EP0268880B1 - Tampon de nettoyage pour éliminer les sulfates de surfaces à fresque - Google Patents

Tampon de nettoyage pour éliminer les sulfates de surfaces à fresque Download PDF

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Publication number
EP0268880B1
EP0268880B1 EP87116146A EP87116146A EP0268880B1 EP 0268880 B1 EP0268880 B1 EP 0268880B1 EP 87116146 A EP87116146 A EP 87116146A EP 87116146 A EP87116146 A EP 87116146A EP 0268880 B1 EP0268880 B1 EP 0268880B1
Authority
EP
European Patent Office
Prior art keywords
anion
coatings according
sulphation
exchange material
paste
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP87116146A
Other languages
German (de)
English (en)
Other versions
EP0268880A2 (fr
EP0268880A3 (en
Inventor
Giuseppe Pizzigoni
Paolo Parrini
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.)
Larac SpA
Original Assignee
Larac SpA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Larac SpA filed Critical Larac SpA
Priority to AT87116146T priority Critical patent/ATE90113T1/de
Publication of EP0268880A2 publication Critical patent/EP0268880A2/fr
Publication of EP0268880A3 publication Critical patent/EP0268880A3/en
Application granted granted Critical
Publication of EP0268880B1 publication Critical patent/EP0268880B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • B08B7/0014—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by incorporation in a layer which is removed with the contaminants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/049—Cleaning or scouring pads; Wipes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/12—Carbonates bicarbonates

Definitions

  • the present invention relates to flexible coatings for the sulphation-removing cleaning of frescoed surfaces.
  • the present invention relates to flexible coatings for the sulphation-removing cleaning of frescoed surfaces on plasters of prevailingly carbonatic nature.
  • a classic method for removing the sulphation consists in acting on it with ammonium carbonate solutions, according to such modalities as not to endanger the integrity of the work of art, and in such a way as to restore a carbonatic surface, with the sulphate ion being removed as ammonium sulphate, by means of a double-exchange reaction.
  • a subsequent treatment with barium hydroxide solutions is carried out, which causes a sulphate to be formed, having a low specific volume, and a high chemical inertness.
  • barium hydroxide can turn again into barium carbonate, contributing to strengthen the plaster.
  • Said formulates are carefully applied and removed by sponging and other delicate mechanical actions after rigorously controlled times of contact with the surfaces.
  • EP-A-0 210 603 (forming part of the state of the art by virtue of Article 54(3) EPC) has proposed compositions for the sulphation-removing cleaning and the analysis of the sulphation of frescoes surfaces comprising a mixture, generally having a paste form, of an aqueous solution of ammonium carbonate with an anion-exchange resin in powder form.
  • EP-A-0 189 866 discloses a composition for restoring frescoed surfaces which comprises an aqueous solution of ammonium carbonate containing an anion-exchange material in powder form.
  • the granulometry of the ion-exchange materials must be carefully selected so to minimize their penetration into the microcavities and surface interstices.
  • the need generally causes the increase of the particle size of the ion-exchange materials, with a consequent loss of effectiveness of the treatment, caused by a reduction in the contact surface areas.
  • the not particularly small particle dimensions have a negative influence on the characteristics of spreadability and self-support of the paste-like mixtures, of not suitable consistency for the sulphation-removing treatments.
  • a protective layer such as, e.g., of light paper, non-woven fabrics, etc., with the effectiveness of the ion exchange being furthermore impaired, and/or to support the same paste by means of suitable gauze fabrics, non-woven fabrics, filter papers, and the like.
  • the object of the present invention are therefore flexible coatings for the sulphation-removing cleaning of frescoed surfaces of prevailingly carbonatic nature comprising a fibrous support impregnated with a binding agent and with a paste-like mixture, comprising water or an aqueous solution of ammonium carbonate and/or bicarbonate and an anion-exchange material in powder form.
  • fibrous supports suitable for preparing the flexible coatings of the present invention comprise the filter papers, the papers endowed with high enough wet- resistance, the so-said dry-papers, i.e, those papers which are prepared from cellulose fibres and synthetic binding agents, cellulosic non-woven fabrics with or without synthetic fibres, woven fabrics endowed with the proper compactness, flexibility and hydrophily, of natural and/or synthetic fibres, such as wool, cotton, flax, jute, acrylic fibres, polyester fibres, polyolefinic fibres, and so forth.
  • the anion-exchange material contains preferably the activated functional groups, e.g., in the form of aminic groups or quaternary ammonium bases, free, or salified, and particle dimensions preferably lower than 0.1 mm.
  • anion-exchange materials are supplied by the anion-exchange synthetic resins, provided with basic functional groups, in particular, the resins with a matrix based on polymers or copolymers of styrene, on acrylic monomers or on polycondensation resins, or also on crosslinked and functionalized polysaccharides.
  • the weight ratio of the anion-exchange material to the solution of ammonium carbonate and/or bicarbonate is generally comprised within the range of from 0.5 to 3.
  • Suitable concentrations of the solutions of ammonium carbonate and/or bicarbonate have resulted to be those comprised within the range of from 1 to 20% by weight; this does not however constitute a limitation.
  • Suitable binding agents which can be used in the preparation of the flexible coatings of the present invention comprise the aqueous dispersions of synthetic polymers and/or copolymers with particle charge compatible with that of the necessary anion-exchange materials.
  • acetovinylic binding agents e.g., the ethylene-vinyl acetate (EVA) copolymers in practically non-ionic dispersion
  • EVA ethylene-vinyl acetate
  • polyurethanic binding agents always in non-ionic characteristics dispersion
  • concentrations of the latexes comprised within the range of from 20 to 50% by weight
  • the binding agents comprise co-binding agents, also anionic, such as, e.g., the salified polymers of acrylic and/or methacrylic acid, in the form of ammonium salts.
  • Useful additives for obtaining pastes suitable for coating the fibrous supports can be the kaolinites, the attapulgites, the clay materials in general, with a sufficiently fine granulometry and with a high water retention, at concentrations around 20% by weight relatively to the fine exchange-resin.
  • Useful dimensions have demonstrated to be those equal to, or lower than, 100 micrometres; this is not, however, a limitative criterion.
  • These mineral additives can be useful for improving the rheologic behaviour of the paste and make possible a more regular application thereof.
  • surface-active compounds both of non-ionic and cationic type, can result useful, for improving the wettability of the components, as well as the germicidal compounds, from quaternary ammonium bases, in the amounts which are regarded as being the most suitable.
  • the impregnation of the fibrous support can be accomplished by means of known techniques, such as, e.g., by means of spreading means, brushes, palette-knives, doctors, rollers, spraying equipment, etc., with the desired amounts being deposited.
  • the so-obtained coating may be dried and desiccated at a mild temperature, generally not higher than 50°C, and stored for long time periods.
  • the dried coating When used, it is reconditioned, e.g., by dipping in demineralized water, or in suitable solutions of ammonium carbonate and/or bicarbonate, and is directly applied into contact, from the ion-exchange material side, with the frescoed surface to be treated, thus all of the problems being overcome, which derive from the use of materials having a consistency and rheological characteristics unsuitable for obtaining self-supporting preparates.
  • the flexible coating of the present invention can be used again for sulphation-removing treatments, after a preliminary reactivation by digestion in regenerating solutions, such as, e.g., the ammonium carbonate and/or bicarbonate solutions may be, until the physical-mechanical characteristics of the same coating allow so doing.
  • regenerating solutions such as, e.g., the ammonium carbonate and/or bicarbonate solutions may be, until the physical-mechanical characteristics of the same coating allow so doing.
  • the flexible coating of the present invention can be obtained by impregnating the fibrous support with a paste of an anion-exchange material in powder form and water, and a binding agent.
  • the impregnated support may be dried and desiccated at a mild temperature, generally not higher than 50°C, and is stored for long time periods.
  • the dried coating When used, it can be reconditioned by means of demineralized water, or in suitable aqueous solutions of ammonium carbonate and/or bicarbonate, with concentrations comprised, e.g., within the range of from 1 to 20% by weight.
  • the reconditioning in demineralized water can be necessary in case of treatments of particularly deteriorated frescoed surfaces, so that it is preferable to operate with low-aggressivity coatings. That means eliminating the ammonium salt and operating in the presence of the anion-exchange material only.
  • the flexible coating of the present invention performs its action in the presence of aqueous phase, so, it could be useful, for some applications, to slow down the exsiccation rate thereof, by means of sheets of plastic films, or supplying water or carbonate-containing solution by means of pads or imbibition by capillarity.
  • a preparate obtained according to the following modalities and composition, was spread on dry-paper of approximately 45 g/m2, with the aid of a brush. After drying and desiccation the coating deposit resulted equal to an average of approximately 70 g/m2.
  • the modalities of preparation of the preparate are: To 100 parts of weak anion-exchange resin Kastel A101® by DOW CHEM., in the form of a fine powder with the fraction finer than 0.053 mm constituting more than 95% of its weight, 10 parts were added of an aqueous solution at 25 % of an anionic surfactant, of the ethoxylated alkyl-phenol type; they were then wetted with 175 parts of demineralized water.
  • the following ingredients are prepared and mixed with one another: 75 parts of acetovinylic (EVA) latex Vinnapas EP14® by WACKER, 75 parts of demineralized water, 4 parts of an acidic acrylic latex Crilat D159® by VINAVIL, 80 parts of a 15% solution of ammonium carbonate; this formulation is added, with suitable stirring, to the paste of water and anion-exchange resin.
  • EVA acetovinylic
  • the obtained coating after desiccation, was washed in a stream of demineralized water and was conditioned in a 7% ammonium carbonate solution.
  • Two layers of a preparate, obtained according to the following modalities were applied, by brush, on dry-paper of about 45 g/m2 and on cotton cloths of about 100 g/m2 of weight.
  • the coating deposits were respectively of about 110 and 140 g/m2.
  • Modalities of preparation of the preparate To 100 parts of weak anion-exchange resin Kastel A101® by DOW CHEM., in the form of a fine powder with a content of fraction finer than 0.053 mm higher than 95% of its weight, 17 parts of attapulgite, type Attapulgus clay 100/up by ENGELHARD and 200 parts of an 0.3% solution of benzyltrimethylammonium chloride are added, and the whole mass is homogenized.
  • the following ingredients are prepared by mixing, in the order: 75 parts of acetovinylic (EVA) latex Vinnapas EP14® by WACKER, 80 parts of demineralized water, 4 parts of a 15% solution of ammonium carbonate; this formulation is added, with suitable stirring, to the paste of water and anion-exchange resin.
  • EVA acetovinylic
  • the coatings on the basis of supported anion-exchange material, obtained as said above, were dried, washed in a stream of demineralised water, and conditioned in 7% ammonium carbonate solutions.
  • the sulphation was removed from a portion of the frescoed surface of the Brancacci chapel of Florence, together with the proteinic substances with which the same surfaces had been treated on the occasion of prior restorations.
  • a preparate, obtained according to the following modalities was applied, by palette-knife, on dry-paper of about 45 g/m2.
  • the coating deposits were of the order of 80 g/m2 on the average.
  • Modalities of preparation of the preparate To 100 parts of strong anion-exchange resin, OH form, Kastel A500N® by DOW CHEM., in the form of a fine powder with a content of fraction finer than 0.1 mm higher than 85% of its weight, 17 parts of Attapulgus clay 100/up by ENGELHARD, and 200 parts of an 0.3% solution of benzyltrimethylammonium chloride are added. After homogenization, 77 parts of aqueous polyurethanic dispersion Purbinder N73® by ROL S.p.A., previously diluted with 67 parts of demineralized water, are added. The obtained paste resulted quite well applicable by palette-knife, to outstretched, damp sheets of dry-paper.
  • the coating on the basis of supported anion-exchange material was submitted, after drying, to a washing in a stream of demineralized water, and a part thereof was then conditioned in a 12% ammonium carbonate solutions.
  • the coating of the invention after washing in a stream of demineralized water, and conditioning in a 5% solution of ammonium carbonate, was applied both on a surface of sulphonated limestone, and on a frescoed surface of 1400. In both cases, it was possible to document cleaning and sulphation-removing effects, by means of visual inspections and chemical analyses.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Detergent Compositions (AREA)
  • Laminated Bodies (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Brushes (AREA)

Claims (12)

  1. Revêtements flexibles pour le nettoyage par désulfatation de fresques murales, comprenant un support fibreux imprégné d'un agent liant et d'une pâte d'un matériau échangeur d'anions sous la forme d'une poudre dans l'eau.
  2. Revêtements flexibles selon la revendication 1, pour le nettoyage par désulfatation de fresques murales de nature principalement carbonique dominante, comprenant un support fibreux imprégné d'un agent liant et d'une pâte incluant une solution aqueuse de carbonate et/ou de bicarbonate d'ammonium, et un matériau échangeur d'anions sous forme de poudre.
  3. Revêtements selon la revendication 1 ou 2, dans lesquels le support fibreux inclue des papiers filtres résistants à l'humidité, des papiers secs, des matériaux non-tissés à base de cellulose avec ou sans fibres synthétiques, des matériaux tissés en fibres naturelles et/ou synthétiques, tels que coton, lin, jute, fibres acryliques, fibres polyestères, fibres polyolifiniques.
  4. Revêtements selon l'une quelconque des revendications précédentes, dans lesquels le matériau échangeur d'anions est une résine synthétique échangeuse d'anions ayant une dimension particulaire inférieure à 0,1 mm.
  5. Revêtements selon l'une quelconque des revendications précédentes, dans lesquels le rapport pondéral matériau échangeur d'anions/solution de carbonate et/ou de bicarbonate d'ammonium est compris dans un intervalle allant de 0,5 à 3.
  6. Revêtements selon l'une quelconque des revendications précédentes, dans lesquels l'agent liant est constitué d'une dispersion aqueuse de polymères et/ou de copolymères synthétiques.
  7. Revêtements selon la revendication 6, dans lesquels l'agent liant correspond à des copolymères d'acétate de vinyle-éthylène sous la forme d'une dispersion ou à des polyuréthanes sous la forme d'une dispersion, avec des concentrations en latex comprises dans un intervalle allant de 20 à 50% en poids.
  8. Revêtements selon l'une quelconque des revendications précédentes, dans lesquels les agents liants comprennent des agents co-liants.
  9. Revêtements selon la revendication 8, dans lesquels les agents co-liants sont constitués de produits tels qu'un le polymère salifié d'acide acrylique et/ou méthacrylique sous la forme de sels d'ammonium.
  10. Revêtements selon l'une quelconque des revendications précédentes, dans lesquels des kaolinites, attapulgites ou matériaux argileux, qui ont une granulométrie égale ou inférieure à 100 micromètres, sont ajoutés à la pâte.
  11. Utilisation des revêtements selon l'une quelconque des revendications 1 à 10 dans la détermination quantitative du degré de sulfatation, la désulfatation dans le nettoyage des matériaux de nature protéinique, des fresques murales de plâtre à nature principalement carbonique.
  12. Procédés pour la préparation de revêtements flexibles selon l'une quelconque des revendications 1 à 10, comprenant l'imprégnation d'un support fibreux par un agent liant et par une pâte d'un matériau échangeur d'anions sous forme de poudre dans de l'eau ou une pâte constituée d'une solution aqueuse de carbonate et/ou de bicarbonate d'ammonium et d'un matériau échangeur d'anions sous forme de poudre.
EP87116146A 1986-11-03 1987-11-03 Tampon de nettoyage pour éliminer les sulfates de surfaces à fresque Expired - Lifetime EP0268880B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87116146T ATE90113T1 (de) 1986-11-03 1987-11-03 Reinigungstuch zur sulfatentfernung von freskoartigen oberflaechen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT2221586 1986-11-03
IT22215/86A IT1200526B (it) 1986-11-03 1986-11-03 Rivestimenti flessibili per la pulitura desolfatante di superfici affrescate

Publications (3)

Publication Number Publication Date
EP0268880A2 EP0268880A2 (fr) 1988-06-01
EP0268880A3 EP0268880A3 (en) 1989-05-03
EP0268880B1 true EP0268880B1 (fr) 1993-06-02

Family

ID=11193166

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87116146A Expired - Lifetime EP0268880B1 (fr) 1986-11-03 1987-11-03 Tampon de nettoyage pour éliminer les sulfates de surfaces à fresque

Country Status (5)

Country Link
EP (1) EP0268880B1 (fr)
AT (1) ATE90113T1 (fr)
DE (1) DE3786060T2 (fr)
IT (1) IT1200526B (fr)
PT (1) PT86067B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109971285A (zh) * 2019-04-25 2019-07-05 西北工业大学 一种纳米氢氧化钡/聚丙烯酸树脂复合材料及制备方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1240734B (it) * 1990-04-02 1993-12-17 Syremont Spa Procedimento per la pulitura di matrici porose idrofile
FR2710860B1 (fr) * 1993-10-06 1995-12-15 Lefevre Sa M Procédé de nettoyage d'une surface en pierre et compresse pour l'humidification d'une surface à nettoyer.
ES2102292B1 (es) * 1994-01-14 1998-04-01 Tolsa Sa Composicion a base de sepiolita micronizada, procedimiento para su preparacion y su aplicacion en la limpieza y restauracion de edificios y monumentos
DE19616665A1 (de) * 1996-04-26 1997-11-06 Buelent Oez Transferpapier zur Übertragung von Xerodrucken auf Textilien
ITVE20110053A1 (it) * 2011-07-11 2013-01-12 Paolo Zabeo Metodologia d'intervento per la rimozione di scritte, graffiti, applicazioni varie di deposito superficiale di degrado naturale e non, su qualsiasi superficie, comprensiva dell'uso di un doppio telo di iuta con successive applicazioni e dell'uso di d

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3324500A (en) * 1964-11-24 1967-06-13 Colgate Palmolive Co Scouring pad
IT1212870B (it) * 1983-06-01 1989-11-30 Pouchain Maurizio Porcedimento di riformazione del carbonato di calcio per il restauro di monumenti litici e simili
IT1183310B (it) * 1985-01-25 1987-10-22 Larac Spa Composizioni per la pulitura desolfatante di superfici lapidee carbonatiche
IT1187706B (it) * 1985-07-24 1987-12-23 Larac Spa Composizioni per l'analisi della solfatazione,la pulitura desolfatante di superfici affrescate e la eliminazione per disgregazione progressiva di strati decorati indesiderati su intonaci gessosi

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109971285A (zh) * 2019-04-25 2019-07-05 西北工业大学 一种纳米氢氧化钡/聚丙烯酸树脂复合材料及制备方法
CN109971285B (zh) * 2019-04-25 2021-01-15 西北工业大学 一种纳米氢氧化钡/聚丙烯酸树脂复合材料及制备方法

Also Published As

Publication number Publication date
PT86067A (en) 1987-12-01
IT1200526B (it) 1989-01-18
PT86067B (pt) 1990-11-07
EP0268880A2 (fr) 1988-06-01
IT8622215A0 (it) 1986-11-03
DE3786060T2 (de) 1993-12-09
DE3786060D1 (de) 1993-07-08
EP0268880A3 (en) 1989-05-03
ATE90113T1 (de) 1993-06-15

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