SG187691A1 - Carrier fluids for abrasives - Google Patents

Carrier fluids for abrasives Download PDF

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Publication number
SG187691A1
SG187691A1 SG2013008172A SG2013008172A SG187691A1 SG 187691 A1 SG187691 A1 SG 187691A1 SG 2013008172 A SG2013008172 A SG 2013008172A SG 2013008172 A SG2013008172 A SG 2013008172A SG 187691 A1 SG187691 A1 SG 187691A1
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Singapore
Prior art keywords
cutting
fluid
carrier fluid
grains
weight
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SG2013008172A
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Hans-Peter Seelmann-Eggebert
Andreas Senf
Markus Roesch
Joachim Bentele
Kati Schmidt
Udo Stefanowski
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Basf Se
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34Polyoxyalkylenes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04Elements
    • C10M2201/041Carbon; Graphite; Carbon black
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04Elements
    • C10M2201/05Metals; Alloys
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06Metal compounds
    • C10M2201/061Carbides; Hydrides; Nitrides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06Metal compounds
    • C10M2201/062Oxides; Hydroxides; Carbonates or bicarbonates
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C10M2209/1045Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/02Viscosity; Viscosity index
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09Characteristics associated with water
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02Pour-point; Viscosity index
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/22Metal working with essential removal of material, e.g. cutting, grinding or drilling

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Lubricants (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

Carrier fluids for abrasivesAbstractThe invention relates to improved novel fluids for abrasives, in particular cutting fluids, for wafer production, the use thereof and a method of cutting wafers. No suitable figure

Description

Carrier fluids for abrasives
Description
The invention relates to the use of modified polyglycols for producing carrier fluids for abrasives, novel carrier fluids for abrasives, in particular cutting fluids, the use of the carrier fluid in the removal of material, in particular in the cutting of wafers and also wafers produced with the aid of the cutting fluid.
Abrasives, also known as grinding agents or abrasive materials, are materials, preferably grains of hard material, which are utilized for removing a material. The use of abrasives as a dispersion in fluids, for example grinding fluids or cutting fluids, is known. Abrasives can in this way be used for polishing wafers, for example silicon wafers, and also for polishing plastics, for example for lenses. Furthermore, the use of abrasives in cutting fluids for cutting wafers is also known. Wafers are thin slices of semiconductors which are used, for example, in photovoltaics. Electronic components, especially integrated circuits, can be produced from wafers. The wafers generally comprise a brittle material, for example silicon, but may also be made of gallium arsenide or cadmium telluride, etc. Wafers are generally produced from cylindrical or cubic monocrystals or polycrystals which are sawn into the individual slices, viz. the wafers. The sawing (also referred as cutting or lapping) is an industrial practice carried out by wire sawing. This is a parting process using a thin wire as cutter and using unbounded cutting grains in a carrier fluid. The wire generally has a diameter of from 80 to 180 pm. It dips into a slurry of carrier fluid and cutting grain and draws the cutting grains adhering to the wire surface into the saw cut. The object/silicon block, known as ingot, to be sawn/lapped is cut by means of the cutting grains into wafers, with particles being removed from the solid to be cut. The carrier fluid for the cutting grains is applied together with the cutting grains as slurry via an immersion bath through which the wire runs or, in general, via nozzles. The carrier fluid has, inter alia, the task of effecting adhesion of the cutting grains to the wire and carrying particles of removed material from the solid to be parted. Furthermore, the carrier fluid has the task of providing cooling and transport of the abraded material through the saw cut.
A process for parting a workpiece, for example a wafer, by means of wire sawing is known from EP 1 757 419 A1; here, a slurry applied to the wire is used and the water content of at least part of the gaseous medium surrounding the slurry is regulated or controlled. Furthermore, the use of glycols as carrier substance is known from 40 EP 1757 419 A1.
A cutting oil comprising a) a polyether compound and b) silica particles and the use of this cutting oil composition for cutting an ingot using a wire saw, in particular for cutting silicon ingots, is known from DE 199 83 092 B4 and US 6,383,991 B1.
Water-based lubricants based on polyethers are known from EP 0 131 657 A1 and
US-A-4,828,735. Cutting fluids are likewise known from the Chinese patent application
CN 101205498 A; a reduction in the water uptake is not indicated here. The compounds specifically mentioned are polyalkyleneoxy compounds which are etherified with alcohols having from 1 to 4 carbon atoms.
EP 686 684 A1 discloses a sawing suspension comprising an abrasive material in an aqueous phase comprising one or more water-soluble polymers as thickeners.
US 2007/0010406 A1 discloses hydroxy polyethers as additives for aqueous cutting fluids which can be used, inter alia, for producing silicon wafers.
The known cutting fluids are generally based on an aqueous or water-soluble base.
However, the presence of water is disadvantageous because it can cause corrosion and it is also possible, for example, for hydrogen to be evolved when cutting silicon wafers as a result of reaction of water and silicon. An additional problem here is that silicate or polysilicate formation occurs on the wafer and in the slurry.
The known water-soluble systems, too, can comprise water and, owing io their microscopic properties, atiract water so that the same disadvantages as in aqueous systems can occur.
It was an object of the invention to provide improved carrier fluids for abrasives, in particular cutting fluids, which, in particular, lead to a reduction in the water uptake and a reduction in the energy required for sawing.
The invention provides for the use of compounds of the formula
R' [O (EO) (AO), Hl, where
R' is a z-valent alkyl radical having from 1 to 20 carbon atoms (EO) is an ethyleneoxy radical (AO) is an alkyleneoxy radical having from 3 to 10 carbon atoms
X is an integer from 3 to 12, in particular from 5 to 10 40 y is an integer from 0 to 10, in particular from 4 to 8 z is an integer from 1 to 6, in particular from 1 to 3, for producing carrier fiuids for abrasives, in particular cutting fluids, having a reduced water uptake for removal of material, in particular for sawing wafers by means of a wire saw,
The invention further provides carrier fluids for abrasives, in particular cutfing fluids, comprising at least one compound of the formula
R' [0 (EO): (AO), HI where
R! is a z-valent alkyl radical having from 5 to 10 carbon atoms (EQ) is an ethyleneoxy radical {AO) is an alkyleneoxy radical having from 3 to 10 carbon atoms
X is an integer from 3 to 12, in particular from 5 to 10 y is an integer from 0.5 to 10, in particular from 4 to 8 z is an integer from 1 to 6, in particular from 1 fo 3.
The invention further provides novel compounds Il of the formula
R' O (EO), (AQ), H where
R! is 2-methylbutyl or 3-methylbuty! (EO) is an ethyleneoxy radical (AO) is an alkyleneoxy radical having from 3 to 10 carbon atoms
X is an integer from 3 to 12, in particular from 5 to 10 y is an integer from 0 to 10, in particular from 4 to 8
Zz is an integer from 1 to 6, in particular from 1 to 3
In preferred compounds of the formula Il, at least as many EO units as PO units are present. Very particularly preferred compounds of the formula II are shown in the following table: (Compound [R[x | yy 2melhylbuty
Zmeftybutl | 50 | Go
In a preferred embodiment, the ratio of x to y in the compound of the formulae | and lI is equal to or less than 1.
For the purposes of the present invention, compounds of the formula Il are particularly preferred embodiments of compounds of the formuia I.
In a preferred embodiment, in formula I: R'is a pentyl radical, preferably
H3C-CHCH3-CH,-CHz- (3-methylbutyl) and
H3C-CHa-CHCHa-CHz~ (2-methylbutyl), in particular at least 10% of 3-methyibutyl
Informulae | and Il: AO is propyleneoxy, butyleneoxy and pentyleneoxy or a mixture thereof.
In the case of the compounds of the formulae | and li, the recurring units (FO) and (AO) can be present as a block or randomly distributed. In a preferred embodiment, they are randomly distributed. It has surprisingly been found that the viscosity of the compounds is largely independent of temperature when the recurring units (AO) and (EO) are randomly distributed. In particular, when the recurring units (EO) and (AQ) are randomly distributed, the compounds of the formula | to be used according to the invention have a viscosity index in a slurry comprising 40% by weight of silicon carbide of the type Carborex FF 800 PV from Washington Mills AS, NO-7300 Orkanger, Norway, of not more than 45%, preferably less than 30%, in particular less than 20%, with the viscosity index being defined as follows: the viscosity index is, for the purposes of the present invention, the percentage decrease in the viscosity of the compounds of the formula | at 50°C compared to the viscosity at 30°C. The viscosity here is the dynamic viscosity (Brookfield, spindle V-73) determined in accordance with DIN EN 12082.
The carrier fluids of the invention can not only comprise one compound of the formula but also mixtures of compounds of the formula I.
The preparation of compounds of the formula | is known per se, see, for example, Nonionic Surfactants, edited by Martin J. Schick, Volume 2, Chapter 4 (Marcel Dekker,
Inc., New York 1967). The preparation of the novel compounds of the formula Il can be carried out in an analogous way,
In a preferred embodiment, the carrier fluids for abrasives, in particular cutting fluids, 40 consist of the compound of the formula I. The molecular weight of the compound of the formula | is preferably from 200 io 1200 g/mol. In a further preferred embodiment, } alkylene alcohols based on ethylene oxides, propylene oxides or copolymers of ethylene oxides and propylene oxides, preferably having a molecular weight of from 200 fo 800 g/mol are comprised in addition to the compounds of the formufa I. In use 5 for sawing, the cutting fluid comprises abrasives, in particular cutting grains, in addition to the compound of the formula I.
In a further preferred embodiment, the carrier fluids for abrasives, in particular cutting fluids, are combined with at least one further additive, in particular with at least one monoalkylene, oligoalkylene or polyalkylene glycol, wetting agent, thickener, dispersant, corrosion inhibitor, complexing agent and/or other additives such as scale inhibitors to form a carrier fluid.
Preference is given to at least one of the following additives being added in the following parts by weight per 100 parts by weight of the compound I: alkylene glycols: from 10 to 90, in particular from 20 to 80, parts by weight wetting agent: from 1 to 100, in particular from 10 to 40, parts by weight thickener: from 0.5 to 20, in particular from 1 to 10, parts by weight dispersant: from 0.1 fo 20, in particular from 0.5 to 10, parts by weight corrosion inhibitor: from 0.1 to 10, in particular from 0.1 to 3, parts by weight complexing agent: from 0.1 to 10, in particular from 1 fo 5, parts by weight other additives: from 0.05 to 10, in particular from 0.1 to 5, parts by weight
The water content of the composition according to the invention is, based on the tofal composition, not more than 10% by weight, preferably not more than 5% by weight, in particular less than 1% by weight.
Particularly preferred additives are indicated below:
Wetting agents
In addition to the compounds of the formula 1 fo be used according to the invention, it is possible to use further wetting agents, in particular (1) Poly(oxyalkylene) derivatives of a) sorbitan esters, e. g. poly(oxyethylene)sorbitan monolaurate, poly(oxyethylene)sorbitan monooleate, poly(oxyethylene)sorbitan trioleate b} fatty amines, e.g. tallow amino ethoxylates, soy amino ethoxylates, c) castor oil, e.g. castor ofl ethoxylates, d) alkanolamidas, e.g. coconut oil alkanclamide ethoxylates, e) fatty acids, e.g. oleic acid ethoxylates, lauric acid ethoxylates, palmitic acid ethoxylates, f) fatty alcohols, a) linear alcohol ethoxylates, nony!phenol ethoxylates, octylphenol ethoxylates (2) Hydrophilic polydimethylsiloxanes a) poly(dimethyl)siloxane substituted by at least one carbonyl end group, poly(dimethyl)siloxane copolymers, c) poly(dimethylsiloxane)-b-poly(propylene oxide)-b-poly(ethylene oxide} copolymers, d) polyquarternary {dimethylsiloxane) copolymers (3) Fatty imidazolines (4) Fatty acid esters of a) phosphates, b) sorbitans, c) glycerol compounds, e.g. glyceryl monooleate, glyceryl dioleafe, glyceryl tricleate, dilaurate, e) sulfosuccinic acid, (5) Quaternary compounds e.g. quaternary ammonium methosulfate.
Further suitable nonionic, cationic, anionic or amphoteric wetting agents are, in particular
- alkoxylated C;-Cx-alcohols such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. These can be alkoxylated by ethylene oxide, propylene oxide and/or butylene oxide. All alkoxylated alcohols which have at least two molecules of one of the abovementioned alkylene oxides added on can be used as wetting agenis.
Possible compounds of this type are block polymers of ethylene oxide, propylene oxide andfor butylene oxide or addition products which comprise the abovementioned alkylene oxides distributed randomly or in blocks. The nonionic wetting agents generally comprise from 2 to 50 mol, preferably from 3 to 20 mol, of at least one alkylene oxide per mole of aicohol. The alcohols preferably have from 10 to 18 carbon atoms. Depending on the type of alkoxylation catalyst used in the preparation, the method of preparation and the work-up, the alkoxylates have a broad or narrow alkylene oxide homologue distribution; - alkylphenol alkoxylates such as alkyiphenol ethoxylates having Ce-Cis-alkyl chains and from 5 to 30 alkylene oxide units; -~ alkyl polygiucosides having from 8 to 22, preferably from 10 to 18, carbon atoms in the alkyl chain and generally from 1 to 20, preferably from 1.1 to 5, glucoside units, sorbitan alkanoates, also alkoxylated; - N-alkylglucamides, fatty acid alkoxylates, fatty acid amine alkoxylates, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates, alkoxylated, block copolymers of ethylene oxide, propylene oxide and/or butylene oxide, polyisobutene ethoxylates, polyisobutene-maleic anhydride derivatives, optionally alkoxylated monoglycerides, glyceryl monostearates, sorbitan esters and bisglycerides.
Particularly useful nonionic wetting agenis are alkyl alkoxylates or mixtures of alkyl alkoxylates, as are described, for example, in DE-A 102 43 363, DE-A 102 43 361,
DE-A 102 43 360, DE-A 102 43 365, DE-A 102 43 366, DE-A 102 43 362 or
DE-A 43 25 237. These are alkoxylation products obtained by reaction of alkanols with alkylene oxides in the presence of alkoxylation catalysts or mixtures of alkoxylation products. Particularly suitable starter alcohols are the Guerbet alcohols, in particular ethylhexanol, propylheptanol and butyloctanol. Particular preference is given fo propytheptanol. Preferred alkylene oxides are propylene oxide and ethylene oxide, with alkyl alkoxylates having a direct bond between a preferably short polypropylene oxide block and the starter alcohol, as are described, for example, in DE-A 102 43 365, being particularly preferred because of their low residual alcohol content and their good biodegradability.
A preferred class of suitable nonionic wetting agents are the alcohol alkoxylates of the general formula (NI)
R'-0-(CHz-CHR®-0-){CHz-CHg-0-)o(CHa-CHR-0-)(CHz-CHR?0-)nH (NI) where
R is an at least singly branched C4as-alkyl or -alkylphenal,
R? is Cay-alkyl,
R® is Cisalkyl,
R® is methy! or ethyl, n is an average value of from 1 to 50, m is an average value of from 0 to 20, preferably from 0.5 to 20, r is an average value of from 0 to 50,
Ss is an average value of from 0 fo 50, where n is at least 0.5 when R® is methyl or ethyl or ris 0.
A mixture of from 20 to 85% by weight, preferably from 30 to 95% by weight, of at least one abovementioned alkyl alkoxylate and from 5 to 80% by weight, preferably from 5 to 70% by weight, of a corresponding alcohol alkoxylate in which R' is, however, an unbranched alky! radical having the same number of carbon atoms is also possible.
Furthermore, alcohol alkoxylates of the general formula (Nil)
R®-0-(CHz-CHz-0), (CH-CHR*-0-);H (NII) where
R® is branched or unbranched C,.0-alkyl or -alkylphenol,
R'is Cys-alkyl, p is an average value of from 1 to 50, preferably from 4 to 15, q is an average value of from 0.5 to 20, preferably from 0.5 to 4, more preferably from 0.5 to 2, are also suitable.
A mixture of from 5 to 95% by weight of at least one branched alcohol alkoxylate (NII) as described directly above and from 5 to 95% by weight of a corresponding alcohol alkoxylate in which, however, an unbranched alkyi radical is present in place of a branched alkyl radical is also possible.
In the alcohol alkoxylates of the general formula (NI), R? is preferably propyl, in 40 particular n-propyl.
In the alcohol alkoxylates of the general formula (NII), n preferably has an average value of from 4 to 15, particularly preferably from 6 to 12, in particular from 7 to 10. m preferably has an average value from 0.5 to 4, particularly preferably from 0.5 fo 2, in particular frem 1 to 2.
The radical R' is preferably a Cg 15-, particularly preferably Ca.a-, in particular Ca.qp-alkyl radical which is at least singly branched. It is also possible for a plurality of branches te be present.
R® is preferably methyl or ethyl, in particular methyl.
R® is preferably ethyl.
In the mixtures, compounds having unbranched and branched alcohol radicals R' are present. This is the case, for example, for oxo alcohols which have a proportion of linear alcchol chains and a proportion of branched alcehol chains. For example, a Gias oxo alcohol frequently has about 60% by weight of completely linear alcohol chains together with about 40% by weight of a-methyl-branched and Cs-branched alcohol chains.
In the alcohol alkoxylates of the general formula (NI), R® is preferably a branched or unbranched Cgqs-alkyl radical, particularly preferably a branched or unbranched
Caa-alkyl radical and in particular a branched or unbranched Cs.1z-alkyl radical. R* is preferably propyl, in particular n-propyl. p preferably has an average value of from 4 to 15, particularly preferably an average value of from 6 to 12 and in particular an average value of from 7 to 10. q preferably has an average value of from 0.5 to 4, particularly preferably from 0.5 to 2, in particular from 1 to 2,
In a manner analogous to the alcohol alkoxylates of the general formula (NI), the alcohol alkoxylates of the general formula (NII) can also be present as mixtures having unbranched and branched alcohol radicals.
Possible alcohol components on which the alcohol alkoxylates are based include not only pure alkanols but also homolcgous mixtures having a range of carbon atoms.
Examples are Cgpp-alkanols, Cipnz-alkanols, Cqas-alkanocls, Cias-alkanols. Mixtures of a plurality of alkanols are also possible.
The above alkanol alkoxylates or mixtures according to the invention are preferably 40 prepared by reacting alcohols of the general formula R™-OH or R®-OH or mixiures of corresponding branched and unbranched alcohols optionally firstly with Cyg-alkylene oxide, then with ethylene oxide and subsequently optionally with Cs4-alkylene oxide and then with an appropriate Csg-alkylene oxide. The alkoxylations are preferably carried out in the presence of alkoxylation catalysts. In particular, basic catalysts such as potassium hydroxide are used here. The random distribution of the amounts of the alkylene oxides incorporated can be greatly restricted by means of specific alkoxylation catalysts such as modified bentonites or hydrotalcites as are described, for example, in
WO 95/04024, so that "narrow-range” alkoxylates are obtained.
In a particular embodiment of the present invention, the alkoxylates are alkoxylate mixiures comprising alkoxylates of the general formula (NII!)
CsH11CH(C3H7)CHa0(B )o(A)a(B)m{A)gH (NII) where
A is ethyleneoxy, the radicals B are each, independently of one another, Cs.p-alkyleneoxy, preferably propyleneoxy, butyleneoxy, pentyleneoxy or mixtures thereof, where groups A and B are present in the form of blocks in the order indicated, p is from 0 to 10, n is from > 0 to 20, m is from > 0. to 20, q is from > 0 fo 10, p+n+m+q is atleast, where from 70 to 99% by weight of alkoxylates A1 in which CsHyq is n-CsHyy and from 1 to 30% by weight of alkoxylates A2 in which CsH4; is CoHsCH(CH3)CH; and/or
CH3CH({CH3)CH2CH,,
are present in the mixture.
In the general formula (NIII), p is from 0 to 10, preferably from 0 to 5, in particular from 0 to 3. If blocks (B), are present, p is preferably from 0.1 to 10, particutarly preferably from 0.5 to 5, in particular from 1 to 3. in the general formula (Nill), n is preferably in the range from 0.25 fo 10, in particular from 0.5 to 7, and m is preferably in the range from 2 to 10, in particular from 3 fo 6. B is preferably propyleneoxy and/or butyleneoxy, especially propyleneoxy in both positions. q is preferably in the range from 1 fo 5, particularly preferably in the range from 2 to 3.
The sum p + n+ m + q is at least 1, preferably from 3 to 25, particularly preferably from 51io 15, in particular from 7 to 13.
Preference is given ioc 3 or 4 alkylene oxide blocks being present in the alkoxylates. In one embodiment, firstly ethyleneoxy units, then propylene oxide units and then ethyleneoxy units are adjoined to the alcohol radical. In a further embodiment, firstly propyleneoxy units, then ethyleneoxy units, then propyleneoxy units and finally ethyleneoxy units are adjoined to the alcohol radical. It is also possible for the other alkyleneoxy units indicated to be present in place of the propyleneoxy units. p, Nn, m and q are each a value averaged over the alkoxylates. For this reason, p, n, m, q can also have nonintegral values. The alkoxylation of alkanols generally gives a distribution of the degree of alkoxylation which can to a certain exient be set by use of different alkoxylation catalysts. The choice of appropriate amounts of the groups A and
B enables the property spectrum of the alkoxylate mixtures according to the invention to be matched to practical requirements.
The alkoxylate mixtures are obtained by alkoxylation of the parent alcohols
CsH1CH(C3sH7)CH,OH. The starting alcohols can be mixed from the individual components so {o as give the ratio according to the invention. They can be prepared by aldol condensation of valeraldehyde and subsequent hydrogenation. The preparation of valeraldehyde and the corresponding isomers is carried out by hydroformylation of bufene, as described, for example, in US 4,287 370; Beilstein E IV 1, 32 68, Ulimanns
Encyclopedia of Industrial Chemistry, 5th Edition, Volume A1, pages 323 and 328 ff.
The subsequent aldol condensation is described, for example, in US 5,434,313 and
Rompp, Chemie Lexikon, 9th Edition, keyword “Aldol-Addition”, page 21. The hydrogenation of the aldol condensation product follows general hydrogenation conditions.
Furthermore, 2-propylheptancl can be prepared by condensation of 1-pentanol (as mixture of the corresponding 1-methylbutanols) in the presence of KOH at elevated temperatures, see, for example, Marcel Guerbet, C.R. Acad Sci Paris 128, 511, 1002 (1899). Reference may also be made to Rémpp, Chemie Lexikon, 9th Edition, Georg
Thieme Verlag Stuttgart, and the references cited therein and also Tetrahedron, Vol. 23, pages 1723 to 1733. in the general formula (NHI), the radical CsHy4 can be n-CsHq4, C2HsCH(CH3)CH, or
CHaCH(CH3)CH,CH,. The alkoxylates are mixtures in which - from 70 to 89% by weight, preferably from 85 to 96% by weight, of alkoxylates A1 in which CsHyq4 is n-CsHy4 are present and - from 1 to 30% by weight, preferably from 4 to 15% by weight, of alkoxylates A2 in which CsHyq is CoHsCH(CH3)CH, and/or CH3CH{CH3)CH,CH; are present.
The radical CsHy is preferably n-CsHy.
The alkoxylates can also be block isotridecanol alkoxylates of the general formula (NV)
R-O-(CriHamO)(CpH20)-H (NV) where :
R is an isotridecyl radical, m is 2 and at the same time nis 3or4 or m is 3 or 4 and at the same time nis 2 and xandy are, independently of one another, from 1 to 20, where in the case of m = 2/n = 3 or 4, the variable x is greater than or equal fo y.
These block isotridecanol alkoxylates are described, for example, in DE 196 21 843
Al.
Another suitable class of nonionic surfactants are end-capped alcohol alkoxylates, in particular of alcohol alkoxylates mentioned above. In a particular embodiment, the end- capped alcohol alkoxylates are the end-capped alcohol alkoxylates corresponding to the alcohol alkoxylates of the general formulae {NI}, (NII}, {NIll) and (NV). The end cap can be produced, for example, by means of dialkyl sulfate, Ci.qe-alkyl halides,
Ciio-pheny! halides, preferably chlorides, bromides, particularly preferably cyclohexyl 40 chloride, cyclohexyl bromide, phenyl chloride or phenyl bromide.
Examples of end-capped alkoxylates are also described in DE-A 37 26 121, the entire relevant disclosure of which is incorporated by reference info the present invention. In a preferred embodiment, these alcohol alkoxylates have the general structure (NVI),
RL0O-(CH»-CHR"0)(CHz-CHR"0),RY (NVI) where
R is hydrogen or Cy-Cao-alkyl,
R'"and R" are identical or different and are each, independently of one another, hydrogen, methyl or ethyl,
RY is C4~Co-alkyl, preferably C;-C,-alkyl, or cyclohexyl or phenyl, m’ and n’ are identical or different and are each greater than or equal to 0, with the proviso that the sum of m' and n’ is from 3 to 300.
Another class of nonionic wetting agents are alkyl polyglucosides which preferably have from 6 to 22, particularly preferably from 10 to 18, carbon atoms in the alkyl chain.
These compounds generally comprise from 1 to 20, preferably from 1.1 to 5, glucoside units.
Further possible nonionic wetting agents are the end-capped fatty acid amide alkoxylates of the general formula
R-CO-NH- (CHa),-0- (A'0),-R? known from WO-A 85/11225, where
R' is a Cs-Ca-alkyl or alkenyl radical,
R* isa CrCsalkyl group,
Al is C;-Csalkylene, y is2or3and
X is from 1 fo 6.
Examples of such compounds are the reaction products of n-butyl triglycolamine of the formula HaN-(CHz-CH2-0)3-C4Hy with methyl dodecanoate or the reaction products of ethyl tetraglycolamine of the formula HaN-(CHz-CH.-O)4-C;Hs with a commercial mixture of saturated Cg-Cig methyl fatty acid esters.
Further suitable nonionic wetting agents are polyhydroxy or polyalkoxy fatty acid derivatives such as polyhydroxy fatty acid amides, N-alkoxy or N-aryloxy polyhydroxy fatty acid amides, fatty acid amide ethoxylates, in particular end-capped fatty acid amide sthoxylates, and also fatty acid alkanolamide alkoxylates.
Further suitable nonionic wetting agents are block copolymers of ethylene oxide, propylene oxide and/or butylene oxide (Pluronic® and Tetronic® grades from BASF SE and BASF Corp.). In a preferred embodiment, these copolymers are triblock copolymers having polyethylene/polypropylene/polyethylene blocks and a molecular weight of from 4000 to 16 000, with the proportion by weight of the polyethylene blocks being from 55 to 90%, based on the triblock copolymer. Particular preference is given to triblock copolymers having a molecular weight of more than 8000 and a polyethylens content of from 60 to 85% by weight, based on the triblock copolymer. These preferred triblock copolymers are, in particular, commercially available under the trade names
Pluronic F127, Pluronic F108 and Pluronic F98, in each case from BASF Corp., and are described in WO 01/47472 A2, the enfire relevant disclosure of which is incorporated by reference into the present invention.
In addition, preference is also given to using block copolymers of ethylene oxide, propylene oxide and/or butylene oxide capped at one or both ends. Capping at one end is achieved, for example, by using an alcohol, in particular a Cy.x-alkyl alcohol, for example methanol, as starting compound for the reaction with an alkylene oxide. In addition, two-ended end capping, for example, can be produced by reacting the free block copolymer with dialkyl sulfate, Cy.sp-alky! halides, Ci.qo-phenyl halides, preferably chlorides, bromides, particularly preferably cyclohexyl chloride, cyclohexyl bromide, phenyl chloride or phenyl bromide.
Individual nonionic wetting agents or a combination of different nonionic surfactants can also be used. It is possible to use nonionic wetting agents from only one class, in particular only alkoxylated C4-Cyp-alcohols. However, as an alternative, wetting agent mixtures from various classes can also be used.
The concentration of nonionic wetting agent in the composition according to the invention can vary as a function of the leaching conditions, in particular as a function of the material to be leached.
Suitable anionic wetting agents are alkanesulfonates such as Cg-Cy4-, preferably Cp-
Cig-alkanesulfonates, and also soaps such as the Na and K salts of saturated and/or unsaturated Cg Cos-carboxylic acids.
Further suitable anionic wetting agents are linear Cg-Czp-alkylbenzenesulfonates ("LAS"), preferably linear Cs-C4s-alkylbenzenesulfonates and -aikyltoluenesulfonates.
Thickeners
Thickeners are compounds which increase the viscosity of the chemical composition.
Nonlimiting examples are given, for example, in WO 2009/090162 A1: polyacrylates and hydrophobically modified polyacrylates. The advantage of the use of thickeners is that liquids having a relatively high viscosity have a higher residence time on inclined or vertical surfaces than liquid having a lower viscosity. This increases the interaction time between composition and surface.
Further particularly preferred thickeners are, for example, benfonite, xanthan and cellulose and also cellulose derivatives, in particular cellulose ethers and cellulose esters, in particular methylcellulose, hydroxyethylcellulose and carboxymethylcellulose.
Further examples of thickeners are polyacrylamides, polyethers or associative polyurethane thickeners, polyvinyl alcohols and polyvinylpyrrolidones.
Dispersants/scale inhibitors
Furthermore, it is possible, according to the invention, to make addiiional use of at least one dispersant, for example selected from the group consisting of salts of naphthalenesulfonic acids, condensation products of naphthalenesulfonic acids and formaldehyde and also polycarboxylates. Dispersants of this type are commercially available, for example, under the trade names Tamol®, Sokalan® and Nekal® from
BASF SE and under the trade name Solsperse® from Lubrizol. These dispersants may also act as scale inhibitors {deposit preventers) since they disperse the calcium carbonate CaCO; formed in alkaline medium and thus prevent, for example, blockage of nozzles or formation of deposits in pipes. Independently of this, the composition according fo the invention can additionally comprise at least one further scale inhibitor.
Suitable scale inhibitors are described, for example, in WO 04/0992092, which describes (meth)acrylic acid copolymers which comprise (@) from 50 to 80% by weight, preferably from 50 to 75% by weight, particularly preferably from 55 to 70% by weight, of a poly(meth)acrylic acid skeleton, % (b) from 1 to 40% by weight, preferably from 5 to 20% by weight, particularly preferably from 7 to 15% by weight, of at least one unit which is selected from the group consisting of isobutene units, terelactone units and isopropanol units and is bound to the skeleton and/or incorporated into the skeleton and
(c) from 5 to 50% by weight, preferably from 5 to 40% by weight, particularly preferably from 10 to 30% by weight, of amide units based on aminoalkylsulfonic acids, where the total weight of the units in the (meth)acrylic acid copolymer is 100% by weight and all percentages by weight are based on the (meth)acrylic acid copolymer.
The (meth)acrylic acid copolymers provided according to WO 04/099092 preferably have a weight average molecular weight of the polymer comprising sulfone groups of from 1000 to 20 000 g/mol and can preferably be prepared by means of the following process steps; (1) free-radical polymerization of (meth)acrylic acid in the presence of isopropanol and optionally water, resulting in a polymer 1, and (2) amidation of the polymer { from process step (1) by reaction with at least one amincalkanesulfonic acid.
Further suitable scale inhibitors are, for example: - semiamides of polycarboxylic acids, which can be obtained by reaction of polymers comprising anhydride groups with compounds comprising amino groups {as described in DE 195 48 318), - vinyllactic acid and/or isopropenyilactic acid (as described in DE 197 195 16), - homopolymers of acrylic acid (as described in US-A-3 756 257), - copolymers of acrylic acid and/or {meth)acrylic acid and vinyllactic acid and/or isopropenyllactic acid, - copolymers of styrene and vinyllactic acid, - copolymers of maleic acid and acrylic acid, - water-soluble or water-dispersible graft polymers, which can be obtained by free-radically initiated graft polymerization of (I) atleast one monoethylenically unsaturated monomer, (Hl) polymers having a molar mass of from 200 to 5000 g/mol of monoethylenically unsaturated dicarboxylic acids or anhydrides thereof, (11) where from 5 to 20 000 paris by weight of (1) are used per 100 parts by weight of the graft base (II) {DE 195 03 546), : - optionally hydrolyzed polymaleic anhydrides and salts thereof (as described in
US-A-3 810 834, GB-A-1 454 657 and EP-A-0 261 589), - iminodisuccinates (as described in DE 101 02 209), - formulations comprising complexing agents such as ethylenediaminetetraacetic 40 acid (EDTA) and/or diethylenetriaminepentaacetic acid (DTPA) (as described in
US 5,366,016),
- phosphonates, - polyacrylates, - polyaspariic acids or polyaspartic acids which have been modified as described in DE-A-44 34 463, - polyaspartimides, - polymers comprising hydroxamic acid, hydroxamic ether and/or hydrazide groups {as described in DE 44 27 630), - optionally hydrolyzed polymers of maleimide (as described in DE 43 42 930), - naphthylamine polycarboxylates (as described in EP 0 538 969), - oxaalkanepolyphosphonic acids (as described in EP 330 075), - polyhydroxyalkaneaminobismethylenephosphonic acids (as described in DE 40 16 753) and - oxidized polyglucosanes (as described in DE 43 30 339).
Particularly preferred dispersants are polyacrylic acid, for example the Sokalan® grades from BASF SE, and polyaspartic acids, in particular B-polyaspartic acids, having a molecular weight of from 2000 to 10000 g/mol. Preferred polymeric compounds comprising carboxylic acid groups are the acrylic acid homopolymers indicated in
EP 2083 067 Al. These preferably have a number average molecular weight in the range from 1000 to 50 000, particularly preferably from 1500 to 20 000. Homopolymers of acrylic acid which are particularly suitable as polymeric compounds comprising carboxylic acid groups are the Sokalan ® PA grades from BASF SE.
Further suitable polymeric compounds comprising carboxylic acid groups are oligomaleic acids as are described, for example, in EP-A 451 508 and EP-A 396 303.
Other compounds which are preferred as polymeric compounds comprising carboxylic acid groups are copolymers comprising at least one unsaturated monocarboxylic or dicarboxylic acid or a dicarboxylic anhydride or a salt thereof as monomer A) and at least one comonomer B) in copolymerized form. The monomer A) is preferably selected from among C;-Cio-monocarboxylic acids, salts of Cs-Cig-monocarboxylic acids, C4-Cs-dicarboxylic acids, anhydrides of C,-Cs-dicarboxylic acids, salis of
C,-Cp-dicarboxylic acids and mixtures thereof. Monomers A) in salt form are preferably used in the form of their water-soluble salts, in particular the alkali meifal salts such as potassium and especially sodium salts or the ammonium salts. The monomers A) can in each case be entirely or partly present in anhydride form. Of course, it is also possible to use mixtures of monomers A).
The monomers (A) are preferably selected from among acrylic acid, methacrylic acid, 40 crotonic acid, vinylacetic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, itaconic acid and mixtures thereof. Pardicularly preferred monomers A) are acrylic acid, methacrylic acid, maleic acid, maleic anhydride and mixtures thereof. These copolymers preferably comprise at least one monomer A) in an amount of from 5 to 895% by weight, particularly preferably from 20 to 80% by weight, in particular from 30 to 70% by weight, based on the fotal weight of the monomers used for the polymerization, in copolymerized form.
Corrosion inhibitors
The agents, e.g. carboxylic acids, indicated in, for example, WO 2008/071582 A1 act as corrosion inhibitors. These can be linear or branched. Mixtures of various carboxylic acids can be particularly preferred. Caprylic acid, ethylhexanoic acid, isononanocic acid and isodecanoic acid are particularly preferred carboxylic acids. Since corrosion protection emulsions are frequently neutral to weakly aikaline, it can be advantageous to use the carboxylic acids at least partly in neutralized form, i.e. as salt. Sodium hydroxide and/or potassium hydroxide and also alkanolamines are particularly suitable for neutralization. Particular preference is given to using monoalkanolamines and/or trialkanolamines. The use of dialkanclamines is less preferred because of the risk of formation of nitrosamines. Dialkanolamines can be used equally well either alone or together with monoalkanolarnines and/or trialkanolamines for neutralization.
Suitable corrosion inhibitors are, in particular:
Aliphatic carboxamides having from 14 to 36 carbon atoms, for example myristamide, palmitamide and oleamide; alkenylsuccinamides having from 6 to 36 carbon atoms, for example octenylsuccinamide, dodecenylsuccinamide; mercatobenzothiazoles.
Particularly preferred corrosion inhibitors are alkylene oxide adducts with aliphatic amines, in particular triethanolamines and ethylenediamine adducts with from 2 to 8 mol% of propylene oxide,
Complexing agents
Complexing agents are compounds which bind cations. Typical examples are: EDTA (N,N,N',N'-ethylenediaminetetraacetic acid), NTA (N,N,N-nitrilotriacetic acid), MGDA (2-methylglycine-N,N-diacetic acid), GLDA (glutamic acid diacetate), ASDA (aspartic acid diacetate), IDS (iminodisuccinate), HEIDA (hydroxyethylimine diacetate), EDDS
(ethylenediamine disuccinate), citric acid, oxodisuccinic acid and butanetetracarboxylic acid and completely or partially neutralized alkali metal or ammonium salts thereof.
Other Additives
Further suitable additives are, for example, bonding agents. Suitable bonding agents are, for example, the amphiphilic water-soluble alkoxylated polyalkyleneimines of the general formula Al indicated in WO 2008/018856 A2 tif
EN—RIFN—RIN—R NE, Al where the variables have the following meanings: the radicals R are identical or different, linear or branched C2-C6-alkyiene radicals;
B is a branch;
E is an alkyleneoxy unit of the formula 1 2 3 4 —{R-o otro {RoR where
R1 is 1,2-propylene, 1,2-butylene and/or 1,2-isobutylene;
R2 is ethylene;
R3 is 1,2-propylene;
R4 are identical or different radicals: hydrogen; C1-C4-alkyl;
Xx v.z are each from 2 to 150, where the sum x+y+z is the number of alkyleneimine units and corresponds to an average molecular weight Mw of the polyalkyleneimine before the alkoxylation of from 300 fo 10 000; m is a rational number from 0 fo 2; n is a rational number from 6 to 18; p is arational number from 3 to 12, where 0.8 < n/p < 1.0 (x+y+2)1/2.
The invention further provides a slurry composed of the carrier fluid, in particular cutiing fluid, abrasives, in particular grinding and/or cutting grains, and optionally additives.
It is possible to use the customary abrasives, in particular grinding and/or cutfing grains, for example metal, metal or semimetal, carbide, nitride, oxide, boride or diamond grains. Particularly preferred cutting grains are carbide and boride grains, in particular silicon carbide (SiC) grains. The culling grains preferably have a geometry matched to the materials and the wafers fo be cut. A preferred particle size is in the range from 0.5 io 50 um. The cutting grains can be present in heterodisperse or homodisperse form. The cutting grains are preferably comprised in the cutting fluid composition in a concentration of from 25 to 60% by weight, in particular from 40 to 50% by weight.
In a particularly preferred embodiment, the carrier fluid, in particular cutting fluid, has a contact angle to V2A steel of from 5 to 40°, in particular from 10 to 30°, The contact angle is determined here at 25°C on a steel plate made of V2A steel whose surface has been rinsed with water and acetone.
In a further preferred embodiment, the carrier fluids, in particular cutting fluids, of the invention lead to an average weight decrease over two tests of not more than 20-60 mg in one minute on a stainless steel cylinder MTMB/05R, Terrington, having a diameter of 12mm on a MDDZ2 balance from Hermann Reichert Maschinenbau, Heidenhof
Backnang, at a loading of 300 N and over a distance of 110 m.
In a further preferred embodiment, the carrier fluids, in particular cutting fluids, of the invention take up not more than 30%, preferably not more than 15%, of water after storage for 10 hours in a Heraeus BBD 6220 CO, incubator at 38°C and 78% relative atmospheric humidity. For the storage test, 1 g of carrier fluid, in particular cutting fluid, in Petri dishes having an internal diameter of 80 mm is used in each case. The average of a duplicate determination is determined in each case. [n a very particularly preferred embodiment, this water uptake does not increase even on further exposure.
A slurry composed of a carrier fluid, in particular cutting fluid, according to the invention and 40% by weight of the abrasives indicated below, In particular grinding and/or cutting grains, preferably has a viscosity measured at 30°C using a Brookfield LVDV4l
Ultra apparatus (spindle V-73) of from 140 to 200 mPas, in particular from 150 to 190 mPas, when Carborex BWF 800 PV silicon carbide grains from Washington Mills are used.
The invention further relates a method of cutting wafers of, in particular, inorganic semiconductors such as silicon ingots or silicon blocks by means of a wire saw using a slurry based on the cutting fluid of the invention and cutting grains.
The invention further relates to a method of grinding or polishing materials derived 40 from, for example, silicon ingots or blocks by, for example, chemomechanical polishing
(CMP) or of grinding polymers, in particular for lenses, using abrasives dispersed in a carrier fluid to be used according to the invention.
Advantages
The carrier fluid, in particular cutting fluid, of the invention and the cutting method of the invention are particularly suitable for sawing ingots, blocks or cylinders of monocrystalline or polycrystalline silicon single crystals or polycrystals, GaAs, CdTe and other semiconductors and ceramics.
The carrier fluid, in particular cutting fluid, of the invention displays little or no foaming, does not require any additives, is pH neutral and is nontoxic. In addition, it does not contain any volatile organic constituents. Furthermore, the carrier fluid, in particular cutting fluid, of the invention is highly suitable for reprocessing by means of a wet chemical work-up, for example as described in WO 02/40407 A1 and EP 1 390 184 A1.
Examples:
General method of preparing polyethers 1-2 mol of the starter alcohol were in each case placed in a water-free, dry 11 pressure reactor, admixed with 0.2% by weight (based on end product) of KOH and flushed with nifrogen. The closed reactor was then heated to 130°C over a period of 30 minutes and a gauge pressure of 1bar was set by means of nitrogen. The molar amounts of propylene oxide (hereinafter PO) and ethylene oxide (hereinafter EO) indicated in table 1 were subsequently metered in in parallel (random process) or in succession (block process} while stirring. In the block process, after PO had been added and a constant pressure had been reached, the mixture was stirred at 130°C for af least “4 hour and the pressure was set fo 1 bar before the addition of EO. The vessel was thermostated to 130°C during the reaction. After a constant pressure had been reached, the mixture was stirred for a further about % hour. After the reaction was complete, the mix was cooled to 80°C, the reactor was depressurized and flushed with nitrogen, the amount of glacial acetic acid calculated for neutralization of the KOH was added and the mixture was stirred for ¥ hour.
The OH number was determined in accordance with DIN 51562, the residual alcohol content was determined by means of gas chromatography and the APHA color number was determined in accordance with EN 1557 (at 23°C).
Table 1: Examples and analytical characterization
Product Chemical composition OH Residual Color (PO here is propyleneoxy, number | alcohol number
EO here is ethyleneoxy) %
Pluriol® E 200 | polyethylene glycol 200 560 DEG max30
Trem p—m———
C1 {3-methylbutan-1-ol) + 1.6 PO + 98.3 0.2 70 8.3EQ block process
C2 (3-methylbutan-1-o0l) + 5.5 PO + 5.5 | 87.0 <0.1 25
EO random process
C3 (3-Methylbutan-1-ol) + 6.0 PO + 5.0 | 85.7 <0.1 20
EO
Cb
C4 n-butan-1-ol + 5.5 PO + 5.5 EO 90.4 <0.1 30
Tf
C5 methyl diglycol + 8.8 EC/ 106.6/ 0.2/<0.1 | 60/50 (3-methyibutan-1-al) + 1.5 PO+7.0 | 112.4
EO in a weight ratio of 6/4 block process
C6 Pluronic® PE 6200/ 112.4 0.1 30 n-pentancl +1.5 PO + 6 EO in a weight ratio of 18/82 block process
C7 Plurafac® LF 401/ 126.2 0.1 25 n-pentanol + 1.5 PO +6 EO in a weight ratio of 3/7 block process
C8 n-hexancl + 5.5 PO + 5.5 EO 84.0 <0.1 20 © fae li.1 2-methylbutan-1-0l + 5.5 PO +55 | 85.2 < 0.1 20
EO random process
EO
Product Chemical composition OH Residual Color (PO here is propyleneoxy, number | aleohol number
EQ here is ethyleneoxy) % Jedempesess
The wetting agents and alkylene glycols Pluronic® PE 6200 and Plurafac® LF 401 added in examples CB and C7 are commercial products of BASF SE, Ludwigshafen.
The analytical data reported are based on the component pentanol + 1.5 PO + 6 EO according to the invention, block process.
Properties/determination of the characteristic values
The properties of the cutting fluids according fo the invention are summarized in table 2. The following properties were determined: » Water uptake
The water uptake of the cutting fluids was determined after storage in a Heraeus BBD 16 6220 CO: incubator at 38°C and 78% relative atmospheric humidity for a time of 10 hours and 24 hours. For storage, 1 g in each case of cutting fluid was used in Petri dishes having an internal diameter of 60 mm. The average of a duplicate determination was determined in each case. The water uptake is in each case reported in percent by weight increase based on the initial weight. « Slurry viscosity
To determine the slurry viscosity, a mixture of 60 percent by weight of the sawing fluid and 40 percent by weight of SiC of the type Carborex BW F 800 PV from Washington
Mills was produced and the viscosity was determined at 30°C and optionally 50°C using a model LVDV-l] Ultra viscosimeter from Brookfield (Spindle V-73). The slurry viscosity is reported in mPas. » Contact angle
The contact angle of the cutting fluids was determined at 25°C one second after application of a droplet to a steel plate made of V2A steel whose surface had been rinsed with water and acetone and subsequently dried in air for 1 hour. A video-aided high-speed contact angle measuring instrument from Dataphysics Instruments GmbH,
RaiffeisenstralRe 34, Filderstadt was used for the determination. The unit of the contact angle is °.
+ Abrasion
The abrasion behavior was determined on a frictional wear balance MDD2 from
Hermann Reichert Maschinenbau, Heidenhof Backnang, at a loading of 300 N and a test distance of 100 m in 54.5 sec. on a stainless steel cylinder M1MB/05R, Torrington having a diameter of 12 mm. A duplicate determination was carried out in each case and the average of the weight decrease of the cylinder was determined. The weight decrease is reported in mg. i0 Table2
Product H,O uptake 10h | Viscosity [mPas] | Contact angle | Abrasion
PuiGGED0 | | 205 (0
CR EX 3
Pluriol® E 200 is a polyethylene glycol having an average molar mass of 200 from
BASF SE, Ludwigshafen. The example represents the prior art and is not according to the invention. The compounds II.1 and }.2 gave results comparable to the compounds
C2 and C3.
Practical test
Sawing tests on polycrystalline silicon blocks were carried out on a DS 265 wire saw from Meyer Burger AG, Allmendstrasse 86, CH 3600 Thun using the sawing fiuids C1 and C3. The test conditions were:
Dimensions of the wafers: 5" x 5”, 150 um
SiC grade: F 88, ds50 = 6.5 um
Advance rate: 0.6 mm/s
Wire speed: 14 m/s
Wire diameter: 120 ym
Wire tension: 20N
Slurry temperature: 22°C
Composition of the slurry: 60% by weight of sawing fluid, 40% by weight of SiC
Compared to the PEG 200 (Pluricl® E 200) which is usually used in industrial practice, the following improvements were found for the cutting fluids according to the invention: TPwiwEa0| of | G3]
Power uptake per wire, [W] 29.5 24.0 268.5 (osmeeconon ||]
TTY, 5—point support, [%] 12.5 11.8 10.5 (vm moron
Similar improvements were also found when using the other products according to the © 10 invention shown in table 1.

Claims (15)

Claims
1. The use of compounds of the formula [ R" [O (EO), (AO), Hl, where R! is a z-valent alkyl radical having from 1 to 20 carbon atoms (EO) is an ethyleneoxy radical (AO) is an alkyleneoxy radical having from 3 to 10 carbon atoms X is an integer from 3 fo 12, in particular from 5 to 10 y is an integer from 0 to 10, in particular from 4 to 8 z is an integer from 1 to 6, in particular from 1 to 3, for producing carrier fluids for abrasives, in particular cutting fluids, having a reduced water uptake for removal of material, in particular for sawing wafers by means of a wire saw.
2. The use according to claim 1, wherein, in the formula I, R! is a z-valent alky! radical having from 5 to 10 carbons, in particular pentyl.
3. The use according to at least one of the preceding claims, wherein the contact angle of the cutting fluid on V2A steel at 25°C is from 25 to 50°.
4. The use according to at least one of the preceding claims, wherein the wafer is a semiconductor, in particular silicon.
5. The use according fo at least one of the preceding claims, wherein the carrier fluid, in particular cutfing fluid, is used in a slurry together with cutting grains, where metal, carbide, nitride, metal oxide, boride or diamond grains are used as cutting grains.
6. The use according to at least one of the preceding claims, wherein the carrier fluid, in particular cutting fluid, is worked up to separate off the resulting abraded 40 material during or after removal of the material, in particular after cutting.
7. A carrier fluid, in particular cutting fluid, comprising at least one compound of the formula R' [O (EO), (AO), Hl, where R' is a z-valent alkyl radical having from 5 to 10 carbon atoms (EO) is an ethyleneoxy radical (AQ) is an alkyleneoxy radical having from 3 to 10 carbon atoms X is an integer from 3 to 12, in particular from 5 to 10 y is an integer from 0.5 to 10, in particular from 4 to 8 z is an integer from 1 to 6, in particular from 1 to 3.
8. The carrier fluid, in particular cutfing fiuid, according to claim 7, wherein R! is pentyl.
8. The carrier fluid, in particular cuiting fluid, according to claim 7, wherein the contact angle of the carrier fluid, in particular cutting fluid, on V2A steel at 25°C is from 25 to 50°.
10. The use of a carrier fluid, in particular cutting fluid, according to at least one of the preceding claims for the removal of material, in particular during sawing of wafers, from an object to be cut, in particular semiconductor, in particular silicon, by means of a saw using cutting grains, in particular siticon carbide grains.
11. The use of a carrier fluid according to at least one of the preceding claims for polishing materials, in particular for polishing wafers of silicon or of materials composed of polymers, in particular for lens production.
12. A method of cutting wafers from an object by means of a saw using a slurry composed of a cutting fluid and cutting grains, in particular cutting grains composed of metal, a carbide, nitride, oxide, boride, a-alumina or diamond, wherein the cutting fluid is a cutting fluid according to at least one of the preceding claims which is optionally worked up to separate off the resulting abraded material during or after removal of the material, in particular after cutting.
13. A method of polishing materials, in particular materials composed of silicon or polymers, using a slurry composed of a carrier fluid and abrasive materials, wherein a carrier fluid according to at least one of the preceding claims is used as carrier fluid.
14. A wafer, in particular silicon wafer, obtained according to at least one of the preceding claims.
15. A compound of the formula II R' 0 (EO), (AQ), H where R! is 2-methylbutyl or 3-methylbutyf and (EQ), (AO), xandy are as defined in claim 1.
SG2013008172A 2010-08-03 2011-08-02 Carrier fluids for abrasives SG187691A1 (en)

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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG10201606190WA (en) * 2012-02-01 2016-09-29 Basf Se Cooling and/or lubricating fluids for wafer production
JP6266337B2 (en) * 2013-12-25 2018-01-24 ニッタ・ハース株式会社 Wetting agent for semiconductor substrate and polishing composition
US20190062670A1 (en) * 2016-02-10 2019-02-28 B Food Science Co., Ltd. Cutting fluid, cutting method, and smoothness improver for cut surface
CN108998188A (en) * 2018-09-10 2018-12-14 洛阳阿特斯光伏科技有限公司 A kind of silicon wafer cut by diamond wire coolant liquid and its preparation method and application

Family Cites Families (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1369429A (en) 1970-11-30 1974-10-09 Ciba Geigy Ag Treatment of water or aqueous systems
US3756257A (en) 1971-10-04 1973-09-04 Magna Corp Acrylic composition for water treatment and process for making same
GB1454657A (en) 1974-04-30 1976-11-03 Ciba Geigy Uk Ltd Method and composition for inhibitng the formation of scale from saline water
DE16286T1 (en) 1979-03-21 1983-05-11 Davy Mckee (London) Ltd., London HYDROFORMYLATION PROCESS.
JPS58122993A (en) 1982-01-19 1983-07-21 Nippon Oil & Fats Co Ltd Aqueous lubricating oil composition
DE3631815A1 (en) 1986-09-19 1988-03-31 Basf Ag METHOD FOR PRODUCING POLYMAL ACID
DE3726121A1 (en) 1987-08-06 1989-02-16 Basf Ag Etherification of polyoxyalkylene derivatives
DE3805663A1 (en) 1988-02-24 1989-09-07 Henkel Kgaa OXAALKANPOLYPHOSPHONIC ACIDS, THEIR USE THRESHOLDER AND COMPOUNDS COMPLEXING THESE COMPOUNDS
ES2069004T3 (en) 1989-04-28 1995-05-01 Nippon Catalytic Chem Ind PROCEDURE FOR THE PRODUCTION AND USE OF IMPROVED MALEIC ACID (CO) POLYMER SALT AS TO BIODEGRADABILITY.
DE4008696A1 (en) 1990-03-17 1991-09-19 Basf Ag METHOD FOR THE PRODUCTION OF HOMO- AND COPOLYMERISES OF MONOETHYLENICALLY DISPRODUCED DICARBONE ACIDS AND THEIR USE
DE4016753A1 (en) 1990-05-25 1991-11-28 Henkel Kgaa Poly:hydroxy:alkan:amino-bis(methylene:phosphonic acid) cpds. - useful as complexing agents, and prevent scaling e.g. machine cleaning and washing plant
US5139702A (en) 1991-10-24 1992-08-18 W. R. Grace & Co.-Conn. Naphthylamine polycarboxylic acids
GB9207756D0 (en) 1992-04-07 1992-05-27 Davy Mckee London Process
DE4325237A1 (en) 1993-07-28 1995-02-02 Basf Ag Process for the preparation of alkoxylation products in the presence of mixed hydroxides modified with additives
DE4330339A1 (en) 1993-09-08 1995-03-09 Henkel Kgaa Carbohydrate-based scale inhibitor
DE4336247A1 (en) 1993-10-22 1995-04-27 Basf Ag Use of end-capped fatty acid amide alkoxylates
US5366016A (en) 1993-12-10 1994-11-22 Mobil Oil Corporation Use of variable density carrier fluids to improve the efficiency of scale dissolution
DE4342930A1 (en) 1993-12-16 1995-06-22 Basf Ag Process for the preparation of maleimide polymers and their use
EP0686684A1 (en) 1994-06-06 1995-12-13 Bayer Ag Slicing slurry
DE4427630A1 (en) 1994-08-04 1996-02-08 Basf Ag Process for the preparation of polymers containing hydroxamic acid, hydroxamic acid ether and / or hydrazide groups in the side chain and their use
DE4434463A1 (en) 1994-09-27 1996-03-28 Basf Ag Process for the preparation of modified polyaspartic acids
DE19503546A1 (en) 1995-02-03 1996-08-08 Basf Ag Water-soluble or water-dispersible graft polymers, processes for their preparation and their use
DE19548318A1 (en) 1995-12-22 1997-06-26 Basf Ag Biodegradable poly:carboxylic acid hemi:amide scale inhibitors
DE19621843A1 (en) 1996-05-30 1997-12-04 Basf Ag Block-shaped iso-tridecanol alkoxylates as low-foam or foam-suppressing surfactants
JPH1053789A (en) * 1996-08-12 1998-02-24 Nippei Toyama Corp Water-base working fluid composition for wire cutter
DE19719516A1 (en) 1997-05-09 1998-11-12 Basf Ag Easily prepared water-soluble copolymers of vinyl-lactic and/or iso-propenyl-lactic acid
WO1999051711A1 (en) 1998-04-03 1999-10-14 Kao Corporation Cutting oil composition
JP4213260B2 (en) * 1998-07-31 2009-01-21 花王株式会社 Cutting oil composition
JP4170436B2 (en) * 1998-05-08 2008-10-22 花王株式会社 Cutting oil for wire saw
JP4237291B2 (en) * 1998-04-03 2009-03-11 花王株式会社 Cutting fluid for wire saw
JP2000192093A (en) * 1998-12-24 2000-07-11 Lion Corp Detergent composition
US6054422A (en) * 1999-02-19 2000-04-25 Ppt Research, Inc. Cutting and lubricating composition for use with a wire cutting apparatus
US6342206B1 (en) 1999-12-27 2002-01-29 Sridhar Gopalkrishnan Aqueous gels comprising ethoxylated polyhydric alcohols
DE10056957C1 (en) 2000-11-17 2002-09-05 Metallkraft As Kristiansand Process for manufacturing non-oxide ceramics
DE10102209A1 (en) 2001-01-19 2002-07-25 Bayer Ag Inhibiting or removing scale, in oil and gas exploration systems, involves using aqueous solution of iminodisuccinate
EP1561557B1 (en) 2001-05-29 2011-03-30 MEMC ELECTRONIC MATERIALS S.p.A. Method for treating an exhausted glycol-based slurry
DE10243363A1 (en) 2002-09-18 2004-04-01 Basf Ag Alkoxylate mixture used as emulsifier, foam regulator and wetting agent, e.g. in detergent, humectant, cosmetic, pharmaceutical, plant protection, coating or emulsion polymerization, contains alkoxylates of 2-propyl-heptan-1-ol isomers
DE10243361A1 (en) 2002-09-18 2004-04-01 Basf Ag Alkoxylate mixture used in laundry and cleaning detergents for washing and cleaning textiles contains alkoxylates of alkanols with different chain lengths with ethylene oxide and optionally other alkylene oxide(s)
DE10243360A1 (en) 2002-09-18 2004-04-01 Basf Ag New and known 2-propyl-heptan-1-ol alkoxylates, used e.g. in cleaning, coating, adhesive, textile treatment, cosmetic, pharmaceutical or plant protection formulations, contain ethylene oxide and other alkylene oxide groups
DE10243362A1 (en) 2002-09-18 2004-04-01 Basf Ag Production of alkoxylates useful as emulsifiers, foam regulators or wetting agents comprises using a binary metal cyanide catalyst and a defined reaction temperature
DE10243365A1 (en) 2002-09-18 2004-04-01 Basf Ag Composition containing propoxylated and ethoxylated alkanol, useful as surfactant in e.g. cleaning compositions and pharmaceuticals, has low free alcohol content
DE10243366A1 (en) 2002-09-18 2004-04-01 Basf Ag Production of alkoxylates useful as emulsifiers, foam regulators or wetting agents comprises using a defined inert gas and ethylene oxide pressure in the induction phase
US20070010406A1 (en) 2003-03-24 2007-01-11 Sanyo Chemical Industries, Ltd. Lubricant for water-miscible metal working oil
DE10320388A1 (en) 2003-05-06 2004-11-25 Basf Ag Polymers for water treatment
CN101160385B (en) 2005-04-15 2011-11-16 巴斯福股份公司 Amphiphilic water-soluble alkoxylated polyalkylenimines with an internal polyethylene oxide block and an external polypropylene oxide block
EP1757419B1 (en) 2005-08-25 2012-10-17 Freiberger Compound Materials GmbH Method, apparatus and slurry for wire sawing
US20070167335A1 (en) * 2006-01-13 2007-07-19 Bayer Materialscience Llc Water-miscible metal working fluids with reduced aerosol inhalation toxicity
US20070167336A1 (en) * 2006-01-13 2007-07-19 Bayer Materialscience Llc Water-miscible metal working fluids with reduced aerosol inhalation toxicity
BRPI0720231A2 (en) 2006-12-14 2013-12-24 Basf Se CHEMICAL COMPOUND, EMULSIFIER, CONCENTRATED IN EMULSION, EMULSION, AND USE OF A CONCENTRATE IN EMULSION OR AN EMULSION
CN101205498B (en) * 2007-12-17 2010-06-09 辽宁奥克化学股份有限公司 Cutting fluid for hard brittle material and uses thereof
EP2237874B1 (en) 2008-01-15 2012-05-30 Basf Se Fragrance-containing microcapsules with improved release properties
EP2083067A1 (en) 2008-01-25 2009-07-29 Basf Aktiengesellschaft Use of organic complexing agents and/or polymeric compounds containing carbonic acid groups in a liquid washing or cleaning agent compound
CN101712907A (en) * 2009-08-26 2010-05-26 辽阳科隆化学品有限公司 Composition and application combination of water-soluble silicon material cutting fluid

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ES2525017T3 (en) 2014-12-16
AU2011287623A1 (en) 2013-02-21
WO2012016976A1 (en) 2012-02-09
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JP5543030B2 (en) 2014-07-09
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JP2013534262A (en) 2013-09-02
CA2806936A1 (en) 2012-02-09
AU2011287623B9 (en) 2014-11-06
EP2601280B1 (en) 2014-10-08
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CN103154214A (en) 2013-06-12
BR112013002486A2 (en) 2016-05-31

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