 12h à 90°C. Il est ensuite mélangé en mélangeur cube pendant 10 minutes avec du PEBD Lacqtène 1020FN24, du PEG 400 (agent collant) et un antioxydant Irganox B225. Les formulations mises en œuvre sont les suivantes :This example illustrates the use in an polymer film of an additive according to the invention. The product obtained in Example 1 is steamed for 12 hours at 90 ° C. It is then mixed in a cube mixer for 10 minutes with LDPE Lacqtène 1020FN24, PEG 400 (sticky agent) and an antioxidant Irganox B225. The formulations used are as follows:
PEBD Lacqtène 1020FN24 1495,5gLDPE Lacqtène 1020FN24 1495.5g
Silicate exemple 1 1 ,5gSilicate example 1 1, 5g
Irganox B225 (0,1%) 1 ,5gIrganox B225 (0.1%) 1.5g
PEG 400 (0,1%) 1 ,5gPEG 400 (0.1%) 1.5g
Total 1500gTotal 1500g
La mise en œuvre est réalisée sur une extrudeuse double vis ZSK30 sur laquelle est adaptée une filière plate de 30cm de largeur et d'ouverture réglable ainsi qu'une machine de film cast permettant d'étirer le film en sortie d'extrudeuse afin de l'amener à l'épaisseur de 100μm.The implementation is carried out on a ZSK30 twin screw extruder on which is adapted a flat die of 30cm width and adjustable opening as well as a cast film machine allowing to stretch the film at the extruder outlet in order to l '' bring to the thickness of 100μm.
La température dans l'extrudeuse et dans la filière pour film est de 180°C. La température à l'entrée de la machine film cast est de 70°C. Les autres conditions sont les suivantes :The temperature in the extruder and in the film die is 180 ° C. The temperature at the inlet of the film cast machine is 70 ° C. The other conditions are as follows:
Le film obtenu émet une couleur pourpre lorsqu'il est soumis à un éclairage d'une longueur d'onde de 370nm.The film obtained emits a purple color when subjected to lighting with a wavelength of 370nm.
EXEMPLE 4EXAMPLE 4
Cet exemple donne des résultats de mesures colorimétriques faites sur un polymère du type de celui de l'exemple 3.This example gives the results of colorimetric measurements made on a polymer of the type of that of Example 3.
On prépare des films de la même manière que dans l'exemple 3 avec le produit de l'exemple 1 qui, toutefois, n'a pas subi de traitement à l'étuve.Films are prepared in the same manner as in Example 3 with the product of Example 1 which, however, has not undergone oven treatment.
On donne ci-dessous les formulations mises en œuvre dans les différents essais. The formulations used in the various tests are given below.
HALS est un additif connu anti-UV (50% Tinuvin622-50% Chimasorb 944).HALS is a known anti-UV additive (50% Tinuvin622-50% Chimasorb 944).
Les films réalisés ont une épaisseur comprise entre 110 μm et 130 μm.The films produced have a thickness of between 110 μm and 130 μm.
Les films obtenus sont placés sur une carte contraste et on mesure les coordonnées chromatiques L, a et b sur un fond blanc avec un spectrocolorimètre Minolta 508d, la composante spéculaire étant inclue. Ces coordonnées sont données dans le système CIE 1976 (L, a et b) tel que défini par la Commission Internationale d'Eclairage et répertorié dans le Recueil des Normes Françaises (AFNOR), couleur colorimétrique n° X08-12, n° X08-14 (1983). On effectue aussi une mesure de Haze avec un haze-mètre XL-211 Hazegard de Byk-Garner.The films obtained are placed on a contrast card and the chromaticity coordinates L, a and b are measured on a white background with a Minolta 508d spectrocolorimeter, the specular component being included. These coordinates are given in the CIE 1976 system (L, a and b) as defined by the International Lighting Commission and listed in the Collection of French Standards (AFNOR), colorimetric n ° X08-12, n ° X08- 14 (1983). A Haze measurement is also carried out with an XL-211 Hazegard haze meter from Byk-Garner.
On donne ci-dessous les valeurs obtenues.The values obtained are given below.
Le film de l'essai 1 est incolore. Le ΔE blanc varie dans des proportions qui sont en deçà des incertitudes de la mesure ce qui montre que l'addition du composé de l'invention n'entraîne pas de modification de la couleur du film, il n'y a pas de jaunissement par exemple. Enfin, la mesure Haze permet d'évaluer la transparence du film. Il n'y a pas non plus de variation significative de la transparence.The film of test 1 is colorless. The white ΔE varies in proportions which are below the measurement uncertainties, which shows that the addition of the compound of the invention does not cause the color of the film to change, there is no yellowing by example. Finally, the Haze measurement makes it possible to assess the transparency of the film. There is also no significant variation in transparency.
Enfin, dans la gamme de longueur d'ondes de 250 nm à 750 nm on n'observe aucune modification notable du spectre de transmission entre le film de l'essai témoin 1 et le film de l'essai 2 ni entre celui de l'essai 3 et celui de l'essai témoin 4.Finally, in the wavelength range from 250 nm to 750 nm, no significant modification of the transmission spectrum between the film is observed. of control test 1 and the film of test 2 or between that of test 3 and that of control test 4.
EXEMPLE 5 Cet exemple concerne l'utilisation du produit de l'exemple 1 dans la préparation d'un vernis à ongles.EXAMPLE 5 This example relates to the use of the product of Example 1 in the preparation of a nail varnish.
Ce vernis est une base transparente commercialisée par la société GEMEY (3,55 g) et contenant :This varnish is a transparent base marketed by the company GEMEY (3.55 g) and containing:
- à titre de solvant : de l'acétate d'éthyle, de l'acétate de butyle et de la nitrocellulose- as solvent: ethyl acetate, butyl acetate and nitrocellulose
- un copolymère anhydride phtalique/glycerine/décanoate de glycidyle- a phthalic anhydride / glycerine / glycidyl decanoate copolymer
- de l'alcool isopropylique- isopropyl alcohol
- un citrate d'acétyle et de tributyle- an acetyl and tributyl citrate
- du stéaralkonium hectorite - de l'éthyl tosylamide- stearalkonium hectorite - ethyl tosylamide
- de l'acide citrique- citric acid
- de l'oxyde de polyéthylène- polyethylene oxide
- du mica- mica
On ajoute 3% en masse du produit de l'exemple dans la base ci-dessus. Sous un rayonnement UV de 370 nm, le vernis obtenu émet une lumière pourpre.3% by mass of the product of the example is added to the above base. Under UV radiation of 370 nm, the varnish obtained emits a purple light.
EXEMPLE 6EXAMPLE 6
Cet exemple concerne l'utilisation du produit de l'exemple 1 dans la préparation d'un gel coiffant.This example relates to the use of the product of Example 1 in the preparation of a styling gel.
On utilise un gel coiffant commercialisé par la société Garnier (FRUCTIS STYLE) et contenant :A styling gel sold by the company Garnier (FRUCTIS STYLE) and containing:
- de l'eau- some water
- de l'alcool dénaturé - un copolymère PVP/Diméthylaminoéthylméthacrylate- denatured alcohol - a PVP / Dimethylaminoethylmethacrylate copolymer
- un guar hydroxypropyl- a hydroxypropyl guar
- de l'hydroxypropylcellulose- hydroxypropylcellulose
- une huile de castor hydrogénée PEG40- PEG40 hydrogenated beaver oil
- du PEG -192 (apricot kernel glycerides) - du PEG 70 (mango glycerides)- PEG -192 (apricot kernel glycerides) - PEG 70 (mango glycerides)
- de la triéthanolamine- triethanolamine
- du polyquaternium - 11- polyquaternium - 11
- du diméthicone copolyol - du pentenate de pentasodium- dimethicone copolyol - pentasodium pentenate
- du 4-benzophenone- 4-benzophenone
- du propylène glycol- propylene glycol
- un carbomer - un actif de fruit (citrus limonum)- a carbomer - a fruit active ingredient (citrus limonum)
- un parfum- a perfume
On ajoute au gel ci-dessus 0,5% en masse de produit de l'exemple . Sous un rayonnement UV de 370 nm, le gel obtenu émet une lumière pourpre. 0.5% by mass of product of the example is added to the above gel. Under UV radiation of 370 nm, the gel obtained emits purple light.

Claims

REVENDICATIONS
1- Matériau transformant la lumière du type comprenant une matrice et un additif, caractérisé en ce qu'il comprend à titre d'additif un composé de formule : dans laquelle 0 < x < 0,3 et 0 < y < 0,3.1- Material transforming light of the type comprising a matrix and an additive, characterized in that it comprises, as an additive, a compound of formula: in which 0 <x <0.3 and 0 <y <0.3.
2- Matériau selon la revendication 1 , caractérisé en ce que la matrice est à base d'un polymère.2- Material according to claim 1, characterized in that the matrix is based on a polymer.
3- Matériau selon la revendication 1 , caractérisé en ce que la matrice est à base d'une peinture ou vernis ou d'un latex.3- Material according to claim 1, characterized in that the matrix is based on a paint or varnish or a latex.
4- Matériau selon l'une des revendications précédentes, caractérisé en ce qu'il comprend un composé de formule (1 ) précitée dans laquelle 0,0001 < x < 0,25 et 0,0001 < y < 0,25.4- Material according to one of the preceding claims, characterized in that it comprises a compound of formula (1) above in which 0.0001 <x <0.25 and 0.0001 <y <0.25.
5- Matériau selon l'une des revendications précédentes, caractérisé en ce qu'il comprend un composé de formule (1) précitée dans laquelle 0,01 < x < 0,03 et 0,04 < y < 0,06.5- Material according to one of the preceding claims, characterized in that it comprises a compound of formula (1) above in which 0.01 <x <0.03 and 0.04 <y <0.06.
6- Matériau selon l'une des revendications 2 et 4 à 5, caractérisé en ce que la matrice est à base d'un polymère choisi dans le groupe comprenant les polyéthylenes basse densité, les polyéthylenes basse densité linéaires, les polyéthylenes obtenus par synthèse métallocène, le polychlorure de vinyle, le polyéthylène téréphtalate, le polystyrène, le polyméthylméthacrylate, le polyéthylène d'alcool vinylique, les mélanges et copolymères à base de ces (co)polymères, le polycarbonate.6- Material according to one of claims 2 and 4 to 5, characterized in that the matrix is based on a polymer chosen from the group comprising low density polyethylenes, linear low density polyethylenes, polyethylenes obtained by metallocene synthesis , polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethylmethacrylate, polyvinyl alcohol, mixtures and copolymers based on these (co) polymers, polycarbonate.
7- Matériau selon l'une des revendications 1 à 5, caractérisé en ce que la matrice est un vernis à ongles.7- Material according to one of claims 1 to 5, characterized in that the matrix is a nail varnish.
8- Matériau selon l'une des revendications 1 à 5, caractérisé en ce que la matrice est un gel coiffant. 9- Parois de serre, caractérisée en ce qu'elle comprend un matériau selon l'une des revendications 1 , 2, 4 à 6. 8- Material according to one of claims 1 to 5, characterized in that the matrix is a styling gel. 9- Greenhouse walls, characterized in that it comprises a material according to one of claims 1, 2, 4 to 6.
EP03767895A 2002-11-05 2003-11-04 Light transforming material comprising as additive a barium and magnesium silicate Withdrawn EP1570023A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0213832 2002-11-05
FR0213832A FR2846663B1 (en) 2002-11-05 2002-11-05 LIGHT-EMITTING MATERIAL, PARTICULARLY FOR GREENHOUSE WALLS, COMPRISING AS A BARIUM AND MAGNESIUM SILICATE ADDITIVE
PCT/FR2003/003283 WO2004044090A1 (en) 2002-11-05 2003-11-04 Light transforming material comprising as additive a barium and magnesium silicate

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BR0315798A (en) 2005-09-13
JP2006505659A (en) 2006-02-16
FR2846663B1 (en) 2006-08-11
JP4358748B2 (en) 2009-11-04
CN1714134A (en) 2005-12-28
US7536834B2 (en) 2009-05-26
WO2004044090A1 (en) 2004-05-27
US20060168905A1 (en) 2006-08-03
ECSP055779A (en) 2005-08-11
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CN1312251C (en) 2007-04-25
AP1904A (en) 2008-10-15
KR100713763B1 (en) 2007-05-07
MXPA05004781A (en) 2005-11-04
AP2005003327A0 (en) 2005-06-30
AU2003292329A1 (en) 2004-06-03
ZA200503582B (en) 2006-08-30
FR2846663A1 (en) 2004-05-07

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