EP3480287B1 - Composition de nettoyage solide soluble dans l'eau - Google Patents

Composition de nettoyage solide soluble dans l'eau Download PDF

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Publication number
EP3480287B1
EP3480287B1 EP17199802.4A EP17199802A EP3480287B1 EP 3480287 B1 EP3480287 B1 EP 3480287B1 EP 17199802 A EP17199802 A EP 17199802A EP 3480287 B1 EP3480287 B1 EP 3480287B1
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EP
European Patent Office
Prior art keywords
composition
alkali metal
acid
composition according
aqueous solution
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.)
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Application number
EP17199802.4A
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German (de)
English (en)
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EP3480287A1 (fr
Inventor
Sebastian Wagner
Axel Nawrath
Thomas RÜBENER
Daniel LAMBERTUS
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.)
Dalli Werke GmbH and Co KG
Original Assignee
Dalli Werke GmbH and Co KG
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Publication date
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Priority to EP17199802.4A priority Critical patent/EP3480287B1/fr
Priority to PL17199802T priority patent/PL3480287T3/pl
Publication of EP3480287A1 publication Critical patent/EP3480287A1/fr
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Publication of EP3480287B1 publication Critical patent/EP3480287B1/fr
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Classifications

    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D7/06—Hydroxides
    • 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
    • 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
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof

Definitions

  • the present invention refers to solid water-soluble cleaning compositions usable for removing support material from three-dimensional objects formed by additive manufacturing, an aqueous solution prepared from such a composition and a method for removing support material from a three-dimensional object formed by additive manufacturing.
  • the present invention refers to a solid water-soluble cleaning composition for removing support material from a three-dimensional object formed by additive manufacturing, said composition comprising (a) at least 50 wt.% of at least one inorganic carbonate, (b) 0.1 to 15 wt.% of at least one alkali metal hydroxide, (c) 0.1 to 30 wt.% of at least one organic acid, and (d) 0.1 to 5 wt.% of at least one surfactant, wherein the weight percentages are based on the total weight of the composition.
  • the present invention relates to a package containing said solid water-soluble composition, to a kit comprising said package and instructions comprising information of dosing and/or use of the composition, to an aqueous solution obtainable by dissolution of the composition according to the invention, and to a method for removing support material from a three-dimensional object formed by additive manufacturing comprising (a) providing an aqueous solution obtained or obtainable by dissolution of a composition according to the invention, and (b) contacting the three-dimensional object formed by additive manufacturing with the aqueous solution to remove at least a part of the support material from the three-dimensional object, as well as to the use of a composition, package, kit or aqueous solution according to the invention for removing support material from a three-dimensional object formed by additive manufacturing.
  • Additive manufacturing is a technology enabling fabrication of arbitrarily shaped structures directly from computer data via additive formation steps (additive manufacturing).
  • the basic operation of any additive manufacturing system consists of slicing a three-dimensional computer model into thin cross sections, translating the result into two-dimensional position data and feeding the data to control equipment, which fabricates a three-dimensional structure in a layer-wise manner.
  • Additive manufacturing comprises several building techniques, including three-dimensional printing such as three-dimensional (3D) inkjet printing, electron beam melting, stereolithography, selective laser sintering, laminated object manufacturing, and fused deposition modeling.
  • 3D inkjet printing processes is performed by a layer-by-layer inkjet deposition of building materials.
  • the building material is dispensed from a dispensing head having a set of nozzles to deposit layers on a supporting structure.
  • the layers may then be cured or solidified using a suitable device.
  • the building material may include "object material”, which is deposited to produce the desired model object, and frequently, another material is used to provide temporary support to the model object as it is being built.
  • the other material is referred to herein and in the art as “support material”, and is used to support specific areas of the object during building and for assuring adequate vertical placement of subsequent object layers.
  • support material is used to support specific areas of the object during building and for assuring adequate vertical placement of subsequent object layers.
  • model objects include overhanging features or shapes, e.g. curved geometries, negative angles, and/or voids, and the like
  • objects are typically constructed using adjacent support constructions, which are used during the printing and then subsequently removed in order to reveal the final shape of the fabricated model object.
  • the present invention concerns amongst others the provision of a solid water-soluble cleaning composition to address this removal process of support material from the object material after completion of the additive manufacturing process.
  • the object material and the supporting material are initially liquid and subsequently hardened to form the required layer shape.
  • the hardening process may be performed by a variety of methods, such as UV curing, phase change, crystallization, drying, etc.
  • the support material is deposited in proximity of the object material, enabling the formation of complex object geometries and filling of object voids. In such cases, the removal of the hardened support material is liable to be difficult and time consuming, and may damage the formed final object.
  • the support material should harden rapidly in order to allow building of subsequent layers. Additionally, the hardened support material should have sufficient mechanical strength for holding the model material in place, and low distortion for avoiding geometrical defects.
  • Break-away support materials may be manually broken away from the resulting 3D models by hand or using tools.
  • soluble support materials may be dissolved in aqueous solutions, typically requiring heat and agitation for optimal dissolution.
  • the mechanical methods are labor intensive and are often unsuited for small intricate parts, and therefore chemical dissolution methods are preferably used.
  • the fabricated/printed object is commonly immersed in water or in a solvent that is capable of dissolving the support material, while not affecting the object material.
  • the solutions utilized for dissolving the support material are also referred to herein and in the art as "cleaning solution” or “cleaning composition”.
  • cleaning solution or “cleaning composition”.
  • the support removal process may involve hazardous materials, manual labor and/or special equipment requiring trained personnel, protective clothing and expensive waste disposal.
  • the dissolution process is usually limited by diffusion kinetics and may require very long periods of time, especially when the support constructions are large and bulky.
  • post-processing may be necessary to remove traces of a 'mix layer' on model object surfaces.
  • the term “mix layer” refers to a residual layer of mixed hardened object and support materials formed at the interface between the two materials on the surfaces of the object being fabricated, by object and support materials mixing into each other at the interface between them.
  • the cleaning composition of the present invention hence, by a solid water-soluble cleaning composition for removing support material from a three-dimensional object formed by additive manufacturing, the composition comprising (a) at least 50 wt.% of at least one inorganic carbonate, (b) 0.1 to 15 wt.% of at least one alkali metal hydroxide, (c) 0.1 to 30 wt.% of at least one organic acid, and (d) up to 5 wt.% of at least one surfactant, wherein the weight percentages are based on the total weight of the composition.
  • composition of the present invention provides when dissolved in an aqueous solution, preferably in water, high alkalic reserves, allowing a prolonged use of the solution for dissolving the support material. Concurrently said solution is less harmful for the user and the environment as compositions of the prior art.
  • the definition "at least one” means that at least one type of a particular defined compound is comprised in the composition, but also more than one type of a compound falling under the according definition can be present.
  • “at least one” includes one, two, three, four, five or more compounds differing from each other, but falling under the mentioned definition. If the term “at least one” is used in combination with a range of an amount, the range refers to the whole amount of the compound(s) present in the composition, which means that the combined amounts of the several types of compounds falling under the compound definition represent the claimed range.
  • the composition comprises less than 10 wt.% of any oxidizing per-compound(s), preferably less than 5 wt.%, more preferred less than 2 wt.%. Most preferably the cleaning composition is substantially free of any oxidizing per-compound(s). Furthermore, the composition preferably comprises less than 1 wt.% of an alkali metal silicate, preferably less than 0.5 wt.%, more preferred less than 0.3 wt.%. Most preferably the cleaning composition is substantially free of any alkali metal silicate. Furthermore, preferably the composition is substantially free of any enzyme(s), zeolites, polymers and/or phosphates, since such components are not necessary for the present approach.
  • substantially free of means that the respective compound is not volitionally added to the composition, thus, the composition doesn't comprise more than 0.1 wt.%, preferably not more than 0.05 wt.%, even more preferred less than 0.02 wt.% of the respective compound.
  • oxidizing per-compound(s) refers to any compound comprising a -O-O- group, including inorganic or organic peroxy compounds, in particular such per-compounds usually included in detergent compositions for bleaching, e.g. H 2 O 2 or H 2 O 2 generating compositions like peroxy acids, percarbonates, perborates, natrium persulfate, peroxide disulfate, etc.
  • the solid water-soluble cleaning composition of the present invention comprises as component (a) at least 50 wt.% based on the total weight of the composition of at least one inorganic carbonate.
  • Said component (a) may preferably represent 50 wt.% to 95 wt.%, more preferred 55 to 90 wt.%, even more preferred 60 to 80 wt.% of the total cleaning composition.
  • the composition preferably comprises as the at least one inorganic carbonate component (a) at least one alkali metal carbonate, wherein the amount of alkali metal carbonate preferably is in an amount in the range from 50 to 100 wt.%, more preferred in the range of 60 to 98 wt.%, even more preferred in the range of 70 to 95 wt.% based on the total weight of the carbonate component (a).
  • the inorganic carbonate component (a) may also comprise at least two different alkali metal carbonates in a combined amount in the range from 50 to 100 wt.%, more preferred in the range of 60 to 98 wt.%, even more preferred in the range of 70 to 95 wt.%, based on the total weight of the carbonate component (a).
  • suitable alkali metal carbonates are all salts of the formula M 2 CO 3 , wherein M is selected from alkali earth metals, preferably M is Na or K.
  • the composition of the present invention comprises at least two alkali metal carbonates, wherein said two compounds are present in a weight ratio from 3:1 to 1:3, such as from 2:1 to 1:2 or from 1.2:1 to 1:1.2.
  • said compounds are Na 2 CO 3 and K 2 CO 3 .
  • the inorganic carbonate component (a) of the solid water-soluble cleaning composition of the present invention may comprise at least one alkali metal bicarbonate wherein the amount of alkali metal bicarbonate preferably is in the range from 5 to 20 wt.%, based on the total weight of the carbonate component (a).
  • the inorganic carbonate component (a) may also comprise at least two different alkali metal bicarbonates in a combined amount in the range from 5 to 20 wt.%, preferably in the range of 8 to 15 wt.%, based on the total weight of the carbonate component (a).
  • Suitable bicarbonate compounds are compounds of the formula MHCO 3 , wherein M is selected from alkali earth metals, preferably M is Na or K. Particularly preferred M is Na.
  • the inorganic carbonate component (a) may comprise (i) at least one alkali metal carbonate and (ii) at least one alkali metal bicarbonate wherein the total amount of the alkali metal carbonate(s) and the alkali metal bicarbonate(s) is in an amount in the range from 50 to 100 wt.%, based on the total weight of the carbonate component (a).
  • the weight ratio of the (combined) carbonate(s) to the (combined) bicarbonate(s) is preferably in the range from 20:1 to 2:1, preferably in the range of from 15:1 to 5:1, more preferred of from 12:1 to 8:1.
  • the composition of the present invention comprises an alkali metal hydroxide in an amount of 0.1 to 15 wt.%, preferably in an amount of 0.5 to 10 wt.%, more preferred in an amount of 0.8 to 5 wt.% and most preferred in an amount of 1 to 3 wt.% based on the total cleaning composition.
  • Said alkali hydroxide preferably is selected from sodium hydroxide (NaOH) and potassium hydroxide (KOH) and is most preferred sodium hydroxide.
  • the cleaning composition of the present invention further comprises as component (c), an organic acid component in an amount of 0.1 to 30 wt.% based on the total amount of the cleaning composition.
  • the organic acid component (c) comprises a polybasic carboxylic acid (polycarboxylic acid), which means a carboxylic acid having more than one acid group, preferably at least two, more preferred at least three carboxylic acid groups.
  • polybasic carboxylic acids are succinic acid, maleic acid, malonic acid, fumaric acid, adipinic acid, glutaric acid, tartaric acid and citric acid.
  • the polybasic carboxylic acid preferably comprises citric acid, wherein the citric acid preferably is present in the composition in the form of coated particles or core-shell particles having a core comprising citric acid, and a coating comprising a water-soluble compound.
  • a preferred coating comprises sugar polymers like cellulose, starch, starch derivatives, maltodextrin, pectines like glycogene, preferably maltodextrin, or salts of low molecular weight acids, preferably acids comprising one, two or three acid groups.
  • a particular preferred coating is a coating comprising or consisting of a salt of a low molecular weight acid.
  • low molecular weight acid an acid (as free acid) is meant having a molecular weight of below 400g/mol, preferably below 350 g/mol, more preferred below 300 g/mol.
  • Said low molecular weight acid comprises at least one carboxyl group, preferably at least two, more preferred three carboxyl groups.
  • the preferred salt of a low molecular acid is an alkali metal citrate, preferably Na-citrate.
  • a coating with Tri-Na citrate is particularly preferred.
  • Another suitable water soluble low molecular weight compound is any type of a low molecular weight sugar or an amino acid or a salt thereof having a molecular weight of below 400g/mol, preferably below 350 g/mol, more preferred below 300 g/mol.
  • low molecular weight compounds are C 3 -C 6 sugars in aldose or ketose form like allose, altrose, glucose, mannose, gulose, idose, galactose, talose, psicose, fructose, sorbose, tagatose, xylulose, ribulose, ribose, arabinose, xylose, lyxose, threose, erythrose, erythrulose, dihydroxy acetone or glycerol aldehyde or disaccharides like for example saccharose, lactose, maltose or Isomalt or oligosaccharides comprising 3 to 10 sugar units or amino acids, preferably natural amino acids (commonly contained in natural proteins) without being restricted to the mentioned examples.
  • One preferred low molecular weight compound is the sugar Isomalt ST, comprising 6-O- ⁇ -D-glucopyranosyl-D-sorbite
  • the coating consists essentially of the mentioned water dissolvable material(s)l, this means that the coating comprises less than 10 wt.%, preferably less than 5 wt.%, more preferred less than 2 wt.%, even more preferred less than 1 wt.% and most preferred less than 0.5 wt.% of other materials.
  • a material herein is defined as being “water-soluble/dissolvable/dispersible” when more than 99% of a coating (layer) with a thickness of up to 0.5 mm of such material dissolves within 10 minutes, preferably within 5 min in a common 2L beaker containing 1 L of deionised water at 40° C which is stirred with a stirrer revolving at 200 r. p.m. It is pointed out that materials can be used as ingredients for the coating which itself may not be soluble, but e.g. dispersible, as long as the coating comprising said material is dissolved by water.
  • component (c) comprising a core of citric acid and a water dissolvable coating
  • component (c) comprising a core of citric acid and a water dissolvable coating
  • Citrocoat® N represents particles having a core of citric acid coated with sodium citrate, prepared by applying NaOH-solution to the surface of granulated citric acid
  • citric acid DC comprises a core of citric acid, coated with maltodextrin.
  • the most preferred embodiment is Citrocoat® N.
  • component (d) is at least one surfactant.
  • the surfactant(s) representing component (d) comprise at least one surfactant selected from the group consisting of non-ionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and mixtures or combinations thereof. If present, the surfactant(s) of component (d) are present in the cleaning composition in a total amount of 0.1 to 5 wt.%, preferably in an amount of 0.2 to 3 wt.%, more preferred in an amount of 0.3 to 1 wt.% based of the total amount of the cleaning composition.
  • the surfactant(s) comprise(s) at least one anionic surfactant e.g. selected from an alkyl sulfate, alkyl sulfonate, sulfosuccinate or alkoxylated derivatives of any of the foregoing or a mixture or combination thereof.
  • anionic surfactant e.g. selected from an alkyl sulfate, alkyl sulfonate, sulfosuccinate or alkoxylated derivatives of any of the foregoing or a mixture or combination thereof.
  • composition according to further may preferably comprise as a further compound (e) at least one chelating agent, e.g. in an amount of up to 1 wt.%, preferably in an amount of 0.01 to 0.5 wt.% of the total composition.
  • at least one chelating agent e.g. in an amount of up to 1 wt.%, preferably in an amount of 0.01 to 0.5 wt.% of the total composition.
  • the at least one chelating agent preferably comprises a nitrogen-containing compound having a plurality of acetate groups such as salts, particularly sodium salts, of nitrilotriacetic acid, methylglycinediacetic acid, ethylenediaminetetraacetic acid, iminodisuccinic acid, ethylenediamine iminodisuccinic acid or diethylenetriaminepentaacetic acid, preferably tetrasodium- N , N -bis(carboxylatomethyl)-L-glutamate, an oxalate such as disodium oxalate salt or a combination of any of the foregoing.
  • a nitrogen-containing compound having a plurality of acetate groups such as salts, particularly sodium salts, of nitrilotriacetic acid, methylglycinediacetic acid, ethylenediaminetetraacetic acid, iminodisuccinic acid, ethylenediamine iminodisuccin
  • composition of the present invention may comprise minor amounts of up to 1 wt.% of further ingredients, e.g. fillers, perfumes, dyes, or similar, however, according to the present invention this is not necessary.
  • said cleaning composition may consist of the ingredients (a), (b), (c), (d), (e) and (f), or even of the ingredients (a), (b), (c), (d) and (e).
  • composition according to the invention preferably is provided in the form of a powder, granulate or compacted body, wherein said powder or granulate optionally is provided in form of a packaged unit dose or the compacted body preferably is a compressed tablet, particularly preferred prepared from the powder or granulate of the composition.
  • the composition may be provided in powder or granulate form either in a container containing the composition for self-dosing by the user, thus, the container comprises the composition as a free-flowing powder or granulate, or the composition is provided in form of a pre-dosed composition as a unit dose, e.g. a compressed tablet, a bag or a small package or a pouch comprising the composition including a portion of the composition for a single use.
  • a unit dose may comprise the composition in an amount in the range of from 10 to 400 g, e.g. from 15 to 200 g, from 20 to 100 g or from 25 to 50 g, dependent from the desired amount for a single use.
  • the unit doses are in a weight range of from 10 to 60 g, in particular if it is provided as a pouch or tablet.
  • a water-soluble material is used to wrap the cleaning composition.
  • Providing the composition in a water-soluble material e.g. a water-soluble film or water-soluble container, has the advantage that the user doesn't come in direct contact with the cleaning composition.
  • Suitable water-soluble materials for packaging cleaning compositions are known in the art and include e.g. polyvinyl alcohol, polylactic acid, gelatine, however, any other suitable material, which can be provided in form of a water-soluble film can be used.
  • a material herein is defined as being "water-soluble/dissolvable/dispersible” when more than 99% of a film (layer) with a thickness of up to 0.5 mm of such a material dissolves within 10 minutes, preferably within 5 min in a 2 L beaker containing 1 L of deionised water at 40° C which is stirred with a stirrer revolving at 200 r. p.m, wherein in case of the film it should be considered as sufficiently dissolved, when the content of the package is completely delivered into the water.
  • the invention further refers to an aqueous solution obtainable by adding the composition of any of claims 1 to 12 to water or an aqueous buffer.
  • Said aqueous solution can be obtained by adding an amount of 5 to 60 g, preferably an amount of 10 to 40 g/l, more preferably an amount of 15 to 35 g/l, even more preferably an amount of 20 to 30 g/l and most preferred an amount of 23 to 25 g/l of a composition as described above in 1 I of water or an aqueous buffer, preferably in water.
  • aqueous solution can be obtained by adding at least ingredients corresponding to ingredients (a) to (d) and optionally (e) and/or (f) in amounts as defined above to water or an aqueous solution, resulting in a solution corresponding to the present invention.
  • the solution obtained or obtainable by adding the composition to water as defined above commonly has a pH in the range of from pH 9 to 12, preferably in the range of from pH 10 to 11.
  • the powder, granulate, compressed tablet or pouch comprising the cleaning composition can be provided together with any instructions for dosing and/or preparing the aqueous solution in form of a kit comprising said composition in any of the mentioned forms and said instructions.
  • Said kit furthermore might comprise any device or further instructions suitable for carrying out a method for removing any support material from a three-dimensional object formed by additive manufacturing, particularly a method as described below.
  • the solution obtainable by adding the cleaning composition according to the present invention to water (or an aqueous buffer) can be used longer for the removing of support material from an object prepared by additive manufacturing compared to known compositions provided on the market, due to the high alkali reserves of the composition.
  • the usage of the present cleaning composition reduces the need of changing the cleaning solution, thus, a higher amount (in gram) of the support material can be dissolved per liter of the cleaning solution compared to formerly known solutions offered on the market. This reduces the costs and the necessary handling steps.
  • any change of the cleaning solution is less harmful for the user, since the cleaning solution comprises less, or even doesn't comprise any oxidizing per-compounds and less or even no highly alkalic silicates.
  • a method for removing support material from a three-dimensional object formed by additive manufacturing comprising:
  • the solution in step (a) can be provided as described above, either by dissolving the mentioned amount of the cleaning composition of the present invention in water (or an aqueous buffer), or by adding the ingredients (a) to (d) and optionally (e) and/or (f) separately to water in according amounts.
  • step (b) a three-dimensional object formed by additive manufacturing and comprising support material which preferably should not be comprised in the final product is contacted with the aqueous solution provided in step (a).
  • This can be carried out e.g. either by immersing said three-dimensional object in the aqueous solution, e.g. in a bath, preferably under agitation of the solution, or by spraying said aqueous solution onto the three-dimensional object, e.g. like in a dishwashing machine or a car wash site.
  • the aqueous solution is heated and preferably maintained to a temperature in the range of from 60 to 90 °C, preferably 65 to 75°C, for and/or during the contact with the three-dimensional object. It is preferred that the three-dimensional object is subjected to the heated aqueous solution in step (b) for a time period of from 20 min to 12 hours to remove the support material successfully.
  • the aqueous solution is used in such an amount that an amount corresponding to 0.1 to 2 g of the solid cleaning composition of the present invention is contacted with 1 g of the support material to be dissolved.
  • the support material to be dissolved is material any commonly used for these purposes, which itself is not dissolvable in distilled water, however, is dissolvable in the aqueous solution of the present invention.
  • the three-dimensional object optionally, but preferably might be rinsed with water or an aqueous, preferably non-alkalic solution after step (b).
  • the invention refers also to the use of a composition according to any of the embodiments described herein or to a package, tablet or pouch as described herein, a kit or an aqueous solution for removing a support material from a three-dimensional object formed by additive manufacturing, wherein said removing preferably is carried out by a method as described herein.
  • the support material preferably is a polymeric material which is soluble in the aqueous solution as described herein, in particular an acid functional polymer or copolymer material, without being limited. Examples of the state of the art are e.g.
  • Support materials for the purpose of forming three-dimensional objects by additive manufacturing are well known in the art and readily available on the market, e.g. the support materials sold by Stratasys, USA under the tradenames SR-10, SR-20, SR-30, SR-35, SR-100 and SR110.
  • the dissolving performance of different aqueous solutions were considered by measuring the time needed for dissolving a predetermined amount of support material from a three-dimensional object formed by additive manufacturing.
  • the dissolution time was measured in (A1) an aqueous solution comprising 12 g/l of a composition according to the invention, (A2) an aqueous solution comprising 24 g/l of a composition according to the invention, (B) an aqueous solution obtained by dissolution of 36.5 g/l of a composition known in the art (Ecoworks® support removal composition of Stratasys; as disclosed in US 2011/0186081 A1 , prepared according to the instructions of the manufacturer).
  • Composition A comprised
  • the aqueous solutions comprising the compositions of the present invention dissolve considerably more of the support material during the same program of the HP removal system as the solution comprising the composition of the art, even though noticeably less amount of the composition was used. This shows that the dissolution performance obtainable with the composition according to the invention allows saving of costs, time and handling steps.

Claims (15)

  1. Composition de nettoyage solide soluble dans l'eau pour éliminer du matériau de soutien d'un objet tridimensionnel formé par fabrication additive, la composition comprenant :
    (a) au moins 50 % en poids d'au moins un carbonate inorganique,
    (b) 0,1 à 15 % en poids d'au moins un hydroxyde de métal alcalin,
    (c) 0,1 à 30 % en poids d'au moins un acide organique, et
    (d) 0 à 5 % en poids d'au moins un tensioactif,
    les pourcentages en poids étant basés sur le poids total de la composition.
  2. Composition selon la revendication 1, où la composition comprend moins de 10 % en poids de composé(s) per oxydant(s) quelconque(s) et/ou moins de 1 % en poids d'un silicate de métal alcalin.
  3. Composition selon l'une quelconque des revendications précédentes, dans laquelle le composant carbonate inorganique (a) comprend au moins un carbonate de métal alcalin, ledit au moins un carbonate de métal alcalin étant présent de préférence en une quantité dans la plage de 50 à 100 % en poids, par rapport au poids total du composant carbonate (a).
  4. Composition selon la revendication 3, comprenant un mélange de deux carbonates de métaux alcalins différents, de préférence en un rapport pondéral de 5:1 à 1:5, de façon encore plus particulièrement préférée en un rapport pondéral de 4:1 à 1:4, de façon encore plus particulièrement préférée en un rapport pondéral de 3:1 à 1:3, de façon encore plus particulièrement préférée en un rapport pondéral de 2:1 à 1:2, et de façon tout particulièrement préférée en un rapport pondéral de 1,2:1 à 1:1,2.
  5. Composition selon l'une quelconque des revendications précédentes, dans laquelle le composant carbonate (a) comprend au moins un bicarbonate de métal alcalin, de préférence en une quantité dans la plage de 5 à 20 % en poids, par rapport au poids total du composant carbonate (a), de préférence au moins un bicarbonate de métal alcalin étant le bicarbonate de sodium.
  6. Composition selon l'une quelconque des revendications précédentes, dans laquelle le composant carbonate (a) comprend (i) au moins un carbonate de métal alcalin et (ii) au moins un bicarbonate de métal alcalin, le rapport pondéral de (i) et (ii) étant de préférence dans la plage de 20:1 à 2:1.
  7. Composition selon l'une quelconque des revendications précédentes, dans laquelle le composant hydroxyde de métal alcalin (b) comprend l'hydroxyde de potassium et/ou l'hydroxyde de sodium, de préférence l'hydroxyde de sodium.
  8. Composition selon l'une quelconque des revendications précédentes, dans laquelle le composant acide organique (c) comprend un acide carboxylique polybasique, l'acide carboxylique polybasique comprenant de préférence l'acide citrique, l'acide citrique étant de préférence présent dans la composition sous la forme de particules enrobées ou de particules à noyau-enveloppe comportant un noyau comprenant de l'acide citrique, qui est au moins partiellement enrobé par une couche comprenant du citrate.
  9. Composition selon l'une quelconque des revendications précédentes, dans laquelle le composant tensioactif (d) comprend au moins un tensioactif choisi dans l'ensemble consistant en des tensioactifs non ioniques, des tensioactifs anioniques, des tensioactifs cationiques, des tensioactifs amphotères et des mélanges ou associations de tels tensioactifs, de préférence comprenant un tensioactif anionique tel qu'un alkylsulfate, alkylsulfonate, sulfosuccinate ou des dérivés alcoxylés de l'un quelconque des précédents ou un mélange ou une association de ceux-ci.
  10. Composition selon l'une quelconque des revendications précédentes, comprenant en outre au moins un agent chélateur, ledit au moins un agent chélateur comprenant de préférence un composé azoté comportant une pluralité de groupes acétate tels que des sels, en particulier des sels de sodium, d'acide nitrilotriacétique, d'acide méthylglycinediacétique, d'acide éthylènediaminetétraacétique, d'acide iminodisuccinique, d'acide éthylènediamine-iminodisuccinique ou d'acide diéthylène-triaminepentaacétique, de préférence le N,N-bis(carboxylatométhyl)-L-glutamate tétrasodique, un oxalate tel que le sel oxalate disodique ou une association de n'importe lesquels des précédents.
  11. Composition selon l'une quelconque des revendications précédentes, qui est une poudre ou composition granulée comprenant :
    (a1) 60 à 85 % en poids d'au moins un carbonate de métal alcalin,
    (a2) 5 à 20 % en poids d'au moins un bicarbonate de métal alcalin,
    (b) 1 à 5 % en poids d'au moins un hydroxyde de métal alcalin,
    (c) 5 à 15 % en poids d'au moins un acide organique,
    (d) 0,1 à 1 % en poids d'au moins un tensioactif, et
    (e) 0,01 à 0,5 % en poids d'au moins un agent chélateur,
    (f) 0 à 1 % en poids d'autres composants choisis parmi une charge, un parfum ou des colorants
    les pourcentages en poids étant basés sur le poids total de la composition.
  12. Composition selon l'une quelconque des revendications précédentes, où la composition est sous la forme d'une poudre, d'un produit granulé ou d'un corps compacté, ladite poudre ou ledit produit granulé étant en option fourni(e) sous forme d'une dose unitaire conditionnée ou le corps compacté étant de préférence un comprimé formé par compression.
  13. Solution aqueuse pouvant être obtenue par addition à de l'eau ou une solution aqueuse et dissolution dans celle-ci de la composition selon l'une quelconque des revendications 1 à 12, de préférence par addition d'une quantité de 5 à 60 g, de préférence 10 à 40 g/l, de façon plus particulièrement préférée 15 à 35 g/l, de façon encore plus particulièrement préférée 20 à 30 g/l et de façon tout particulièrement préférée d'une quantité de 23 à 25 g/l d'une composition selon l'une quelconque des revendications 1 à 12, à 1 l d'eau ou d'un tampon aqueux.
  14. Procédé pour éliminer du matériau de soutien d'un objet tridimensionnel formé par fabrication additive, comprenant les étapes consistant à :
    (a) fournir une solution aqueuse selon la revendication 13, et
    (b) mettre l'objet tridimensionnel formé par fabrication additive en contact avec la solution aqueuse pour éliminer de l'objet tridimensionnel au moins une partie du matériau de soutien.
  15. Procédé selon la revendication 14, dans lequel la mise en contact dans l'étape (b) comprend l'immersion de l'objet tridimensionnel dans un bain de la solution aqueuse, ou dans lequel la mise en contact dans l'étape (b) comprend la pulvérisation de la solution aqueuse sur l'objet tridimensionnel, par exemple dans une machine à laver la vaisselle.
EP17199802.4A 2017-11-03 2017-11-03 Composition de nettoyage solide soluble dans l'eau Active EP3480287B1 (fr)

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EP17199802.4A EP3480287B1 (fr) 2017-11-03 2017-11-03 Composition de nettoyage solide soluble dans l'eau
PL17199802T PL3480287T3 (pl) 2017-11-03 2017-11-03 Stała, rozpuszczalna w wodzie kompozycja czyszcząca

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GB2585077A (en) * 2019-06-28 2020-12-30 Nanexa Ab Apparatus
WO2023108087A1 (fr) * 2021-12-08 2023-06-15 Oryx Additive, Inc. Procédé, appareil, et système d'élimination de matériau de support d'un objet imprimé en 3d
CN115197794A (zh) * 2022-07-19 2022-10-18 广州黑格智造信息科技有限公司 用于清洗3d打印构件的清洗剂、清洗方法及清洗机

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US6228923B1 (en) 1997-04-02 2001-05-08 Stratasys, Inc. Water soluble rapid prototyping support and mold material
US20030207959A1 (en) 2000-03-13 2003-11-06 Eduardo Napadensky Compositions and methods for use in three dimensional model printing
US6569373B2 (en) 2000-03-13 2003-05-27 Object Geometries Ltd. Compositions and methods for use in three dimensional model printing
US7546841B2 (en) * 2003-11-19 2009-06-16 David Jonathan Tafoya Apparatus and method of removing water soluble support material from a rapid prototype part
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