WO2002032989A1 - Antimicrobial methacrylic polymer material and shaped articles obtained from same - Google Patents

Antimicrobial methacrylic polymer material and shaped articles obtained from same Download PDF

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Publication number
WO2002032989A1
WO2002032989A1 PCT/FR2001/003142 FR0103142W WO0232989A1 WO 2002032989 A1 WO2002032989 A1 WO 2002032989A1 FR 0103142 W FR0103142 W FR 0103142W WO 0232989 A1 WO0232989 A1 WO 0232989A1
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weight
methyl methacrylate
material according
compound
agent
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PCT/FR2001/003142
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French (fr)
Inventor
Yannick Ederle
Jean-Yves Barbin
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Atofina
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Application filed by Atofina filed Critical Atofina
Priority to EP01976397A priority Critical patent/EP1328575A1/en
Priority to AU2001295682A priority patent/AU2001295682A1/en
Publication of WO2002032989A1 publication Critical patent/WO2002032989A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides

Definitions

  • the invention relates to methacrylic antimicrobial polymeric materials comprising a matrix formed of thermoplastic methacrylic polymer or copolymer material mainly containing units derived from the methyl methacrylate monomer and at least two specific antimicrobial agents, these (co) polymeric materials exhibit effective protection. especially against bacteria, mold
  • thermoformed sanitary articles such as baths, sinks, shower trays, sinks, shower stalls, basins, etc.
  • These shaped articles must, in addition, retain the properties inherent in the methacrylic (co) polymer material, that is to say the mechanical, thermal, resistance to solvents, thermoforming capacity, good resistance to aging and the optical properties.
  • Methacrylic (co) polymers mainly containing units derived from the methyl methacrylate monomer are thermoplastic polymers increasingly used because of their exceptional optical properties (gloss, very high transparency with at least 90% light transmission in the visible ), their hardness, their ability to be pigmented, to be thermoformed, their resistance to aging, corrosion and atmospheric agents and the ease with which they can be transformed (cutting, polishing, gluing, folding).
  • methacrylic (co) polymers can be in the form of beads or granules allowing the manufacture of shaped articles by molding, in particular by extrusion, injection, compression, etc., or else in the form of plates.
  • Methacrylic (co) polymer plates can be obtained by extrusion or by casting.
  • a polymerizable composition which mainly contains methyl methacrylate monomer (or a syrup formed from methyl methacrylate prepolymer and methyl methacrylate monomer) and, optionally, copolymeric comonomers with methacrylate methyl.
  • This composition is introduced into a mold consisting of two glass plates separated by a polymer seal (polyvinyl chloride, for example) which ensures the seal and whose thickness determines the thickness of the polymer plate.
  • the mold is placed in a ventilated oven or in a heated swimming pool to allow the polymerization of the monomers.
  • the plate is recovered in methacrylic (co) polymer by demolding.
  • Methacrylic (co) polymer plates find use particularly in the sanitary field. Sanitary shaped articles are generally obtained by thermoforming of methacrylic (co) polymer plates manufactured by the cast process.
  • shaped articles obtained from methacrylic polymer (or copolymer) materials, when used under unhygienic conditions, bacteria, fungi, algae, etc. can develop, which it is necessary to reduce or even 'eliminate; this is particularly the case with shaped articles used in the sanitary field.
  • the antimicrobial methacrylic polymer material according to the invention which has these characteristics, comprises
  • I - a matrix formed of thermoplastic methacrylic polymer or copolymer material, formed, by weight, from 80 to 100%, preferably from 90 to 99.5% of methyl methacrylate monomer units and from 0 to 20%, preferably from 0 , 5 to 10% of units deriving from monoethylenically unsaturated comonomer (s) copolymerable (s) with the methyl methacrylate monomer and,
  • At least two bacterial agents consisting of (A) at least one halogenated phenoxy compound and (B) at least one thiazolinone, isothiazolinone and / or sulfonylpy ⁇ dine compound, the amount of agents A + B being , by weight, from 20 ppm to 20,000 ppm and the weight ratio of agent A and agent B being from 0.02 to 50, preferably from 0.1 to 10.
  • the antimicrobial methacrylic polymer material preferably comprises from 100 ppm to 10,000 ppm of antimicrobial agents (A + B), the remainder consisting of the matrix formed by the methacrylic (co) polymer material.
  • antimicrobial agents must provide at least one of the desired properties, that is to say protection against bacteria, fungi, algae
  • the halogenated phenoxy compound (A) is, in particular, 2,4,4'-tr ⁇ chloro-2'-hydroxy-diphenyl ether
  • the compound (B) can be a thiazolinone, an isothiazolinone and / or a sulfonylpy ⁇ dine compound.
  • thiazolinone compound l, 2-benzoth ⁇ azol ⁇ n-3-one can be used; as isothiazolinone, 5-chloro-2-methyl-4- ⁇ soth ⁇ azol ⁇ n-3-one, 2 methyl- 4- ⁇ soth ⁇ azol ⁇ n-3-one or 2-n-octyl-4- ⁇ soth ⁇ azol ⁇ n-3-one.
  • sulfonylpy ⁇ dine compound 2,3,5,6-tetrachloro-4- (methylsulfonyl) -py ⁇ d ⁇ ne (TMSP) or 2,3,5-t ⁇ chloro-4-propylsulfonylpy ⁇ d ⁇ ne can be used.
  • TMSP 2,3,5,6-tetrachloro-4- (methylsulfonyl) -py ⁇ d ⁇ ne
  • 2,3,5-t ⁇ chloro-4-propylsulfonylpy ⁇ d ⁇ ne 2,3,5-t ⁇ chloro-4-propylsulfonylpy ⁇ d ⁇ ne
  • the methacrylic (co) polymer material constituting the matrix (I) is advantageously formed by weight from 80 to 100%, preferably from 90 to 99.5%, of units derived from the methyl methacrylate monomer and from 0 to 20 % and preferably from 0.5 to 10% by weight of units deriving from monoethylenically unsaturated comonomer (s) copolymeric (s) with the methyl methacrylate monomer.
  • These monoethylenically unsaturated comonomers copolymerizable with the methyl methacrylate monomer are especially chosen from acrylic, methacrylic and vmylaromatic monomers.
  • acrylic monomers of acrylic acid, allyl acrylates in which the alkyl group has from 1 to 8 carbon atoms (such as n-butyl, ethyl, 2-ethylhexyl acrylate, isobutyl), hydroxyalkyl or alkoxyalkyl acrylates, in which the alkyl group has from 1 to 4 carbon atoms, acrylamide, acrylonitrile.
  • methacrylic monomers mention may be made of methacrylic acid, alkyl methacrylates in which the alkyl group has from 2 to 10 carbon atoms (such as ethyl methacrylate, isobutyl, secondary butyl, tertiary butyl) , isobomyl methacrylate, methacrylonitrile, hydroxyalkyl or alkoxyalkyl methacrylates in which the alkyl group has from 1 to 4 carbon atoms.
  • alkyl methacrylates in which the alkyl group has from 2 to 10 carbon atoms
  • isobomyl methacrylate methacrylonitrile
  • hydroxyalkyl or alkoxyalkyl methacrylates in which the alkyl group has from 1 to 4 carbon atoms.
  • styrene As vmylaromatic monomers, mention may be made of styrene, substituted styrenes (such as ⁇ -methyl-styrene, monochlorostyrene and tert.-butyl-styrene).
  • the methacrylic (co) polymer material which must form the matrix (I) can be obtained by any known method, for example by suspension or bulk polymerization. It can then be in the form of granules or pearls.
  • the pearls are obtained by the well-known process of polymerization in aqueous suspension of the monomer (s) in the presence of an initiator soluble in the monomer (s) and of a suspending agent.
  • the granules can be obtained from these beads which are melted in an extruder to form rods; these are then cut into granules.
  • the granules can also be prepared by bulk polymerization, a well-known process, consisting in polymerizing the monomer (s) or else a prepolymer syrup dissolved in the monomer (s), by presence of an initiator and a chain transfer agent to control the molecular weight of the polymer.
  • the antimicrobial methacrylic (co) polymer material according to the invention can be obtained by mixing the methacrylic (co) polymer material, for example in the form of pearls or granules, and antimicrobial agents, the latter possibly being in the form of a masterbatch and, optionally other additives such as dyes, pigments and / or UV stabilizers. This mixing can be carried out in any suitable device, for example in an extruder. The mixture is then in the form of granules which can be used to manufacture shaped articles for example by extrusion, injection, compression or any other known shaping process. These shaped articles can be in the form of plates or products of various shapes.
  • the antimicrobial (co) polymer material according to the invention can also be obtained from a polymerizable composition
  • a polymerizable composition comprising (a) a polymerizable element mainly comprising a methyl methacrylate component and, (b) dissolved in this polymerizable element or in the component methyl methacrylate, at least two antimicrobial agents, these agents consisting of (A) at least one halogenated phenoxy compound and (B) at least one thiazolinone, isothiazolinone and / or sulfonylpy ⁇ dine compound
  • the polymerizable element advantageously comprises, by weight, from 80 to 100%, preferably from 90 to 99.5%, of methyl methacrylate component and from 0 to 20% and, preferably, from 0.5 to 10% by weight. weight of monoethylenically unsaturated comonomer (s) copolymerable (s) with the methyl methacrylate monomer, such as those mentioned above.
  • the polymerizable element of said polymerizable composition can also comprise other additives copolymerable or not with the methyl methacrylate monomer.
  • the content of additives can be determined with respect to the methyl methacrylate component or with respect to the polymerizable composition.
  • the methyl methacrylate component is generally formed, by weight, from 85 to 100% of methyl methacrylate monomer and from 0 to 15% of a methyl methacrylate prepolymer having a conversion rate of 0.06 to 0.15.
  • the methyl methacrylate component is formed from a mixture (also called syrup) of methyl methacrylate monomer and methyl methacrylate prepolymer, it is advantageous for this mixture (or syrup) to have a viscosity of 100 to 500 mPa.s , preferably from 200 to 400 mPa.s so as to facilitate the implementation of the casting process (processability)
  • the syrup is prepared in a known manner, by partial polymerization of methyl methacrylate up to a conversion rate of 0.06 to 0.15
  • polyfunctional crosslinking agent (s) copolymerizable with the methyl methacrylate monomer mention may be made of polyfunctional monomers polyacrylates and polymethacrylates of polyols, such as diacrylates or dimethacrylates of alkylene glycol (such as diacrylates or dimethacrylates of ethylene glycol, of 1,3-butylene glycol, of 1,4-butylene glycol), polyfunctional vinylbenzene monomers (such as divinylbenzene or t ⁇ vinylbenzene), vinyl acrylate or methacrylate, allyl esters, such as methacrylate or allyl acrylate.
  • this agent or these agents can be used in an amount by weight relative to the methyl methacrylate component, from 0 to 0.2%,
  • At least one usual radical polymerization initiator such as an azo or peroxide compound, such as the azobis-isobutyronitrile compounds, dibenzoyl peroxide, tertiary peroxide. butyl, isobutyl peroxide, etc.
  • an azo or peroxide compound such as the azobis-isobutyronitrile compounds, dibenzoyl peroxide, tertiary peroxide. butyl, isobutyl peroxide, etc.
  • these compounds can be used in an amount by weight of 0 to 0.2%, preferably from 0.002 to 0.2%, very particularly from 0.01 to 0.2% relative to the methyl methacrylate component.
  • the polymerizable element can contain, in particular, at least one chain transfer agent, at least one release agent, at least one antioxidant agent and at least one pigment and / or dye.
  • Chain transfer agents make it possible to control the molecular mass of the polymer obtained from the composition. They are alkyl- or arylmercaptans, such as octylmercaptan, laurylmercaptan, t-dodecylmercaptan, polymercaptans, polyhalogen compounds, monoterpenes, such as terpinenes, monounsaturated diterpenes, thioglycolic acid and isooctyl thioglycolate. This or these compound (s) are advantageously added in an amount of 0 to 0.2%, preferably from 0.01 to 0.1% by weight relative to the methyl methacrylate component.
  • the polymerizable composition can also contain pigments or dyes, such as titanium dioxide, calcium carbonate, calcium sulfate, barium sulfate, carbon black.
  • pigments or dyes such as titanium dioxide, calcium carbonate, calcium sulfate, barium sulfate, carbon black.
  • they are added to the polymerizable composition in the form of a paste comprising a plasticizer, for example alkyl phthalate, in which they are dispersed in a homogeneous manner
  • This or these pasta (s) are advantageously added at a rate of 0 to 5 %, preferably from 0.1 to 5% and very particularly from 0.5 to 2% by weight relative to the polymerizable composition.
  • the polymerizable composition to be used for the manufacture of the antimicrobial (co) polymer material according to the invention comprises at least two antimicrobial agents dissolved in the polymerizable element or in its methyl methacrylate component.
  • These antimicrobial agents comprise at least one halogenated phenoxy compound (A) and at least one thiazolinone, isothiazolinone and / or sulfonylpy ⁇ dine compound (B) and are those mentioned above.
  • These compounds are used, in the polymerizable composition, in an amount of 20 ppm to 20,000 ppm, preferably from 100 ppm to 100,000 ppm. They can be added together or separately to the polymerizable element in the form of solution (s) in a plasticizer system common to the antimicrobial agents used, for example a t ⁇ arylphosphate, such as t ⁇ aryl phosphate isopropylated, t ⁇ xilyl phosphate (TXP), dioctylphthalate (DOP ), dioctyladipate (DOA), to facilitate their dissolution in the polymerizable element.
  • the weight ratio of agent A and agent B is advantageously from 0.02 to 50, preferably from 0.1 to 10.
  • the polymerizable composition which can be used in the invention is prepared by dissolving the antimicrobial additives (or their solution (s)) in the polymerizable element comprising the methyl methacrylate monomer (or the syrup formed from methyl methacrylate and a prepolymer of methyl methacrylate) and the other desired additives or they are dissolved in the methyl methacrylate component, then the other additives are added.
  • the polymerization of the polymerizable composition which can be used in the invention can take place by the known process known as casting.
  • a shaped product is then obtained directly in the form of a plate.
  • the polymerizable composition is introduced into a mold formed by two glass plates separated by a seal (or rod) made of polyvinyl chloride for example.
  • the mold is placed in a ventilated oven in order to follow the polymerization cycle which includes a polymerization step at a temperature of the order of 70 ° C to obtain a conversion rate of approximately 95%, then a post-polymerization step at a temperature of the order of 120 ° C.
  • the plate obtained is removed from the mold.
  • the plates obtained have a thickness which corresponds to the thickness of the rod.
  • These plates can be used as glazing, noise barriers, etc. or be transformed into various articles by thermoforming, cutting, polishing, gluing, folding.
  • the plates are particularly suitable for making sanitary articles (baths, sinks, shower trays, etc.).
  • the plates can be thermoformed. For this, they are heated to temperatures of at least 140 ° C to obtain their softening. The heating time necessary for complete softening depends on the thickness of the plate and the heating means. Then the softened plate is fixed on the edges of a mold in which the vacuum is created to allow the plate conforming to the shape During thermoforming, the thickness of the plate, which is initially 3 to 8 mm for example, can be reduced to a value between less than 1 mm and 4 mm.
  • AIBN azobisisobutyronit ⁇ le (initiator)
  • Example 1 a cast plate for sanitary product is prepared
  • the polymerizable element is prepared by adding to 100 parts by weight of a syrup (this syrup is formed from 10 parts by weight of methyl methacrylate prepolymer (conversion rate of 0.1) and of MMA (90 parts by weight ):
  • antioxidant agent Tinuvin P ® product sold by Gba- Ceigy
  • the polymerizable composition obtained in (1) is introduced into a mold formed by two glass plates (500 x 300 mm) separated by a polyvinyl chloride joint to obtain a plate with a thickness of 4 mm
  • the mold is placed in a ventilated oven.
  • the composition is polymerized for 5 hours at 70 ° C. A conversion rate of around 95% is obtained; then heated to 120 ° C for 1 hour. After cooling the mold, the plate is recovered.
  • the plate obtained is thermoformed in the form of a bathtub, as indicated above, without breakage.
  • Example 2 The procedure is as in Example 1, but to 99 parts by weight of polymerizable material, 1 part of a mixture of 2,4,4'-t ⁇ chloro-2'-hydroxy-d ⁇ phenyl ether and 2.3 is added, 5,6-tetrachloro-4- (methylsulfonyl) -pyr ⁇ d ⁇ ne (TMSP) in solution in a phosphate-based plasticizer.
  • TMSP 5,6-tetrachloro-4- (methylsulfonyl) -pyr ⁇ d ⁇ ne
  • This mixture is sold under the trade name "Sanitized PL 98-36" by the company Cla ⁇ ant.
  • Antibacterial and antimycotic activity is measured, as indicated above. The results are shown in the table.
  • Example 2 The procedure is as in Example 1, but a polymerizable composition using no antimicrobial agent is used. We measure, as indicated above, the antibacterial and anti-fungal activity. The results are shown in the table.

Abstract

The invention concerns an antimicrobial methacrylic polymer comprising a matrix formed of thermoplastic methacrylic polymer or copolymer material, consisting, by weight, of: 80 to 100 %, preferably 90 to 99.5 % of methyl methacrylate monomer units and 0 to 20 %, preferably 0.5 to 10 % of units derived from monoethylenically unsaturated comonomer(s) compolymerisable with the methyl methacrylate monomer and, dispersed in said matrix, at least two antibacterial agents consisting of (A) at least a halogenated phenoxy compound and (B) at least a thiazolinone, isothiazolinone and/or sulphonylpyridine compound, the amount in agents A + B being, by weight, from 20 ppm to 20000 ppm and the weight ratio in agent A and agent B being 0.02 to 50, preferably 0.1 to 10. The invention is useful for making antimicrobial cast or extruded plates, in particular for use in the field of sanitary ware.

Description

MATERIAU POLYMERE METHACRYLIQUE ANTIMICROBIEN ET ARTICLES FAÇONNES ANTIMICROBIAL METHACRYLIC POLYMER MATERIAL AND SHAPED ARTICLES
OBTENUS A PARTIR DE CE MATERIAU DESCRIPTIONOBTAINED FROM THIS MATERIAL DESCRIPTION
L'invention est relative à des matériaux polymères méthacryliques antimicrobiens comprenant une matrice formée de matière polymère ou copolymère méthacrylique thermoplastique contenant majoritairement des motifs dérivant du monomère methacrylate de méthyle et au moins deux agents antimicrobiens spécifiques, ces matériaux (co)polymères présentent une protection efficace notamment contre les bactéries, les moisissuresThe invention relates to methacrylic antimicrobial polymeric materials comprising a matrix formed of thermoplastic methacrylic polymer or copolymer material mainly containing units derived from the methyl methacrylate monomer and at least two specific antimicrobial agents, these (co) polymeric materials exhibit effective protection. especially against bacteria, mold
(champignons) et les algues ; ils permettent de fabriquer des articles façonnés présentant cette protection, en particulier des plaques, et tout particulièrement des plaques utiles pour former des articles thermoformés sanitaires, tels que baignoires, éviers, receveurs de douche, lavabos, cabines de douche, vasques etc Ces articles façonnés doivent, en outre, conserver les propriétés inhérentes à la matière (co)polymère méthacrylique, c'est-à-dire les propriétés mécaniques, thermiques, résistance aux solvants, aptitude au thermoformage, bonne tenue au vieillissement et les propriétés optiques(mushrooms) and algae; they make it possible to manufacture shaped articles exhibiting this protection, in particular plates, and very particularly plates useful for forming thermoformed sanitary articles, such as baths, sinks, shower trays, sinks, shower stalls, basins, etc. These shaped articles must, in addition, retain the properties inherent in the methacrylic (co) polymer material, that is to say the mechanical, thermal, resistance to solvents, thermoforming capacity, good resistance to aging and the optical properties.
Les (co)polymères méthacryliques, contenant majoritairement des motifs dérivant du monomère methacrylate de méthyle sont des polymères thermoplastiques de plus en plus utilisés en raison de leurs propriétés optiques exceptionnelles (brillance, transparence très élevée avec au moins 90 % de transmission lumineuse dans le visible), leur dureté, leur aptitude à être pigmentés, à être thermoformés, leur tenue au vieillissement, à la corrosion et aux agents atmosphériques et la facilité avec laquelle on peut les transformer (découpage, polissage, collage, pliage).Methacrylic (co) polymers, mainly containing units derived from the methyl methacrylate monomer are thermoplastic polymers increasingly used because of their exceptional optical properties (gloss, very high transparency with at least 90% light transmission in the visible ), their hardness, their ability to be pigmented, to be thermoformed, their resistance to aging, corrosion and atmospheric agents and the ease with which they can be transformed (cutting, polishing, gluing, folding).
Ces (co)polymères méthacryliques peuvent se trouver sous forme de perles ou de granulés permettant la fabrication d'articles façonnés par moulage, en particulier par extrusion, injection, compression, etc, ou bien sous forme de plaquesThese methacrylic (co) polymers can be in the form of beads or granules allowing the manufacture of shaped articles by molding, in particular by extrusion, injection, compression, etc., or else in the form of plates.
Des plaques en (co)polymère méthacrylique peuvent être obtenues par extrusion ou par coulé.Methacrylic (co) polymer plates can be obtained by extrusion or by casting.
Pour obtenir des plaques selon le procédé coulé, on utilise une composition polyméπsable contenant principalement le monomère methacrylate de méthyle (ou un sirop formé de prépolymère de methacrylate de méthyle et de monomère methacrylate de méthyle) et, éventuellement, des comonomères copolyméπsables avec le methacrylate de méthyle. On introduit cette composition dans un moule constitué de deux plaques en verre séparées par un joint en polymère (polychlorure de vinyle, par exemple) qui assure l'étanchéité et dont l'épaisseur détermine l'épaisseur de la plaque de polymère. Le moule est placé dans une etuve ventilée ou en piscine chauffée afin de permettre la polymérisation des monomères En fin de polymérisation, on récupère la plaque en (co)polymère méthacrylique par démoulage. Les plaques en (co)polymère méthacrylique trouvent une utilisation particulièrement dans le domaine sanitaire. Les articles façonnés sanitaires sont généralement obtenus par thermoformage de plaques en (co)polymere méthacrylique fabriquées par procédé coulé.To obtain plates according to the cast process, a polymerizable composition is used which mainly contains methyl methacrylate monomer (or a syrup formed from methyl methacrylate prepolymer and methyl methacrylate monomer) and, optionally, copolymeric comonomers with methacrylate methyl. This composition is introduced into a mold consisting of two glass plates separated by a polymer seal (polyvinyl chloride, for example) which ensures the seal and whose thickness determines the thickness of the polymer plate. The mold is placed in a ventilated oven or in a heated swimming pool to allow the polymerization of the monomers. At the end of polymerization, the plate is recovered in methacrylic (co) polymer by demolding. Methacrylic (co) polymer plates find use particularly in the sanitary field. Sanitary shaped articles are generally obtained by thermoforming of methacrylic (co) polymer plates manufactured by the cast process.
Sur les articles façonnés, obtenus à partir des matières polymères (ou copolymères) méthacryliques, lorsqu'ils sont utilisés dans des conditions non hygiéniques, peuvent se développer des bactéries, champignons, algues, etc, qu'il est nécessaire de réduire, voire d'éliminer; ceci est particulièrement le cas avec des articles façonnés utilises dans le domaine du sanitaire.On shaped articles, obtained from methacrylic polymer (or copolymer) materials, when used under unhygienic conditions, bacteria, fungi, algae, etc. can develop, which it is necessary to reduce or even 'eliminate; this is particularly the case with shaped articles used in the sanitary field.
Il est donc souhaitable de trouver des matériaux polymères méthacryliques à partir desquels on peut fabriquer des articles façonnés, en particulier des plaques, de préférence obtenues par procédé coulé, présentant une protection efficace notamment contre les bactéries, champignons et les algues, tout en conservant notamment leurs propriétés mécaniques, thermiques, optiques, la résistance aux solvants, l'aptitude au thermoformage et une bonne tenue au vieillissement. Le matériau polymère méthacrylique antimicrobien selon l'invention, qui présente ces caractéristiques, comprendIt is therefore desirable to find methacrylic polymeric materials from which it is possible to manufacture shaped articles, in particular plates, preferably obtained by casting process, having effective protection in particular against bacteria, fungi and algae, while preserving in particular their mechanical, thermal and optical properties, resistance to solvents, ability to thermoform and good resistance to aging. The antimicrobial methacrylic polymer material according to the invention, which has these characteristics, comprises
I - une matrice formée de matière polymère ou copolymère méthacrylique thermoplastique , formée, en poids, de 80 à 100 %, de préférence de 90 a 99,5 % de motifs monomère methacrylate de méthyle et de 0 à 20 %, de préférence de 0,5 à 10 % de motifs dérivant de comonomère(s) à insaturation monoéthylénique copolymérιsable(s) avec le monomère methacrylate de méthyle et,I - a matrix formed of thermoplastic methacrylic polymer or copolymer material, formed, by weight, from 80 to 100%, preferably from 90 to 99.5% of methyl methacrylate monomer units and from 0 to 20%, preferably from 0 , 5 to 10% of units deriving from monoethylenically unsaturated comonomer (s) copolymerable (s) with the methyl methacrylate monomer and,
II - dispersés dans cette matrice, au moins deux agents a nti bactérien s constitués par (A) au moins un composé phénoxy halogène et (B) au moins un composé thiazolinone, isothiazolinone et/ou sulfonylpyπdine, la quantité en agents A + B étant, en poids, de 20 ppm à 20000 ppm et le rapport en poids d'agent A et d'agent B étant de 0,02 à 50, de préférence de 0,1 à 10.II - dispersed in this matrix, at least two bacterial agents consisting of (A) at least one halogenated phenoxy compound and (B) at least one thiazolinone, isothiazolinone and / or sulfonylpyπdine compound, the amount of agents A + B being , by weight, from 20 ppm to 20,000 ppm and the weight ratio of agent A and agent B being from 0.02 to 50, preferably from 0.1 to 10.
Le matériau polymère méthacrylique antimicrobien comprend, de préférence de 100 ppm à 10000 ppm d'agents antimicrobiens (A + B), le reste étant constitué par la matrice formée par la matière (co)polymere méthacrylique. Ces agents antimicrobiens doivent apporter au moins l'une des propriétés souhaitées, c'est-à-dire une protection contre les bactéries, les champignons, les alguesThe antimicrobial methacrylic polymer material preferably comprises from 100 ppm to 10,000 ppm of antimicrobial agents (A + B), the remainder consisting of the matrix formed by the methacrylic (co) polymer material. These antimicrobial agents must provide at least one of the desired properties, that is to say protection against bacteria, fungi, algae
Le composé phénoxy halogène (A) est, en particulier, du 2,4,4'-trιchloro-2'-hydroxy- diphényl étherThe halogenated phenoxy compound (A) is, in particular, 2,4,4'-trιchloro-2'-hydroxy-diphenyl ether
Le composé (B) peut être une thiazolinone, une isothiazolinone et/ou un compose sulfonylpyπdine. Comme compose thiazolinone, on peut utiliser la l,2-benzothιazolιn-3-one ; comme isothiazolinone, on peut utiliser la 5-chloro-2-méthyl-4-ιsothιazolιn-3-one, la 2 methyl- 4-ιsothιazolιn-3-one ou la 2-n-octyl-4-ιsothιazolιn-3-one. On préfère utiliser cette dernière isothiazohne. Comme composé sulfonylpyπdine, on peut utiliser la 2,3,5,6-tetrachloro-4- (méthylsulfonyl)-pyπdιne (TMSP) ou la 2,3,5-tπchloro-4-propylsulfonylpyπdιne.The compound (B) can be a thiazolinone, an isothiazolinone and / or a sulfonylpyπdine compound. As thiazolinone compound, l, 2-benzothιazolιn-3-one can be used; as isothiazolinone, 5-chloro-2-methyl-4-ιsothιazolιn-3-one, 2 methyl- 4-ιsothιazolιn-3-one or 2-n-octyl-4-ιsothιazolιn-3-one. We prefer to use the latter isothiazohne. As the sulfonylpyπdine compound, 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyπdιne (TMSP) or 2,3,5-tπchloro-4-propylsulfonylpyπdιne can be used.
La matière (co)polymère méthacrylique constituant la matrice (I) est formée, avantageusement, en poids, de 80 à 100%, de préférence de 90 à 99,5%, de motifs dérivant du monomère methacrylate de méthyle et de 0 à 20% et, de préférence, de 0,5 à 10 % en poids de motifs dérivant de comonomère(s) à insaturation monoéthylénique copolyméπsable(s) avec le monomère methacrylate de méthyle.The methacrylic (co) polymer material constituting the matrix (I) is advantageously formed by weight from 80 to 100%, preferably from 90 to 99.5%, of units derived from the methyl methacrylate monomer and from 0 to 20 % and preferably from 0.5 to 10% by weight of units deriving from monoethylenically unsaturated comonomer (s) copolymeric (s) with the methyl methacrylate monomer.
Ces comonomères à insaturation monoéthylénique copolyménsables avec le monomère methacrylate de méthyle sont notamment choisis parmi les monomères acryliques, méthacryliques et vmylaromatiques.These monoethylenically unsaturated comonomers copolymerizable with the methyl methacrylate monomer are especially chosen from acrylic, methacrylic and vmylaromatic monomers.
Comme monomères acryliques, on peut citer l'acide acrylique, les acrylates d'al yle dans lesquels le groupe alkyle a de 1 à 8 atomes de carbone (comme l'acrylate de n-butyle, d'éthyle, de 2-éthylhexyle, d'isobutyle), les acrylates d'hydroxyalkyle ou d'alkoxyalkyle, dans lesquels le groupe alkyle a de 1 à 4 atomes de carbone, l'acrylamide, l'acrylonitπle.Mention may be made, as acrylic monomers, of acrylic acid, allyl acrylates in which the alkyl group has from 1 to 8 carbon atoms (such as n-butyl, ethyl, 2-ethylhexyl acrylate, isobutyl), hydroxyalkyl or alkoxyalkyl acrylates, in which the alkyl group has from 1 to 4 carbon atoms, acrylamide, acrylonitrile.
Comme monomères méthacryliques, on peut citer l'acide méthacrylique, les méthacrylates d'alkyle dans lesquels le groupe alkyle a de 2 à 10 atomes de carbone (comme le methacrylate d'éthyle, d'isobutyle, de butyle secondaire, de butyle tertiaire), le methacrylate d'isobomyle, le méthacrylonitπle, les méthacrylates d'hydroxyalkyle ou d'alcoxyalkyle dans lesquels le groupe alkyle a de 1 à 4 atomes de carbone.As methacrylic monomers, mention may be made of methacrylic acid, alkyl methacrylates in which the alkyl group has from 2 to 10 carbon atoms (such as ethyl methacrylate, isobutyl, secondary butyl, tertiary butyl) , isobomyl methacrylate, methacrylonitrile, hydroxyalkyl or alkoxyalkyl methacrylates in which the alkyl group has from 1 to 4 carbon atoms.
Comme monomères vmylaromatiques, on peut citer le styrène, les styrènes substitués (comme l'α-méthyl-styrène, le monochlorostyrène et le tert.-butyl-styrène).As vmylaromatic monomers, mention may be made of styrene, substituted styrenes (such as α-methyl-styrene, monochlorostyrene and tert.-butyl-styrene).
La matière (co)polymère méthacrylique devant former la matrice (I) peut être obtenue par tout procédé connu, par exemple par polymérisation en suspension ou en masse. Elle peut alors se trouver sous forme de granulés ou de perles.The methacrylic (co) polymer material which must form the matrix (I) can be obtained by any known method, for example by suspension or bulk polymerization. It can then be in the form of granules or pearls.
Les perles sont obtenues par le procédé bien connu de polymérisation en suspension aqueuse du ou des monomère(s) en présence d'un amorceur soluble dans le ou les monomères et d'un agent de suspension. Les granulés peuvent être obtenus à partir de ces perles qui sont fondues en extrudeuse pour former des joncs ; ceux-ci sont ensuite découpés en granulés Les granulés peuvent aussi être prépares par polymérisation en masse, procédé bien connu, consistant à polyméπser le ou les monomère(s) ou bien un sirop de prépolymère dissous dans le ou les monomère(s), en présence d'un amorceur et d'un agent de transfert de chaîne pour contrôler la masse moléculaire du polymère. Le polymère obtenu est forcé en fin de ligne dans une filière pour obtenir des joncs qui sont découpés ensuite en granulés. Le matériau (co)polymere méthacrylique antimicrobien selon l'invention peut être obtenu par mélange de la matière (co)polymère méthacrylique, par exemple sous forme de perles ou de granulés, et des agents antimicrobiens, ces derniers pouvant être sous forme de mélange-maître et, éventuellement d'autres additifs tels que des colorants, des pigments et/ou des stabilisants UV. Ce mélange peut être réalisé dans tout dispositif approprie, par exemple en extrudeuse Le mélange se trouve alors sous forme de granulés qui peuvent être utilisés pour fabriquer des articles façonnés par exemple par extrusion, injection, compression ou tout autre procédé de façonnage connu. Ces articles façonnés peuvent se présenter sous forme de plaques ou de produits de formes variées.The pearls are obtained by the well-known process of polymerization in aqueous suspension of the monomer (s) in the presence of an initiator soluble in the monomer (s) and of a suspending agent. The granules can be obtained from these beads which are melted in an extruder to form rods; these are then cut into granules The granules can also be prepared by bulk polymerization, a well-known process, consisting in polymerizing the monomer (s) or else a prepolymer syrup dissolved in the monomer (s), by presence of an initiator and a chain transfer agent to control the molecular weight of the polymer. The polymer obtained is forced at the end of the line into a die to obtain rods which are then cut into granules. The antimicrobial methacrylic (co) polymer material according to the invention can be obtained by mixing the methacrylic (co) polymer material, for example in the form of pearls or granules, and antimicrobial agents, the latter possibly being in the form of a masterbatch and, optionally other additives such as dyes, pigments and / or UV stabilizers. This mixing can be carried out in any suitable device, for example in an extruder. The mixture is then in the form of granules which can be used to manufacture shaped articles for example by extrusion, injection, compression or any other known shaping process. These shaped articles can be in the form of plates or products of various shapes.
Le matériau (co)polymère antimicrobien selon l'invention peut aussi être obtenu à partir d'une composition polyméπsable comprenant (a) un élément polyméπsable comprenant majoritairement un composant methacrylate de méthyle et, (b) dissous dans cet élément polyméπsable ou dans le composant methacrylate de méthyle, au moins deux agents antimicrobiens, ces agents étant constitués par (A) au moins un composé phénoxy halogène et (B) au moins un composé thiazolinone, isothiazolinone et/ou sulfonylpyπdineThe antimicrobial (co) polymer material according to the invention can also be obtained from a polymerizable composition comprising (a) a polymerizable element mainly comprising a methyl methacrylate component and, (b) dissolved in this polymerizable element or in the component methyl methacrylate, at least two antimicrobial agents, these agents consisting of (A) at least one halogenated phenoxy compound and (B) at least one thiazolinone, isothiazolinone and / or sulfonylpyπdine compound
L' élément polyméπsable comprend avantageusement, en poids, de 80 à 100%, de préférence de 90 à 99,5%, de composant methacrylate de méthyle et de 0 à 20% et, de préférence, de 0,5 à 10 % en poids de comonomère(s) à insaturation monoéthylénique copolymérιsable(s) avec le monomère methacrylate de méthyle, tels que ceux mentionnés précédemment.The polymerizable element advantageously comprises, by weight, from 80 to 100%, preferably from 90 to 99.5%, of methyl methacrylate component and from 0 to 20% and, preferably, from 0.5 to 10% by weight. weight of monoethylenically unsaturated comonomer (s) copolymerable (s) with the methyl methacrylate monomer, such as those mentioned above.
L'élément polyméπsable de ladite composition polyméπsable peut aussi comprendre d'autres additifs copolyméπsables ou non_avec le monomère methacrylate de méthyle La teneur en additifs peut être déterminée par rapport au composant methacrylate de méthyle ou par rapport à la composition polyméπsable.The polymerizable element of said polymerizable composition can also comprise other additives copolymerable or not with the methyl methacrylate monomer. The content of additives can be determined with respect to the methyl methacrylate component or with respect to the polymerizable composition.
Le composant methacrylate de méthyle est généralement formé, en poids, de 85 à 100 % de monomère methacrylate de méthyle et de 0 à 15 % d'un prépolymère de methacrylate de méthyle ayant un taux de conversion de 0,06 à 0,15.The methyl methacrylate component is generally formed, by weight, from 85 to 100% of methyl methacrylate monomer and from 0 to 15% of a methyl methacrylate prepolymer having a conversion rate of 0.06 to 0.15.
Lorsque le composant methacrylate de méthyle est formé d'un mélange (appelé aussi sirop) de monomère methacrylate de méthyle et de prépolymère de methacrylate de méthyle, il est avantageux que ce mélange (ou sirop) présente une viscosité de 100 à 500 mPa.s, de préférence de 200 à 400 mPa.s de manière à faciliter la mise en œuvre du procédé en coulé (processabilité) Le sirop est préparé d'une manière connue, par polymérisation partielle de methacrylate de méthyle jusqu'à un taux de conversion de 0,06 a 0,15When the methyl methacrylate component is formed from a mixture (also called syrup) of methyl methacrylate monomer and methyl methacrylate prepolymer, it is advantageous for this mixture (or syrup) to have a viscosity of 100 to 500 mPa.s , preferably from 200 to 400 mPa.s so as to facilitate the implementation of the casting process (processability) The syrup is prepared in a known manner, by partial polymerization of methyl methacrylate up to a conversion rate of 0.06 to 0.15
Comme additifs copolyméπsables avec le monomère methacrylate de méthyle, autres que les comonomères à insaturation monoéthylénique mentionnés précédemment, on peut utiliser notamment au moins un agent polyfonctionnel de réticulation. Comme agent(s) polyfonctιonnel(s) de réticulation copolymerιsable(s) avec le monomère methacrylate de méthyle, on peut citer les monomères polyfonctionnels polyacrylates et polyméthacrylates de polyols, tels que les diacrylates ou les diméthacrylates d'alkylène glycol (comme diacrylates ou diméthacrylates d'éthylène glycol, de 1,3- butylèneglycol, de 1,4-butylèneglycol), les monomères polyfonctionnels vinylbenzènes (comme le divinylbenzène ou le tπvinylbenzène), l'acrylate ou le methacrylate de vinyle, les esters d'allyle, comme le methacrylate ou l'acrylate d'allyle. Ainsi, on peut utiliser ce ou ces agents en quantité en poids par rapport au composant methacrylate de méthyle, de 0 à 0,2 %, de préférence 0,01 à 0,1 %.As additives which are copolymeric with the methyl methacrylate monomer, other than the monoethylenically unsaturated comonomers mentioned above, it is possible in particular to use at least one polyfunctional crosslinking agent. As polyfunctional crosslinking agent (s) copolymerizable with the methyl methacrylate monomer, mention may be made of polyfunctional monomers polyacrylates and polymethacrylates of polyols, such as diacrylates or dimethacrylates of alkylene glycol (such as diacrylates or dimethacrylates of ethylene glycol, of 1,3-butylene glycol, of 1,4-butylene glycol), polyfunctional vinylbenzene monomers (such as divinylbenzene or tπvinylbenzene), vinyl acrylate or methacrylate, allyl esters, such as methacrylate or allyl acrylate. Thus, this agent or these agents can be used in an amount by weight relative to the methyl methacrylate component, from 0 to 0.2%, preferably 0.01 to 0.1%.
Pour la polymérisation de l'élément polymérisable, on ajoute, avantageusement, audit élément, au moins un amorceur de polymérisation radicalaire usuel, tel qu'un composé azoïque ou peroxydique, comme les composés azobis-isobutyronitπle, peroxyde de dibenzoyle, peroxyde de tertio-butyle, peroxyde d'isobutyle, etc. On peut utiliser ces composes en quantité en poids de 0 à 0,2 %, de préférence de 0,002 à 0,2 %, tout particulièrement de 0,01 à 0,2 % par rapport au composant methacrylate de méthyle.For the polymerization of the polymerizable element, there is advantageously added to said element, at least one usual radical polymerization initiator, such as an azo or peroxide compound, such as the azobis-isobutyronitrile compounds, dibenzoyl peroxide, tertiary peroxide. butyl, isobutyl peroxide, etc. These compounds can be used in an amount by weight of 0 to 0.2%, preferably from 0.002 to 0.2%, very particularly from 0.01 to 0.2% relative to the methyl methacrylate component.
Comme autres additifs non polyméπsables avec le monomère methacrylate de méthyle, l'élément polymérisable peut contenir, notamment, au moins un agent de transfert de chaîne, au moins un agent démoulant, au moins un agent antioxydant et au moins un pigment et/ou colorant.Like other additives which cannot be polymerized with the methyl methacrylate monomer, the polymerizable element can contain, in particular, at least one chain transfer agent, at least one release agent, at least one antioxidant agent and at least one pigment and / or dye. .
Les agents de transfert de chaîne (ou agent limiteur de chaîne) permettent de contrôler la masse moléculaire du polymère obtenu à partir de la composition. Ce sont des alkyl- ou arylmercaptans, comme l'octylmercaptan, le laurylmercaptan, le t-dodécylmercaptan, les polymercaptans, les composés polyhalogénes, les monoterpènes, comme les terpinènes, les diterpènes monoinsaturés, l'acide thioglycolique et le thioglycolate d'isooctyle. Ce ou ces composés sont ajouté(s) avantageusement à raison de 0 à 0,2 %, de préférence de 0,01 à 0,1 % en poids par rapport au composant methacrylate de méthyle. La composition polymérisable peut aussi contenir des pigments ou des colorants, comme du dioxyde de titane, du carbonate de calcium, du sulfate de calcium, sulfate de baryum, noir de carbone. Généralement, ils sont ajoutés à la composition polymérisable sous forme de pâte comprenant un plastifiant, par exemple du phtalate d'alkyle, dans lequel ils sont dispersés de façon homogène Cette ou ces pâtes sont a outée(s) avantageusement a raison de 0 à 5 %, de préférence de 0,1 à 5 % et tout particulièrement de 0,5 a 2% en poids par rapport à la composition polymérisable.Chain transfer agents (or chain limiting agent) make it possible to control the molecular mass of the polymer obtained from the composition. They are alkyl- or arylmercaptans, such as octylmercaptan, laurylmercaptan, t-dodecylmercaptan, polymercaptans, polyhalogen compounds, monoterpenes, such as terpinenes, monounsaturated diterpenes, thioglycolic acid and isooctyl thioglycolate. This or these compound (s) are advantageously added in an amount of 0 to 0.2%, preferably from 0.01 to 0.1% by weight relative to the methyl methacrylate component. The polymerizable composition can also contain pigments or dyes, such as titanium dioxide, calcium carbonate, calcium sulfate, barium sulfate, carbon black. Generally, they are added to the polymerizable composition in the form of a paste comprising a plasticizer, for example alkyl phthalate, in which they are dispersed in a homogeneous manner This or these pasta (s) are advantageously added at a rate of 0 to 5 %, preferably from 0.1 to 5% and very particularly from 0.5 to 2% by weight relative to the polymerizable composition.
On peut ajouter d'autres composés usuels comme un agent démoulant, des antioxydants, des agents absorbant l'UV, etc, en quantité de 0 à 0,2%, de préférence de 0,01 à 0,1% en poids par rapport au composant methacrylate de méthyle. D'autres additifs peuvent être utilisés en fonction de l'application envisagée. Selon ce mode de réalisation, la composition polymérisable devant servir à la fabrication du matériau (co)polymère antimicrobien selon l'invention comprend au moins deux agents antimicrobiens dissous dans l'élément polymérisable ou dans son composant methacrylate de méthyle. Ces agents antimicrobiens comprennent au moins un composé phénoxy halogène (A) et au moins un composé (B) thiazolinone, isothiazolinone et/ou sulfonylpyπdine et sont ceux mentionnés précédemment. Ces composes sont utilisés, dans la composition polymérisable, en quantité de 20 ppm à 20000ppm, de préférence de lOOppm à lOOOOppm. On peut les ajouter ensemble ou séparément à l'élément polymérisable sous forme de solutιon(s) dans un système plastifiant commun aux agents antimicrabiens utilisés, par exemple un tπarylphosphate, tel que tπaryl phosphate isopropylé, tπxilyl phosphate (TXP), du dioctylphtalate (DOP), dioctyladipate (DOA), pour faciliter leur dissolution dans l'élément polymérisable. Le rapport en poids d'agent A et d'agent B est avantageusement de 0,02 à 50, de préférence de 0,1 à 10.Other usual compounds can be added such as a release agent, antioxidants, UV-absorbing agents, etc., in an amount of 0 to 0.2%, preferably 0.01 to 0.1% by weight relative to to the methyl methacrylate component. Other additives can be used depending on the intended application. According to this embodiment, the polymerizable composition to be used for the manufacture of the antimicrobial (co) polymer material according to the invention comprises at least two antimicrobial agents dissolved in the polymerizable element or in its methyl methacrylate component. These antimicrobial agents comprise at least one halogenated phenoxy compound (A) and at least one thiazolinone, isothiazolinone and / or sulfonylpyπdine compound (B) and are those mentioned above. These compounds are used, in the polymerizable composition, in an amount of 20 ppm to 20,000 ppm, preferably from 100 ppm to 100,000 ppm. They can be added together or separately to the polymerizable element in the form of solution (s) in a plasticizer system common to the antimicrobial agents used, for example a tπarylphosphate, such as tπaryl phosphate isopropylated, tπxilyl phosphate (TXP), dioctylphthalate (DOP ), dioctyladipate (DOA), to facilitate their dissolution in the polymerizable element. The weight ratio of agent A and agent B is advantageously from 0.02 to 50, preferably from 0.1 to 10.
La composition polymérisable utilisable dans l'invention est préparée en dissolvant les additifs antimicrobiens (ou leur(s) solutιon(s)) dans l'élément polymérisable comprenant le monomère methacrylate de méthyle (ou le sirop formé de methacrylate de méthyle et un prépolymère de methacrylate de méthyle) et les autres additifs souhaités ou bien on les dissout dans le composant methacrylate de méthyle, puis on ajoute les autres additifs.The polymerizable composition which can be used in the invention is prepared by dissolving the antimicrobial additives (or their solution (s)) in the polymerizable element comprising the methyl methacrylate monomer (or the syrup formed from methyl methacrylate and a prepolymer of methyl methacrylate) and the other desired additives or they are dissolved in the methyl methacrylate component, then the other additives are added.
La polymérisation de la composition polymérisable utilisable dans l'invention peut avoir lieu par le procédé connu dit coulé On obtient alors directement un produit façonné sous forme de plaque. Comme indiqué précédemment, on introduit la composition polymérisable dans un moule formé de deux plaques en verre séparées par un joint (ou jonc) en polychlorure de vinyle par exemple. Le moule est placé dans une étuve ventilée afin de suivre le cycle de polymérisation qui comprend une étape de polymérisation à une température de l'ordre de 70°C pour obtenir un taux de conversion de 95 % environ, puis une étape de post- polyméπsation à une température de l'ordre de 120°C Après refroidissement, on retire du moule la plaque obtenue. Les plaques obtenues ont une épaisseur qui correspond à l'épaisseur du jonc.The polymerization of the polymerizable composition which can be used in the invention can take place by the known process known as casting. A shaped product is then obtained directly in the form of a plate. As indicated above, the polymerizable composition is introduced into a mold formed by two glass plates separated by a seal (or rod) made of polyvinyl chloride for example. The mold is placed in a ventilated oven in order to follow the polymerization cycle which includes a polymerization step at a temperature of the order of 70 ° C to obtain a conversion rate of approximately 95%, then a post-polymerization step at a temperature of the order of 120 ° C. After cooling, the plate obtained is removed from the mold. The plates obtained have a thickness which corresponds to the thickness of the rod.
Ces plaques peuvent être utilisées comme vitrages, murs antibruit etc ou être transformées en articles divers par thermoformage, découpage, polissage, collage, pliageThese plates can be used as glazing, noise barriers, etc. or be transformed into various articles by thermoforming, cutting, polishing, gluing, folding.
Ces plaques sont particulièrement utilisables pour fabriquer des articles sanitaires (baignoires, éviers, receveurs de douche etc ). Pour fabriquer de tels articles façonnés, les plaques peuvent subir un thermoformage. Pour cela, on les chauffe à des températures d'au moins 140 °C pour obtenir leur ramollissement. La durée de chauffe nécessaire à un complet ramollissement dépend de l'épaisseur de la plaque et des moyens de chauffage Puis la plaque ramollie est fixée sur les bords d'un moule dans lequel le vide est effectué pour permettre a la plaque d'en épouser la forme Lors du thermoformage, l'épaisseur de la plaque, qui est initialement de 3 à 8 mm par exemple, peut être réduite à une valeur comprise entre moins de lmm et 4 mm.These plates are particularly suitable for making sanitary articles (baths, sinks, shower trays, etc.). To manufacture such shaped articles, the plates can be thermoformed. For this, they are heated to temperatures of at least 140 ° C to obtain their softening. The heating time necessary for complete softening depends on the thickness of the plate and the heating means. Then the softened plate is fixed on the edges of a mold in which the vacuum is created to allow the plate conforming to the shape During thermoforming, the thickness of the plate, which is initially 3 to 8 mm for example, can be reduced to a value between less than 1 mm and 4 mm.
Les exemples suivants illustrent l'invention; les composés suivants sont utilisés dans les exemples.The following examples illustrate the invention; the following compounds are used in the examples.
» MAM : methacrylate de méthyle»MAM: methyl methacrylate
» ABu • acrylate de butyle (comonomère)»ABu • butyl acrylate (comonomer)
» AIBN . azobisisobutyronitπle (amorceur)AIBN. azobisisobutyronitπle (initiator)
» BDMA : diméthacrylate de 1,4-butanedιol (agent réticulant) L'activité antimicrobienne (antibactérie et anti-champignons) indiquée dans les exemples a été mesurée sur des plaques en utilisant les méthodes suivantes pour le contrôle de l'activité anti bactérienne ou antimycosique de textiles apprêtés et d'autres matériaux.»BDMA: 1,4-butanedιol dimethacrylate (crosslinking agent) The antimicrobial activity (antibacterial and anti-fungus) indicated in the examples was measured on plates using the following methods for monitoring the anti-bacterial activity or antimycotic of finished textiles and other materials.
* SN 195920 : contrôle de l'activité antibactérienne : test de diffusion dans de l'agar.* SN 195920: control of antibacterial activity: agar diffusion test.
» SN 195921 • contrôle de l'activité antimycosique: test de diffusion dans de l'agar.»SN 195921 • control of antimycotic activity: agar diffusion test.
Exemple 1 : on prépare une plaque coulée pour produit sanitaireExample 1: a cast plate for sanitary product is prepared
1) Elément polymérisable1) Polymerizable element
On prépare l'élément polymérisable en ajoutant à 100 parties en poids d'un sirop (ce sirop est formé de 10 parties en poids de prépolymère de methacrylate de méthyle (taux de conversion de 0,1) et de MAM (90 parties en poids) :The polymerizable element is prepared by adding to 100 parts by weight of a syrup (this syrup is formed from 10 parts by weight of methyl methacrylate prepolymer (conversion rate of 0.1) and of MMA (90 parts by weight ):
- 0,07 partie en poids de AIBN (amorceur)- 0.07 part by weight of AIBN (initiator)
0,04 partie en poids en BDMA (agent réticulant)0.04 parts by weight of BDMA (crosslinking agent)
- 0,05 partie en poids de gamma-terpinèπe (agent de transfert de chaîne)- 0.05 part by weight of gamma-terpinèπe (chain transfer agent)
- 0,02 partie en poids d'agent antioxydant (produit Tinuvin P® vendu par Gba- Ceigy)- 0.02 parts by weight of antioxidant agent (Tinuvin P ® product sold by Gba- Ceigy)
2) Préparation de la composition polymérisable2) Preparation of the polymerizable composition
Dans 99 parties en poids de l'élément polymérisable précèdent, on dissout 1 partie en poids d'un mélange de 2,4,4'-trιchloro-2'-hydroxy-dιphényl éther et de 2-n-octyl-4-ιsothιazolιne- 3-one en solution dans du dioctylphtalate (DOP). Ce mélange est vendu sous la dénomination commerciale « Sanitized PL 91-35 » par la société ClaπantIn 99 parts by weight of the above polymerizable element, 1 part by weight of a mixture of 2,4,4'-trιchloro-2'-hydroxy-dιphenyl ether and 2-n-octyl-4-ιsothιazolιne is dissolved. - 3-one in solution in dioctylphthalate (DOP). This mixture is sold under the trade name "Sanitized PL 91-35" by the company Claπant
On ajoute 1,4 partie en poids (par rapport à la composition polymérisable) de pâte pigmentaire a base de Tι02 et d'acide stéaπque 3) Polymérisation1.4 parts by weight (relative to the polymerizable composition) of pigment paste based on Tι02 and stearic acid are added. 3) Polymerization
On introduit la composition polymérisable obtenue en (1) dans un moule formé de deux plaques en verre ( 500 x 300 mm) séparées par un joint de polychlorure de vinyle pour obtenir une plaque d'une épaisseur de 4 mmThe polymerizable composition obtained in (1) is introduced into a mold formed by two glass plates (500 x 300 mm) separated by a polyvinyl chloride joint to obtain a plate with a thickness of 4 mm
On place le moule dans une étuve ventilée. La composition est polyméπsée pendant 5 heures à 70°C. Un taux de conversion de 95 % environ est obtenu; puis on chauffe à 120°C pendant 1 heure. Après refroidissement du moule, on récupère la plaque.The mold is placed in a ventilated oven. The composition is polymerized for 5 hours at 70 ° C. A conversion rate of around 95% is obtained; then heated to 120 ° C for 1 hour. After cooling the mold, the plate is recovered.
On mesure, comme indiqué précédemment, l'activité antibactérienne et anti- champignons. Les résultats sont indiqués au tableau.We measure, as indicated above, antibacterial and anti-fungal activity. The results are shown in the table.
4) Thermoforrnaqe4) Thermoforrnaqe
La plaque obtenue est thermoformée sous forme de baignoire, comme indiqué précédemment, sans casse. On mesure aussi, comme indiqué précédemment, l'activité antibactérienne et anti-mycosique. Les résultats sont indiqués au tableau.The plate obtained is thermoformed in the form of a bathtub, as indicated above, without breakage. We also measure, as indicated above, the antibacterial and anti-fungal activity. The results are shown in the table.
Exemple 2Example 2
On opère comme à l'exemple 1, mais on ajoute à 99 parties en poids de matériau polymérisable, 1 partie d'un mélange de 2,4,4'-tπchloro-2'-hydroxy-dιphényl éther et de 2,3,5,6-tétrachloro-4-(méthylsulfonyl)-pyrιdιne (TMSP) en solution dans un plastifiant à base de phosphate. Ce mélange est vendu sous la dénomination commerciale « Sanitized PL 98-36 » par la société Claπant.The procedure is as in Example 1, but to 99 parts by weight of polymerizable material, 1 part of a mixture of 2,4,4'-tπchloro-2'-hydroxy-dιphenyl ether and 2.3 is added, 5,6-tetrachloro-4- (methylsulfonyl) -pyrιdιne (TMSP) in solution in a phosphate-based plasticizer. This mixture is sold under the trade name "Sanitized PL 98-36" by the company Claπant.
On mesure, comme indiqué précédemment, l'activité antibactérienne et antimycosique. Les résultats sont indiqués au tableau. Antibacterial and antimycotic activity is measured, as indicated above. The results are shown in the table.
Exemple 3 : témoinExample 3: witness
On opère comme à l'exemple 1, mais on utilise une composition polymérisable ne contenant pas d'agent antimicrobien. On mesure, comme indiqué précédemment, l'activité antibactérienne et anti-mycosique. Les résultats sont indiqués au tableau.The procedure is as in Example 1, but a polymerizable composition using no antimicrobial agent is used. We measure, as indicated above, the antibacterial and anti-fungal activity. The results are shown in the table.
Figure imgf000011_0001
Figure imgf000011_0001

Claims

REVENDICA TIONSREVENDICA TIONS
1) Matériau polymère méthacrylique antimicrobien comprenant :1) Methacrylic antimicrobial polymer material comprising:
I - une matrice formée de matière polymère ou copolymère méthacrylique thermoplastique, formée, en poids, de 80 à 100 %, de préférence de 90 à 99,5 % de motifs monomère methacrylate de méthyle et de 0 à 20 %, de préférence de 0,5 à 10 % de motifs dérivant de comonomère(s) à insaturation monoéthylénique copolymérιsable(s) avec le monomère methacrylate de méthyle etI - a matrix formed of thermoplastic methacrylic polymer or copolymer material, formed, by weight, from 80 to 100%, preferably from 90 to 99.5% of methyl methacrylate monomer units and from 0 to 20%, preferably from 0 , 5 to 10% of units deriving from monoethylenically unsaturated comonomer (s) copolymerable (s) with the methyl methacrylate monomer and
II - dispersés dans cette matrice, au moins deux agents antibactériens constitués par (A) au moins un composé phénoxy halogène et (B) au moins un composé thiazolinone, isothiazolinone et/ou sulfonylpyπdine, la quantité en agents A 4- B étant, en poids, de 20 ppm à 20000 ppm et le rapport en poids d'agent A et d'agent B étant de 0,02 à 50, de préférence de 0,1 à 10II - dispersed in this matrix, at least two antibacterial agents consisting of (A) at least one halogenated phenoxy compound and (B) at least one thiazolinone, isothiazolinone and / or sulfonylpyπdine compound, the amount of agents A 4- B being, in weight, from 20 ppm to 20,000 ppm and the weight ratio of agent A and agent B being from 0.02 to 50, preferably from 0.1 to 10
2) Matériau selon la revendication 1 caractérisé en ce que le(s) comonomère(s) à insaturation monoéthylénique est (sont) choιsι(s) parmi des monomères acryliques, méthacryliques et vinylaromatiques2) Material according to claim 1 characterized in that the (s) comonomer (s) with monoethylenic unsaturation is (are) choιsι (s) among acrylic, methacrylic and vinylaromatic monomers
3) Matériau selon l'une des revendications 1 et 2, caractérisé en ce que la matière (co)polymère formant la matrice I est réticulée.3) Material according to one of claims 1 and 2, characterized in that the material (co) polymer forming the matrix I is crosslinked.
4) Matériau selon l'une des revendications 1 à 3, caractérise en ce que le composé phénoxy halogène (A) est le 2,4,4'-tπchloro-2'-hydroxydιphényléther et le compose (B) est choisi dans le groupe formé par la i,2-benzothιazolιn-3-one, la 5-chloro-2-methyl-4- ιsothιazolιn-3-one, la 2-méthyl-4-ιsothιazolιn-3-one et la 2-n-octyl-4-ιsothιazolιn-3-one4) Material according to one of claims 1 to 3, characterized in that the halogenated phenoxy compound (A) is 2,4,4'-tπchloro-2'-hydroxydιphenyléther and the compound (B) is chosen from the group formed by i, 2-benzothιazolιn-3-one, 5-chloro-2-methyl-4- ιsothιazolιn-3-one, 2-methyl-4-ιsothιazolιn-3-one and 2-n-octyl- 4-ιsothιazolιn-3-one
5) Matériau selon l'une des revendications 1 et 2 et 4, caractérisé en ce qu'il se trouve sous forme de granulés ou de perles.5) Material according to one of claims 1 and 2 and 4, characterized in that it is in the form of granules or beads.
6) Matériau selon l'une des revendications 1 à 4, caractérisée en ce qu'il se trouve sous forme de plaques6) Material according to one of claims 1 to 4, characterized in that it is in the form of plates
7) Procédé de fabrication du matériau selon la revendication 5, caractérisé en ce que on mélange des granulés ou des perles de matière (co)polymère méthacrylique, les agents antimicrobiens A et B sous forme de mélange maître et, éventuellement d'autres additifs7) A method of manufacturing the material according to claim 5, characterized in that granules or beads of methacrylic polymer (co) material, the antimicrobial agents A and B are mixed in the form of a master mixture and, optionally other additives
8) Procédé de fabrication du matériau selon la revendications 6, caractérise en ce qu' on polyméπse une composition polymérisable comprenant (a) un élément polymérisable comprenant en poids, de 80 a 100 %, de préférence 90 à 99,5 % de composant methacrylate de méthyle et de 0 à 20 %, de préférence de 0,5 à 10 % de comonomère(s) à insaturation monoéthylénique copolymeπsable(s) avec le monomère methacrylate de méthyle, et (b) dissous dans cet élément polymérisable ou dans le composant methacrylate de méthyle, au moins deux agents antimicrobiens constitués par (A) au moins un compose phénoxy halogène et (B) au moins un compose thiazolinone, isothiazolinone et/ou sulfonylpyπdine, la quantité d'agents A + B étant de 20 à 20 000 ppm en poids et le rapport en poids A/B étant de 0,02 à8) A method of manufacturing the material according to claims 6, characterized in that a polymerizable composition is polymerized comprising (a) a polymerizable element comprising by weight, from 80 to 100%, preferably 90 to 99.5% of methacrylate component of methyl and from 0 to 20%, preferably from 0.5 to 10% of comonomer (s) with monoethylenic unsaturation copolymeπsable (s) with the methyl methacrylate monomer, and (b) dissolved in this polymerizable element or in the component methyl methacrylate, at least two antimicrobial agents consisting of (A) at least one halogenated phenoxy compound and (B) at least one thiazolinone, isothiazolinone and / or sulfonylpyπdine compound, the quantity of agents A + B being from 20 to 20,000 ppm by weight and the weight ratio A / B being from 0.02 to
50.50.
9) Procédé conforme à la revendication 8, caractérisé en ce que l'élément polymérisable comprend, en outre, en poids, par rapport à la quantité de composant methacrylate de méthyle, de 0 à 0,2 %, de préférence 0,002 a 0,2 % d'amorceur de polymérisation, de 0 à 0,2 %, de préférence de 0,01 à 0,1 % d'agent(s) polyfonctιonnel(s) de réticulation, de 0 à 0,2 %, de préférence de 0,01 à 0,1 % d'agent de transfert de chaîne, de 0 à9) A method according to claim 8, characterized in that the polymerizable element further comprises, by weight, relative to the amount of methyl methacrylate component, from 0 to 0.2%, preferably 0.002 to 0, 2% of polymerization initiator, from 0 to 0.2%, preferably from 0.01 to 0.1% of polyfunctional crosslinking agent (s), from 0 to 0.2%, preferably from 0.01 to 0.1% chain transfer agent, from 0 to
0,2 %, de préférence de 0,01 à 0,1 % d'agent démoulant, de 0 à 0,2 %, de préférence de 0,01 à 0,1 % d'agent adsorbant l'UV et de 0 à 0,2 %, de préférence 0,01 à 0,1 % d'antioxydant. 10) Procédé conforme à la revendication 8, caractérisé en ce que la composition polymérisable comprend de 0 à 5 %, de préférence de 0,1 à 5 % en poids de pâte contenant un pigment et/ou colorant.0.2%, preferably from 0.01 to 0.1% of release agent, from 0 to 0.2%, preferably from 0.01 to 0.1% of adsorbent UV and from 0 0.2%, preferably 0.01-0.1% antioxidant. 10) Process according to claim 8, characterized in that the polymerizable composition comprises from 0 to 5%, preferably from 0.1 to 5% by weight of paste containing a pigment and / or dye.
11) Article façonné obtenu par extrusion, injection ou compression du matériau conforme à la revendication 5. 12) Article façonné obtenu par thermoformage d'un matériau conforme à la revendication 6. 11) Shaped article obtained by extrusion, injection or compression of the material according to claim 5. 12) Shaped article obtained by thermoforming of a material according to claim 6.
PCT/FR2001/003142 2000-10-19 2001-10-11 Antimicrobial methacrylic polymer material and shaped articles obtained from same WO2002032989A1 (en)

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EP1551366A1 (en) * 2002-07-23 2005-07-13 Microban Products Company Antimicrobial melamine resin and products made therefrom
EP1657978A2 (en) * 2003-08-28 2006-05-24 Microban Products Company Antimicrobial acrylic polymer
EP1743526A2 (en) * 2005-07-11 2007-01-17 Rohm and Haas Company Resin immobilized biocide
WO2007042416A1 (en) * 2005-10-12 2007-04-19 Ciba Specialty Chemicals Holding Inc. Material having antibacterial and antifungal properties

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WO1999047595A1 (en) * 1998-03-17 1999-09-23 Ineos Acrylics Uk Limited Biocidal plastic material
WO2000014128A1 (en) * 1998-09-08 2000-03-16 Microban Products Company Antimicrobial acrylic material

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WO1999047595A1 (en) * 1998-03-17 1999-09-23 Ineos Acrylics Uk Limited Biocidal plastic material
WO2000014128A1 (en) * 1998-09-08 2000-03-16 Microban Products Company Antimicrobial acrylic material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1551366A1 (en) * 2002-07-23 2005-07-13 Microban Products Company Antimicrobial melamine resin and products made therefrom
EP1551366A4 (en) * 2002-07-23 2005-10-19 Microban Products Antimicrobial melamine resin and products made therefrom
AU2008221591B2 (en) * 2002-07-23 2009-06-04 Microban Products Company Antimicrobial Melamine Overlay Component and Methods for Making Same
EP1657978A2 (en) * 2003-08-28 2006-05-24 Microban Products Company Antimicrobial acrylic polymer
EP1657978A4 (en) * 2003-08-28 2012-04-18 Microban Products Antimicrobial acrylic polymer
EP1743526A2 (en) * 2005-07-11 2007-01-17 Rohm and Haas Company Resin immobilized biocide
EP1743526A3 (en) * 2005-07-11 2012-12-26 Rohm and Haas Company Resin immobilized biocide
WO2007042416A1 (en) * 2005-10-12 2007-04-19 Ciba Specialty Chemicals Holding Inc. Material having antibacterial and antifungal properties

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