EP2195142A1 - Composition resinique liquide pour articles abrasifs - Google Patents
Composition resinique liquide pour articles abrasifsInfo
- Publication number
- EP2195142A1 EP2195142A1 EP08843140A EP08843140A EP2195142A1 EP 2195142 A1 EP2195142 A1 EP 2195142A1 EP 08843140 A EP08843140 A EP 08843140A EP 08843140 A EP08843140 A EP 08843140A EP 2195142 A1 EP2195142 A1 EP 2195142A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition according
- resin
- less
- equal
- resin composition
- 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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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
- B24D3/20—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially organic
- B24D3/28—Resins or natural or synthetic macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
- Y10T428/257—Iron oxide or aluminum oxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/259—Silicic material
Definitions
- the present invention relates to a liquid resin composition capable of thermally crosslinking for the manufacture of abrasive articles, and to the resulting abrasive articles.
- Abrasive articles in general contain a multitude of abrasive grains securely bonded to a carrier or to each other via a binder.
- abrasive coated abrasives and abrasive bonded abrasives are distinguished.
- the abrasives applied comprise a support material, generally flexible, on the surface of which are distributed abrasive grains embedded in a binder.
- the flexible support may be a sheet of paper, a film or a network of fibers, for example a mat, a felt, a fabric or a knit of natural or synthetic fibers, in particular made of glass or a polymer.
- These abrasives can adopt various forms: sheets, strips, discs, ...
- the manufacture of the coated abrasives comprises the application of a base coat ("make coat”) on the support material, the distribution of the grains of abrasives on said layer, the heat treatment of the base adhesive layer in order to partially harden it and the application of a superior adhesive layer ("size coat”) which guarantees a firm anchoring of the grains on the support.
- a base coat (“make coat")
- size coat a superior adhesive layer
- An additional adhesive layer (“supersize coat”) may be deposited on the upper adhesive layer and the abrasive grains.
- the base, top and extra adhesive layers are applied in liquid form. They are generally made of a thermosetting resin, in particular a phenolic resin of resol type.
- the agglomerated abrasives consist of abrasive grains bonded together by a binder which provides a three-dimensional structure adapted to ensure the abrasion operations, including the cutting of hard materials such as steel.
- these abrasives have the appearance of a grinding wheel, a grinding wheel segment and a whetstone.
- Agglomerated abrasives in the form of "conventional" grinding wheels consist of a single region composed of abrasive grains embedded in the binder which extends from the bore to the periphery of the grinding wheel.
- the abrasion region is located in the periphery, in the form of a strip supported by a central core generally made of metal, and the abrasive grains consist of a very hard material, for example diamond or cubic boron nitride.
- Agglomerated abrasives are obtained by the process using compression molding techniques, cold or hot.
- cold compression molding (“CoId Molding
- Compression the most widespread, the mixture of constituents of the abrasive, in granular form, is introduced into a mold, then a sufficient compressive force is applied, of the order of 15 to 25 N / mm 2 , for placing said mixture in the shape of the mold and ensuring that after extraction of the mold, the piece obtained (green part or "green item") has sufficient strength to be manipulated without losing its original shape.
- the part is then heated in an oven at a temperature to crosslink the binder, this temperature depending on the nature of the binder used.
- Hot compression molding achieves a higher compaction level than cold molding, which results in a smaller pore volume in the final article.
- the granular mixture introduced into the mold is compacted under pressure and heated simultaneously in order to allow the binder to be better distributed between the abrasive grains and to occupy the empty spaces.
- the part After being removed from the mold, the part generally undergoes a post-crosslinking heat treatment to improve its operating life and abrasion performance.
- the granular mixture is prepared by pre-treating the abrasive grains with a liquid impregnating resin, usually a resol type phenolic resin, and then mixing the wet grains with a novolak type phenolic resin powder containing a crosslinking agent - powder which will subsequently constitute the binder itself - and optionally additives, also in powder form.
- a liquid impregnating resin usually a resol type phenolic resin
- a novolak type phenolic resin powder containing a crosslinking agent - powder which will subsequently constitute the binder itself - and optionally additives, also in powder form.
- the resulting mixture thus consists of abrasive grains on the surface of which are adhered solid particles of resin and additives.
- This mixture has a good ability to be uniformly distributed in the mold (called "flowability") and to be shaped under the effect of pressure.
- thermosetting resins used for the manufacture of coated and agglomerated abrasives have numerous advantages in the intended use conditions, in particular: they ensure a solid connection of the grains with the support material, on the one hand, and grains between them, on the other hand,
- a disadvantage of the aforementioned resols is that they contain formaldehyde detrimental to human health and the environment.
- the resols contain free formaldehyde which can be emitted into the atmosphere during the manufacture of the abrasives, and that they can further generate formaldehyde under the conditions of use of the abrasive, when the temperature reaches a level leading to the degradation of the resol with release of formaldehyde.
- WO 2005/108454 A1 discloses a novolac resin and non-formaldehyde hardener composition for reinforcing composite materials.
- a polymerizable abrasive composition which comprises an aminoplast resin and a reactive diluent which each contain pendant unsaturated groups.
- US 5,178,646 discloses a binder precursor composition for abrasives, especially coated, which comprises a heat-curable resin having a plurality of pendant methylol groups and a reactive diluent having at least one functional group that reacts with the groups of the resin.
- US 5,549,719 discloses a composition for forming the base adhesive layer of coated abrasives.
- the composition comprises an aqueous dispersion of an epoxy resin, an emulsifier and a crosslinking agent, and optionally an agent which aids in abrasion.
- This aqueous composition makes it possible to replace the compositions based on organic solvents, the use of which becomes more restrictive, but in return it is necessary to treat the abrasives in thermal installations to remove the water.
- the present invention aims to reduce the amount of formaldehyde and water in an abrasive product.
- the invention provides a thermally crosslinkable liquid resin composition which is an alternative to aqueous epoxy resins and resins used as an adhesive in coated abrasives and as an impregnating resin in agglomerated abrasives.
- liquid resin composition being characterized in that it comprises at least one resin comprising at least two epoxy groups and at least one reactive diluent, and in that it has a viscosity at 25 ° C of less than or equal to 7000 mPa. s.
- the liquid resin composition has a viscosity of less than or equal to 6000 mPa.s, measured at 25 ° C.
- the epoxy resin may be chosen from any type of resin comprising at least two epoxy functional groups, preferably at most 10.
- "Epoxy functional group” means a group containing an oxirane ring.
- the epoxy resin has an epoxide equivalent mass which varies from 160 to 700, preferably less than or equal to 500 and advantageously less than or equal to 350.
- the epoxy equivalent mass Epoxide Equivalent Weight (EEW) is the ratio of the average molar mass of the resin to the average number of epoxy functional groups per molecule.
- the epoxy resin is chosen from epoxy resins whose main chain is aliphatic, cycloaliphatic or aromatic.
- the epoxy resin is an aromatic epoxy resin, advantageously of the bisphenol A or F type, in particular bisphenol A or F diglycidyl ether of formula:
- the bisphenol A or F epoxy resins can be obtained by reacting a bisphenol A or F with an excess of epichlorohydrin, in the presence of a basic catalyst, for example sodium hydroxide, at a temperature of the order of 10O 0 C.
- a basic catalyst for example sodium hydroxide
- the epoxy resin is chosen from epoxidized novolak resins.
- the epoxidized novolak resin can be obtained by treating a novolac resin with an excess of epichlorohydrin in the presence of a basic catalyst, for example sodium hydroxide, at a temperature of the order of 100 ° C.
- a basic catalyst for example sodium hydroxide
- the novolak resin may be chosen from novolacs known to those skilled in the art which are obtained by reacting a phenolic compound and an aldehyde in an aldehyde / phenol compound molar ratio of less than 1, in the presence of an acid catalyst. .
- the phenolic compound is chosen from phenol and substituted phenols such as cresols, guaiacol, methoxyphenols, catechol, resorcinol, tert-butyl phenol and nonyl phenol, bisphenols such as bisphenol A or F, naphthols and mixtures of these compounds.
- the phenol is selected.
- the aldehyde is selected from alicyclic aldehydes such as formaldehyde, cyclic aldehydes such as furfural, aromatic aldehydes such as benzaldehyde, para-anisaldehyde, orthoanisaldehyde and veratraldehyde, and mixtures of these aldehydes.
- the formaldehyde is chosen.
- the aldehyde / phenol molar ratio ranges from 0.2 to less than 1, preferably from 0.35 to 0.9, and more preferably from 0.5 to 0.9.
- the novolak resin may be prepared using a known acidic catalyst, for example a strong mineral acid such as sulfuric acid, phosphoric acid and hydrochloric acid, or an organic acid such as oxalic acid, acid salicylic acid or anhydrides such as maleic anhydride.
- the amount of acid should be sufficient to allow the condensation of the phenolic compound and the aldehyde.
- the amount of acid used generally represents 0.02 and 1% of the weight of the starting phenolic compound, preferably 0.1 to 0.6% in the case of a strong mineral acid, and 0.3 to 3% of the weight of the starting phenolic compound in the case of an organic acid.
- the novolac resin obtained at the end of the condensation reaction is treated so as to reduce the content of free phenolic compound, for example by distillation under reduced pressure.
- the preferred epoxy novolacs have the formula:
- the novolacs that may be used in the context of the invention contain less than 0.1% by weight of free formaldehyde, and preferably less than 0.05% by weight.
- the epoxy resin may consist of a mixture of at least one epoxidized aromatic resin and at least one epoxidized novolak resin described above.
- the resin composition may also comprise at least one resin different from the epoxy resin according to the invention capable of reacting with said epoxy resin and / or the crosslinking agent as explained later, for example a novolak.
- the proportion of epoxy resin must however remain greater than or equal to 50% by weight of all the resins, epoxy (s) and other (s), preferably greater than or equal to 75% and advantageously the proportion is equal to 100% .
- the epoxy resin represents at least 30% by weight of the resin composition, preferably at least 40%, advantageously at least 50%, and does not exceed 90%.
- the reactive diluent according to the invention is a liquid compound at room temperature, of the order of 20 to 25 ° C, which solubilizes the epoxy resin and adjust the viscosity of the resin composition.
- the reactive diluent has a viscosity of less than or equal to 1000 mPa.s, preferably less than or equal to 700 mPa.s, advantageously less than 500 mPa.s and better still less than 350 mPa.s., measured at 25 mPa.s. ° C.
- the reactive diluent also contains at least one function capable of reacting with the resin and / or the crosslinking agent, which function is chosen from the hydroxy, aldehyde, epoxy, oxazolidine and lactone functions.
- reactive diluents comprising hydroxyl functional groups
- alicyclic alcohols saturated or unsaturated, such as ethylene glycol, 1,3-butylene glycol, glycerol, trimethylolpropane and the monoallyl ethers of these cyclic, saturated or unsaturated alcohols, such as furfuryl alcohol, mono- or polynuclear aromatic alcohols such as benzyl alcohol and its derivatives, m-cresol, 3,5-xylenol, nonylphenol, cardanols and their derivatives such as cardols, methylcardols and the anacardial acids contained in particular in the shell of the cashew nut shell liquid (noted CNSL) and naphthol, and the precursors of these alcohols, including acetals and trioxanes.
- CNSL cashew nut shell liquid
- naphthol the precursors of these alcohols, including acetals and trioxanes.
- reactive diluents comprising aldehyde functions
- reactive diluents comprising epoxy functions
- glycidyl ethers of saturated or unsaturated alcohols such as the diglycidyl ether of butanediol-1,4, the diglycidyl ether of hexane-1,6-diol.
- fatty acids contained in the epoxidized including epoxidized oils, especially soybean oil (Ecocet ®; Arkema) and linseed oil (Vikoflex ®, Arkema), and aromatic epoxy such as epoxidized cardanols including 3-n-pentadécadiénylphénol.
- reactive diluents comprising oxazolidine functional groups
- the preferred lactone functional reactive diluent is gamma-butyrolactone.
- gamma-butyrolactone is used in admixture with triphenylphosphite, which makes it possible to improve the thermal resistance of the liquid resin composition.
- the preferred diluents are furfuryl alcohol, cardols and their derivatives
- CNSL glyoxal
- butanediol-1,4 diglycidyl ether 1,6-hexanediol diglycidyl ether
- epoxidized cardanols bis-oxazolidines and gamma-butyrolactone.
- the reactive diluent represents at least 10% by weight of the resin composition, preferably at least 20%, and advantageously does not exceed 70%, preferably 30%. Below 10%, the viscosity of the resin composition is too great for it to be used in the targeted applications. Above 70%, the mechanical properties of the final abrasive product are not satisfactory.
- the resin composition may further comprise at least one crosslinking agent and / or at least one crosslinking catalyst.
- the crosslinking agent must have a high reactivity with regard to the epoxy resin and / or the reactive diluent.
- the crosslinking agent is chosen from compounds containing at least one amine, hydroxy, aldehyde or carboxylic function, and heterocyclic compounds containing a structure containing a nitrogen atom and an oxygen atom separated by a carbon atom.
- compounds containing at least one amine function mention may be made of aliphatic amines such as triethylenetetramine (TETA) and triethylenepentamine (TEPA), polyamidoamines and aromatic polyamines such as diaminodiphenylmethane (MDA) and diaminodiphenylsulfone. (DDS).
- tris (hydroxymethyl) nitromethane and resins comprising condensates obtained by Mannich reaction of a phenolic compound, an aldehyde and an aminoalcohol such as described in particular in WO2004 / 011519 A1, in particular phenol-formaldehyde-diethanolamine resins.
- heterocyclic compounds containing a nitrogen atom and an oxygen atom separated by a carbon atom there may be mentioned oxazolines such as 1,3-phenylenebisoxazoline, and oxazolidines such as 3 ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine and 1-aza-3,7-dioxa-5-ethylbicyclo (3.3.0) octane.
- oxazolines such as 1,3-phenylenebisoxazoline
- oxazolidines such as 3 ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine and 1-aza-3,7-dioxa-5-ethylbicyclo (3.3.0) octane.
- the preferred crosslinking agent is ths (hydroxymethyl) nitromethane, glyoxal and its derivatives, 2,2-dimethoxyethanal, the resins containing condensates obtained by Mannich reaction of a phenolic compound, an aldehyde and aminoalcohol, homopolymers of acrylic acid, 1,3-phenylene-bisoxazoline, 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine and 1 -aza-3,7 -dioxa-5-éthylbicyclo- (3.3.0) octane.
- the crosslinking agent does not exceed 50% of the weight of the liquid resin composition and preferably does not exceed 30%.
- the liquid resin composition may also comprise at least one crosslinking catalyst selected from Lewis bases such as O- (dimethylaminoethyl) phenol, tris- (dimethylaminoethyl) phenol, 2,4,6-tri (dimethylaminomethyl) phenol, 2-methylimidazole, 2-ethyl-4-methylimidazole and 1-benzyl-2-methylimidazole, and Lewis acids such as boron trifluoride-monoethylamine complex.
- Lewis bases such as O- (dimethylaminoethyl) phenol, tris- (dimethylaminoethyl) phenol, 2,4,6-tri (dimethylaminomethyl) phenol, 2-methylimidazole, 2-ethyl-4-methylimidazole and 1-benzyl-2-methylimidazole
- Lewis acids such as boron trifluor
- the preferred catalyst is 2,4,6-tri (dimethylaminomethyl) phenol, 2-methylimidazole and 2-ethyl-4-methylimidazole.
- the amount of catalyst in the liquid resin composition is less than or equal to 10 parts by weight per 100 parts by weight of epoxy resin, reactive diluent and optionally crosslinking agent, and preferably is less than or equal to 5 parts .
- the preparation of the liquid resin composition can be done by simply mixing the constituents in a suitable container, advantageously provided with stirring means; preferably, the novolak resin is introduced into the reactive diluent, then the crosslinking agent and / or the catalyst is optionally added.
- the mixture of constituents may be at room temperature, of the order of 20 to 25 ° C, or at a higher temperature but which must remain at least 20 ° C below the crosslinking temperature. of the resin composition.
- the viscosity of the liquid resin composition depends on the intended application but remains less than or equal to 7000 mPa.s.
- the liquid resin composition according to the invention is used to manufacture agglomerated abrasives.
- the liquid resin composition is first mixed with abrasive grains in a conventional mechanical mixer until the grains are suitably "wetted”, i.e., coated with the resinous composition, and then the binder powder and the additives, also in powder form, until a homogeneous granular mixture is obtained.
- the liquid resin composition has a viscosity at most equal to 3000 mPa.s, and advantageously greater than or equal to 600 mPa.s., at 25 ° C.
- the starting temperature of crosslinking of the resin in the granular mixture is at most equal to 245 ° C., and advantageously at most equal to 195 ° C.
- the time required to obtain complete crosslinking of the resin composition in the granular mixture is less than or equal to 36 hours, preferably less than or equal to 20 hours.
- the abrasive grains may be any type of known abrasive grains, for example composed of alumina, including fused aluminas and sintered aluminas obtained by sol-gel, seeded or not with a material of the same crystalline nature, chemically modified or not, iron oxide, molybdenum oxide, vanadium oxide, alumina-zirconia, boron-alumina, silicon carbide, aluminum-oxynitride, diamond or cubic boron nitride, and mixtures of such grains.
- the abrasive grains are alumina.
- the abrasive grains are pretreated with an organic compound which improves the adhesion between the grain and the liquid resin composition, chosen from compounds containing silicon, for example a silane functionalized with organic groups such as vinylsilane, especially vinyltriethoxysilane, an aminosilane, especially gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane and diaminopropylethoxysilane, or an epoxysilane.
- gamma-aminopropyltriethoxysilane is used.
- the treatment of the abrasive grains with the organic compound containing silicon can be carried out for example by spraying a solution of said compound in a suitable solvent or by dispersing the grains in the aforementioned solution.
- the treated abrasive grains are dried before being mixed with the liquid resin composition.
- a liquid organic carrier can be added to the abrasive grain mixture and the resinous composition, which aids in grain wetting and the formation of a uniform grain network, and which is subsequently removed in the course of time. crosslinking step.
- the organic carrier may be water, an aliphatic alcohol, a glycol, high molecular weight oil fractions of oily or waxy consistency, mineral oil or any other known vehicle.
- the binder may be a phenol-aldehyde, melamine-aldehyde, urea-aldehyde, polyester, polyimide, epoxy, polyurethane or polybenzimidazole resin.
- the binder is a low formaldehyde resin, advantageously a novolak type phenol-aldehyde resin, and more preferably a phenol-formaldehyde novolac resin.
- the additives are, for example, fillers, crosslinking agents and other compounds which are useful for the manufacture of agglomerated abrasives, in particular bound by an organic resin.
- the fillers are generally in the form of a finely divided powder comprising particles that may have the appearance of granules, spheres or fibers.
- sand silicon carbide
- alumina hollow spheres bauxite
- chromites magnesite
- dolomites hollow mullite spheres
- borides silica fume, titanium dioxide, carbon products (carbon black, coke, graphite, ...), wood flour, clay, talc, hexagonal boron nitride, molybdenum disulfide, feldspar, nepheline syenite and glass, especially in the form of solid, hollow or hollow beads, and fibers.
- the fillers represent 0.1 to 30% by weight of the granular mixture.
- Crosslinking agents are used when the powder binder is a novolac resin. They may be chosen from compounds known to perform the aforementioned function such as hexamethylenetetramine or precursors thereof. The crosslinking agent is added in an amount of 5 to 20 parts by weight per 100 parts by weight of novolac resin powder.
- the additives may further comprise agents which assist in the implementation of the process, for example anti-static agents and lubricants. The amount of these additives can be easily determined by those skilled in the art.
- the granular mixture is subjected to a ripening treatment at room temperature for a period of about 12 hours.
- the granular mixture is then introduced into a mold equipped with compression means making it possible to form a green part which has sufficient cohesion to be able to be handled and treated in the steps following without substantial modification of its shape.
- the binder at this stage is in the uncrosslinked state.
- the green part is then heated to a temperature sufficient for the binder to crosslink and give a rigid polymeric network which gives the piece its final shape.
- the crosslinking is carried out according to a conventional baking cycle which consists of bringing the green part to a temperature of the order of 100 ° C. and keeping it at this temperature for 30 minutes to several hours so that the volatile products formed can be removed. . Then, the room is heated to the final temperature over a period that generally ranges from 10 to 36 hours.
- the final crosslinking temperature depends in particular on the nature of the resin used, the size and shape of the piece to be treated and the cooking time. In general, the final crosslinking temperature is between 100 and 200 ° C.
- the thermal crosslinking is carried out in a controlled atmosphere, preferably with a maximum relative humidity level.
- the agglomerated abrasives obtained may be in the form of grinding wheels, segments of grinding wheels, discs and whetstones.
- the liquid resin composition according to the invention is used to produce coated abrasives.
- the manufacture of the coated abrasives comprises the steps of depositing a base coat ("make coat") on a support material, distributing the grains of abrasives on said layer, subjecting said material to a heat treatment allowing partially cross-linking the resin composition, depositing a top adhesive layer ("size coat”) and subjecting the heat-treated coated material to obtain complete crosslinking of the resin composition. If necessary, an additional adhesive layer may be deposited on the upper adhesive layer and crosslinked by a suitable heat treatment.
- the support material generally has a moderate to strong flexibility, and has the appearance of a sheet, in particular paper, a film, in particular polymer, or a more or less dense network of natural or synthetic fibers, for example. Examples of glass fibers and vulcanized fibers.
- the abrasive grains may be chosen from the grains already mentioned which form part of the agglomerated abrasives.
- the application of the grains on the base adhesive layer can be done by the usual techniques operating by gravity or electrostatically.
- the density of the abrasive grains on the support is to be chosen according to the intended application.
- the liquid resin composition according to the invention may be used to form the base adhesive layer ("make coat"), the upper adhesive layer ("size coat”) or the additional adhesive layer “supersize coat”).
- the liquid resin composition serves to form the base adhesive layer and the upper adhesive layer, and optionally the additional adhesive layer.
- the liquid resin composition has a viscosity of less than or equal to 6000 mPa.s and a starting temperature of crosslinking at most equal to 150 0 C, preferably at most equal to 120 0 C. It advantageously contains at least one agent of crosslinking or at least one crosslinking catalyst.
- the time necessary to obtain complete crosslinking of the resin composition is less than 36 hours, preferably less than 20 hours.
- the basic, superior and additional adhesive layers which are not formed from the liquid resin composition according to the invention may be chosen from phenolic resins, urea-formaldehyde, epoxy, urethane, acrylic, aminoplast, melamine and mixtures thereof. of these resins.
- the resin or resin mixture has the lowest possible free formaldehyde level.
- the liquid resin composition may further comprise additives, for example wetting agents, fillers, coupling agents, dyes, pigments and antistatic agents.
- additives for example wetting agents, fillers, coupling agents, dyes, pigments and antistatic agents.
- the liquid resin composition when used to form the upper adhesive layer and / or the additional adhesive layer, it advantageously comprises at least one agent which enhances the abrasive performance of the final abrasive.
- Such an agent may be chosen from waxes, compounds halogenated organic compounds, halogen salts, metals and metal alloys.
- the heat treatment of the support material coated with the liquid resin composition forming the base adhesive layer is carried out at a temperature of less than or equal to 150 ° C., preferably less than or equal to 120 ° C. for 1 to 120 minutes, preferably 1 to 60 ° C. minutes.
- the conditions of the heat treatment for the crosslinking of the resin composition forming the upper adhesive layer or the additional adhesive layer may be at a temperature of less than or equal to 150 ° C., preferably less than or equal to 120 ° C. for at most 36 hours. preferably at most 20 hours.
- liquid resin compositions are measured under the following conditions:
- the crosslinking start temperature is measured by Dynamic Mechanical Analysis (DMA): the liquid resin composition is introduced between two glass plates and the assembly is placed horizontally on a device comprising two fixed lower jaws remote from each other; 40 mm and an upper jaw applied against the upper sheet located 20 mm from each of the preceding jaws. On the upper jaw, a force of 8OmPa is applied with an oscillation frequency of 1 Hz and heating the whole 25 to 300 ° C at a rate of 4 ° C / minute. The elastic modulus of the resin composition is measured as a function of the temperature and from the established curve the starting temperature of the crosslinking is determined.
- DMA Dynamic Mechanical Analysis
- the loss of mass at 400 ° C. is determined by thermogravimetric analysis (DTA): the liquid resin composition is deposited in an aluminum cup and heated according to a given temperature cycle. 10 to 20 mg of the crosslinked resin composition are placed in an alumina crucible which is placed in an apparatus continuously measuring the loss of mass during a temperature cycle ranging from 25 to 700 ° C. at a rate of 10 ° C. C / minute. On the recorded curve, the loss of mass is determined at 400 ° C.
- DTA thermogravimetric analysis
- the resins are obtained by solubilizing the epoxy resin in the reactive diluent with moderate agitation, and then optionally adding the crosslinking agent and / or the catalyst while maintaining the stirring conditions.
- the solubilization of the resin is carried out at ambient temperature, of the order of 20 to 25 ° C., for the DGEBA resin (epoxy bisphenol A type resin) and at a temperature of the order of 50 ° C. for the resin. epoxidized novolac.
- liquid resin compositions (Examples 1 to 24) and the reference compositions (Ref 1 to 3) are treated according to the following temperature cycles:
- Cycle no. 1 coated abrasives
- Cycle no. 2 (agglomerated abrasives) - cycle no. 1
- Reference compositions 1 and 2 are liquid compositions suitable for producing coated abrasives based on a phenol-formaldehyde resole and a urea-formaldehyde resin, respectively.
- the reference composition 3 (Ref 3) is a liquid composition based on a phenol-formaldehyde resole suitable for the manufacture of agglomerated abrasives.
- the crosslinking start temperature and the mass loss at 400 ° C. of the resin compositions are given in Table 1.
- the liquid resin compositions of Examples 8 and 22, and of reference 3 are used to form blends with a solid novolac resin (12) suitable for making agglomerated abrasives.
- the mixtures comprise (in% by weight): 12.7% of the liquid resin composition and 87.3% of the solid resin.
- the weight loss is determined at 400 and 500 ° C.
- Examples 1 to 24 are used to form liquid resin compositions having the composition given in Table 2.
- the resins are obtained by solubilizing the epoxy resin in the reactive diluent with moderate agitation and then adding the catalyst if necessary while maintaining the stirring conditions.
- the solubilization of the resin is carried out at a temperature of the order of
- liquid resin compositions are treated according to the temperature cycles 1 and 2 described in Examples 1 to 24.
- crosslinking start temperature and the mass loss at 400 ° C. of the resin compositions are given in Table 2.
- HAAS average molecular weight: 4500 (10) based on phenol-formaldehyde-aminoalcohol condensates according to Example 2 (a) of WO2004 / 011519 A1, modified in that the aminoalcohol is diethanolamine (11) sold under the reference " Highlink ® CDO »by the company
- HEXION SPECIALTY CHEMICALS contains 7% by weight of hexamethylenetetramine (HEXA) (13) marketed under the reference “Bakélite ® PF8505F” by the company
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polishing Bodies And Polishing Tools (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0706880A FR2921667B1 (fr) | 2007-10-01 | 2007-10-01 | Composition resinique liquide pour articles abrasifs |
PCT/FR2008/051779 WO2009053581A1 (fr) | 2007-10-01 | 2008-10-01 | Composition resinique liquide pour articles abrasifs |
Publications (1)
Publication Number | Publication Date |
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EP2195142A1 true EP2195142A1 (fr) | 2010-06-16 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08843140A Withdrawn EP2195142A1 (fr) | 2007-10-01 | 2008-10-01 | Composition resinique liquide pour articles abrasifs |
Country Status (8)
Country | Link |
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US (2) | US20100270495A1 (fr) |
EP (1) | EP2195142A1 (fr) |
CN (1) | CN101883664B (fr) |
AR (1) | AR068642A1 (fr) |
CL (1) | CL2008002930A1 (fr) |
FR (1) | FR2921667B1 (fr) |
TW (1) | TWI478965B (fr) |
WO (1) | WO2009053581A1 (fr) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2921666B1 (fr) | 2007-10-01 | 2012-11-09 | Saint Gobain Abrasives Inc | Composition resinique liquide pour articles abrasifs |
FR2930948B1 (fr) | 2008-05-06 | 2013-07-12 | Saint Gobain Abrasives Inc | Composition resinique liquide sans formaldehyde pour articles abrasifs |
DE102010044050A1 (de) | 2010-11-17 | 2012-05-24 | Evonik Degussa Gmbh | Verfahren zur kontinuierlichen Herstellung eines Prepolymers basierend auf Phenolharzen, Oxazolinen und Epoxiden |
DE102012223387A1 (de) * | 2012-12-17 | 2014-06-18 | Evonik Industries Ag | Verwendung von substituierten Benzylalkoholen in reaktiven Epoxy-Systemen |
CN103509519A (zh) * | 2013-04-06 | 2014-01-15 | 连新兰 | 环氧树脂磨具膏 |
KR20160090830A (ko) * | 2013-11-26 | 2016-08-01 | 다우 글로벌 테크놀로지스 엘엘씨 | 경화제 조성물 |
WO2016049832A1 (fr) * | 2014-09-30 | 2016-04-07 | Blue Cube Ip Llc | Composition époxyde |
US9873180B2 (en) * | 2014-10-17 | 2018-01-23 | Applied Materials, Inc. | CMP pad construction with composite material properties using additive manufacturing processes |
US10875145B2 (en) | 2014-10-17 | 2020-12-29 | Applied Materials, Inc. | Polishing pads produced by an additive manufacturing process |
CN113579992A (zh) | 2014-10-17 | 2021-11-02 | 应用材料公司 | 使用加成制造工艺的具复合材料特性的cmp衬垫建构 |
US11745302B2 (en) | 2014-10-17 | 2023-09-05 | Applied Materials, Inc. | Methods and precursor formulations for forming advanced polishing pads by use of an additive manufacturing process |
US10821573B2 (en) | 2014-10-17 | 2020-11-03 | Applied Materials, Inc. | Polishing pads produced by an additive manufacturing process |
US10875153B2 (en) | 2014-10-17 | 2020-12-29 | Applied Materials, Inc. | Advanced polishing pad materials and formulations |
US10399201B2 (en) | 2014-10-17 | 2019-09-03 | Applied Materials, Inc. | Advanced polishing pads having compositional gradients by use of an additive manufacturing process |
KR102625791B1 (ko) * | 2015-10-07 | 2024-01-15 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 에폭시-작용성 실란 커플링제, 표면-개질된 연마 입자, 및 결합된 연마 물품 |
WO2017074773A1 (fr) | 2015-10-30 | 2017-05-04 | Applied Materials, Inc. | Appareil et procédé de formation d'article de polissage ayant un potentiel zêta souhaité |
US10593574B2 (en) | 2015-11-06 | 2020-03-17 | Applied Materials, Inc. | Techniques for combining CMP process tracking data with 3D printed CMP consumables |
US10391605B2 (en) | 2016-01-19 | 2019-08-27 | Applied Materials, Inc. | Method and apparatus for forming porous advanced polishing pads using an additive manufacturing process |
US11471999B2 (en) | 2017-07-26 | 2022-10-18 | Applied Materials, Inc. | Integrated abrasive polishing pads and manufacturing methods |
WO2019032286A1 (fr) | 2017-08-07 | 2019-02-14 | Applied Materials, Inc. | Tampons à polir à distribution abrasive et leurs procédés de fabrication |
DE102017008925A1 (de) * | 2017-09-25 | 2019-03-28 | Hexion GmbH | Imprägnierharzmischung |
CN112654655A (zh) | 2018-09-04 | 2021-04-13 | 应用材料公司 | 先进抛光垫配方 |
US11806829B2 (en) | 2020-06-19 | 2023-11-07 | Applied Materials, Inc. | Advanced polishing pads and related polishing pad manufacturing methods |
US11878389B2 (en) | 2021-02-10 | 2024-01-23 | Applied Materials, Inc. | Structures formed using an additive manufacturing process for regenerating surface texture in situ |
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DE2822910A1 (de) * | 1978-05-26 | 1979-11-29 | Lippert H Gmbh | Schleifscheibe fuer nasschliff |
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US5441549A (en) * | 1993-04-19 | 1995-08-15 | Minnesota Mining And Manufacturing Company | Abrasive articles comprising a grinding aid dispersed in a polymeric blend binder |
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2008
- 2008-10-01 TW TW097137765A patent/TWI478965B/zh active
- 2008-10-01 AR ARP080104283A patent/AR068642A1/es active IP Right Grant
- 2008-10-01 CN CN200880118616.1A patent/CN101883664B/zh active Active
- 2008-10-01 CL CL2008002930A patent/CL2008002930A1/es unknown
- 2008-10-01 WO PCT/FR2008/051779 patent/WO2009053581A1/fr active Application Filing
- 2008-10-01 US US12/681,252 patent/US20100270495A1/en not_active Abandoned
- 2008-10-01 EP EP08843140A patent/EP2195142A1/fr not_active Withdrawn
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2012
- 2012-12-11 US US13/711,107 patent/US8690978B2/en active Active
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PHAM, H.Q. & MARKS, M.J.: "Epoxy Resins", 15 October 2005 (2005-10-15), pages 1-8,48-59, Retrieved from the Internet <URL:http://onlinelibrary.wiley.com/doi/10.1002/14356007.a09_547.pub2/full> [retrieved on 20171017], DOI: 10.1002/14356007.a09.pub2 * |
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Also Published As
Publication number | Publication date |
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CL2008002930A1 (es) | 2009-09-04 |
TWI478965B (zh) | 2015-04-01 |
TW200932797A (en) | 2009-08-01 |
CN101883664B (zh) | 2016-03-30 |
US20100270495A1 (en) | 2010-10-28 |
US8690978B2 (en) | 2014-04-08 |
FR2921667B1 (fr) | 2012-11-09 |
WO2009053581A1 (fr) | 2009-04-30 |
CN101883664A (zh) | 2010-11-10 |
AR068642A1 (es) | 2009-11-25 |
US20130091778A1 (en) | 2013-04-18 |
FR2921667A1 (fr) | 2009-04-03 |
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