EP2601280B1 - Carrier fluids for abrasives - Google Patents

Description

The invention relates to the use of modified polyglycols for the production of carrier liquids for abrasives, new carrier liquids for abrasives, in particular cutting fluids, the use of the carrier liquid in the removal of material, in particular when cutting wafers as well as wafers produced with the aid of the cutting fluid.

Abrasives, also called abrasives or abrasives, are substances, preferably hard-material grains, which are used for the removal of a material. It is known to use abrasives as a dispersion in liquids, for example grinding or cutting fluids. Abrasives can be used in this way for polishing wafers, for example made of silicon, but also for polishing plastics, for example for lenses. It is also known to use abrasives in cutting fluids for cutting wafers. Wafers are thin slices of semiconductors that are used, for example, in photovoltaic. From wafers electronic components, especially integrated circuits can be produced. The wafers are usually made of brittle material, such as silicon, but also of gallium arsenide or cadmium telluride, etc. Basis for the wafer production are usually cylindrical or cubic single or polycrystals, which are sawed into the individual slices, the wafer. Sawing (also referred to as cutting or lapping) is done in practice by wire sawing. This is a separation process using a thin wire as a cutting edge and using unbound cutting grains in a carrier liquid. The wire usually has a diameter of 80 to 180 microns. He immersed in a slurry of carrier liquid and cutting grain and pulls the hanging on the wire surface cutting grains in the kerf. The cutting grains are used to cut the wafer / lapping object / ingot called ingot into wafers, particles being removed from the solid to be cut. The carrier liquid for the cutting grains is applied as a slurry via a dipping bath, through which the wire runs, as well as generally via nozzles together with the cutting grain. Among other things, the carrier liquid has the task of ensuring that the cutting grains adhere to the wire and removing removed particles from the solid to be broken up. Furthermore, the carrier liquid has the task to provide for cooling and the transport of the abrasion through the Sägeschlitz.

From the EP 1 757 419 A1 is already a method for separating a workpiece, such as a wafer, known by means of wire saws, one on the wire applied slurry is used and the water content of at least a portion of the slurry surrounded gaseous medium is regulated or controlled. From the EP 1 757 419 A1 is also known to use as a carrier glycols.

From the DE 199 83 092 B4 and the US 6,383,991 B1 is a cutting oil comprising a) a polyether compound and b) silica particles, and the use of this cutting oil composition for cutting a billet using a wire saw, particularly for cutting silicon ingots.

From the EP 0 131 657 A1 and the US-A-4,828,735 are known water-based lubricants based on polyethers. From the Chinese patent application CN 101205498 A Cutting fluids are also known, with a reduction in water absorption is not specified. The specifically listed compounds are polyalkyleneoxy compounds which have been etherified with alcohols having 1 to 4 carbon atoms.

From the EP 686 684 A1 is a Sägesuspension consisting of an abrasive in the aqueous phase known which contains one or more water-soluble polymers as thickeners. From the US 2007/0010406 A1 Hydroxypolyethers are known as additives for aqueous cutting fluids, which can be used inter alia for the production of Siliziumwafem.

The known cutting fluids are generally based on an aqueous or a water-soluble basis. However, the presence of water is disadvantageous because it both causes corrosion and, for example, when cutting silicon wafers by reaction of water and silicon hydrogen evolution can take place. In this case, there is the additional problem that there is a silicate or polysilicate formation on the wafer and in the slurry.

The known water-soluble systems can also contain water and, because of their microscopic properties, attract water, so that the same disadvantages can occur as with aqueous systems.

The object of the invention was to provide improved carrier liquids for abrasives, in particular cutting fluids, which in particular lead to a reduction in water absorption and a reduction in the energy required for sawing.

R¹

ein z-wertiger Alkylrest mit 1 bis 20 C-Atomen

(EO)

Ethylenoxyrest

(AO)

Alkylenoxyrest mit 3 bis 10 C-Atomen

x

eine Zahl von 3 bis 12, insbesondere 5 bis 10

y

eine Zahl von 0 bis 10, insbesondere 4 bis 8

z

eine Zahl von 1 bis 6, insbesondere 1 bis 3

zur Herstellung von Trägerflüssigkeiten für Abrasiva, insbesondere Schneidflüssigkeiten mit reduzierter Wasseraufnahme zum Abtragen von Werkstoff, insbesondere zum Sägen von Wafern mit einer Drahtsäge, mit einem Wassergehalt von weniger als 1 Gew.-%.The invention relates to the use of compounds of the formula I.

R ¹ [O (EO) _x (AO) _y H] _z

in which mean

R ¹

a z-valent alkyl radical having 1 to 20 carbon atoms

(EO)

Ethylenoxyrest

(AO)

Alkyleneoxy having 3 to 10 carbon atoms

x

a number from 3 to 12, especially 5 to 10

y

a number from 0 to 10, especially 4 to 8

z

a number from 1 to 6, especially 1 to 3

for the production of carrier liquids for abrasives, in particular cutting fluids with reduced water absorption for the removal of material, in particular for sawing of wafers with a wire saw, with a water content of less than 1 wt .-%.

R¹

ein z-wertiger Alkylrest mit 5 bis 10 C-Atomen

(EO)

Ethylenoxyrest

(AO)

Alkylenoxyrest mit 3 bis 10 C-Atomen

x

eine Zahl von 3 bis 12, insbesondere 5 bis 10

y

eine Zahl von 0,5 bis 10, insbesondere 4 bis 8

z

eine Zahl von 1 bis 6, insbesondere 1 bis 3, mit einem Wassergehalt von weniger als 1 Gew.-%.

The invention further relates to carrier liquids for abrasives, in particular cutting fluids, consisting of at least one compound of the formula I.

R ¹ [O (EO) _x (AO) _y H] _z

in which mean

R ¹

a z-valent alkyl radical having 5 to 10 carbon atoms

(EO)

Ethylenoxyrest

(AO)

Alkyleneoxy having 3 to 10 carbon atoms

x

a number from 3 to 12, especially 5 to 10

y

a number from 0.5 to 10, especially 4 to 8

z

a number from 1 to 6, in particular 1 to 3, with a water content of less than 1 wt .-%.

R¹

2-Methylbutyl oder 3-Methylbutyl

(EO)

Ethylenoxyrest

(AO)

Alkylenoxyrest mit 3 bis 10 C-Atomen

x

eine Zahl von 3 bis 12, insbesondere 5 bis 10

y

eine Zahl von 0,5 bis 10, insbesondere 4 bis 8 neue Seite

The invention further relates to novel compounds II of the formula

R ¹ O (EO) _x (AO) _y H

in which mean

R ¹

2-methylbutyl or 3-methylbutyl

(EO)

Ethylenoxyrest

(AO)

Alkyleneoxy having 3 to 10 carbon atoms

x

a number from 3 to 12, especially 5 to 10

y

a number from 0.5 to 10, especially 4 to 8 new page

In preferred compounds of the formula II, at least as many EO units as PO units are present. Very particularly preferred compounds of the formula II are given in the following table: connection R ¹ x y II.1 2-methylbutyl 5.5 5.5 II.2 2-methylbutyl 5.0 6.0

In a preferred embodiment, the ratio x to y in the compound of the formula I and II is equal to or less than 1.

In the context of the present invention, compounds of the formula II are particularly preferred embodiments of compounds of the formula I.

In a preferred embodiment in formula 1: R ^{1 is} pentyl, preferably
H ₃ C-CHCH ₃ -CH ₂ -CH ₂ - (3-methylbutyl) and
H ₃ C-CH ₂ -CHCH ₃ -CH ₂ - (2-methylbutyl), in particular at least 10% of 3-methylbutyl in formulas I and II: AO propyleneoxy, butyleneoxy and pentyleneoxy or mixtures thereof.

In the case of the compounds of the formulas I and II, the recurring units (EO) and (AO) can be present as a block or randomly distributed (random). In a preferred embodiment, they are statistically distributed. Surprisingly, it has been found that in the case of statistical distribution of the recurring units (AO) and (EO), the viscosity of the compounds is largely independent of temperature. Particularly in the case of statistical distribution of the recurring units (EO) and (AO), the compounds of the formula I to be used according to the invention are distinguished by a viscosity index in a slurry with 40% by weight of Carborex F 800 PV silicon carbide from Washington Mills AS, NO -7300 Orkanger, Norway, of not more than 45%, preferably less than 30%, in particular less than 20%, the viscosity index being defined as follows: The viscosity index in the context of the present invention denotes the percentage decrease in the viscosity of the compounds of the formula I. at 50 ° C compared to the viscosity at 30 ° C. The viscosity here is the dynamic viscosity (Brookfield, spindle V-73) determined according to DIN EN 12092.

The carrier liquids according to the invention may contain not only a compound of the formula I but also mixtures of compounds of the formula I.

The preparation of compounds of formula I per se is known, see, for. B. Nonionic Surfactants, edited by Martin J. Schick, Volume 2, Chapter 4 (Marcel Dekker, Inc., New York 1967 ). The preparation of the novel compounds of formula II can be carried out in an analogous manner.

In a preferred embodiment, the carrier liquids for abrasives, in particular cutting fluids, consist of the compound of the formula I. The molecular weight of the compound of the formula I is preferably from 200 to 1200 g / mol. In a further preferred embodiment, in addition to the compounds of the formula I, alkylene alcohols based on ethylene oxides, propylene oxides or copolymers of ethylene and propylene oxides are present, preferably having a molecular weight of from 200 to 800 g / mol. In addition to the compound according to formula I, the cutting fluid in use for sawing contains abrasives, in particular cutting grains.

In a further preferred embodiment, the carrier liquids for abrasives, in particular cutting fluids, are combined with at least one further additive, in particular with at least one
Mono-, oligo- or polyalkylene glycol
Wetting agents,
Thickeners,
dispersants,
Corrosion inhibitor,
Complexing agent and / or
other additives such as scaling inhibitors
to form a carrier fluid (carrier fluid).

• Alkylenglykole: 10 bis 90, insbesondere 20 bis 60 Gewichtsteile
• Netzmittel: 1 bis 100, insbesondere 10 bis 40 Gewichtsteile
• Verdicker: 0,5 bis 20, insbesondere 1 bis 10 Gewichtsteile
• Dispergiermittel: 0,1 bis 20, insbesondere 0,5 bis 10 Gewichtsteile
• Korrosionsinhibitor: 0,1 bis 10, insbesondere 0,1 bis 3 Gewichtsteile
• Komplexbildner: 0,1 bis 10, insbesondere 1 bis 5 Gewichtsteile
• Sonstige Additive: 0,05 bis 10, insbesondere 0,1 bis 5 Gewichtsteile

Preferably, for at least 100 parts by weight of compound I, at least one of the following additives is added to the following parts by weight:

• Alkylene glycols: 10 to 90, especially 20 to 60 parts by weight
• Wetting agent: 1 to 100, especially 10 to 40 parts by weight
• Thickener: 0.5 to 20, in particular 1 to 10 parts by weight
• Dispersant: 0.1 to 20, especially 0.5 to 10 parts by weight
• Corrosion inhibitor: 0.1 to 10, in particular 0.1 to 3 parts by weight
• Complexing agent: 0.1 to 10, in particular 1 to 5 parts by weight
• Other additives: 0.05 to 10, in particular 0.1 to 5 parts by weight

The water content of the composition according to the invention is, based on the total composition, not more than 10, preferably not more than 5, in particular less than 1 wt .-%.

Particularly preferred additives are given below:

wetting agent

1. (1) Poly(oxyalkylen)derivate von
   1. a) Sorbitanestern, z. B. Poly(oxyethylen)sorbitanmonolaurat, Poly(oxyethylen)sorbitanmonooleat, (Poly(oxyethylen)sorbitantrioleat)
   2. b) Fettaminen, z. B. Talgaminooxyethylate, Soyaaminooxyethylate,
   3. c) Rizinusöl, z.B. Rizinusöloxyethylate,
   4. d) Alkanolamide, z. B. Kokosnussölalkanolamidoxyethylate
   5. e) Fettsäuren, z. B. Ölsäureoxyethylate, Laurinsäureoxyethylate, Palmetinsäureoxyethylate
   6. f) Fettsäurealkohole
   7. g) Lineare Alkoholoxyethylate, Nonylphenoloxyethylate, Octylphenoloxyethylate
2. (2) hydrophile Polydimethylsiloxane
   • a) mit wenigstens einer Carbonylendgruppe substituiertes Poly(dimethyl)siloxan, Poly(dimethylsiloxan)copolymere
   • c) Poly(dimethylsiloxan)-b-Poly(propylenoxid)-b-poly(ethylenoxid)-copolymere
   • d) Polyquarternäre(dimethylsiloxan)-copolymere
3. (3) Fettimidazoline
4. (4) Fettsäureester von
   • a) Phosphaten
   • b) Sorbitanen
   • c) Glycerinverbindungen, z. B.
   • Glycerylmonooleat, Glyceryldioleat, Glyceryltrioleat, Dilaurat e) Sulphobernsteinsäure
5. (5) Quarternäre Verbindungen, z. B.
   quarternäres Ammoniumethosulfat.

In addition to the compounds of the formula I to be used according to the invention, further wetting agents can be used, in particular

1. (1) poly (oxyalkylene) derivatives of
   1. a) sorbitan esters, e.g. Poly (oxyethylene) sorbitan monolaurate, poly (oxyethylene) sorbitan monooleate, (poly (oxyethylene) sorbitan trioleate)
   2. b) fatty amines, e.g. Tallow aminooxyethylates, soya aminooxyethylates,
   3. c) castor oil, eg castor oil oxyethylates,
   4. d) alkanolamides, e.g. Coconut oil alkanolamidooxyethylates
   5. e) fatty acids, e.g. B. Olesäureoxyethylate, Laurinsäureoxyethylate, Palmetinsäureoxyethylate
   6. f) fatty alcohols
   7. g) Linear alcoholoxyethylates, nonylphenoloxyethylates, octylphenoloxyethylates
2. (2) hydrophilic polydimethylsiloxanes
   • a) poly (dimethyl) siloxane, poly (dimethylsiloxane) copolymers substituted with at least one carbonyl end group
   • c) poly (dimethylsiloxane) -b-poly (propylene oxide) -b-poly (ethylene oxide) copolymers
   • d) Polyquaternary (dimethylsiloxane) copolymers
3. (3) fatty imidazolines
4. (4) fatty acid esters of
   • a) phosphates
   • b) sorbitans
   • c) glycerol compounds, e.g. B.
   • Glyceryl monooleate, glyceryl dioleate, glyceryl trioleate, dilaurate e) sulphosuccinic acid
5. (5) Quaternary links, e.g. B.
   quaternary ammonium ethosulfate.

• alkoxylierte C₄- bis C₂₂-Alkohole wie Fettalkoholalkoxylate oder Oxoalkoholalkoxylate. Diese können mit Ethylenoxid, Propylenoxid und/oder Butylenoxid alkoxyliert sein. Als Netzmittel einsetzbar sind hierbei sämtliche alkoxylierten Alkohole, die mindestens zwei Moleküle eines der vorstehend genannten Alkylenoxide addiert enthalten. Hierbei kommen Blockpolymerisate von Ethylenoxid, Propylenoxid und/oder Butylenoxid in Betracht oder Anlagerungsprodukte, die die genannten Alkylenoxide in statistischer oder blockweiser Verteilung enthalten. Die nichtionischen Netzmittel enthalten pro Mol Alkohol im allgemeinen 2 bis 50, vorzugsweise 3 bis 20 Mol mindestens eines Alkylenoxids. Die Alkohole haben vorzugsweise 10 bis 18 Kohlenstoffatome. Je nach Art des bei der Herstellung verwendeten Alkoxylierungskatalysators, des Herstellungsverfahrens und der Aufarbeitung weisen die Alkoxylate eine breite oder enge Alkylenoxid-Homologenverteilung auf;
• Alkylphenolalkoxylate wie Alkylphenolethoxylate mit C₆- bis C₁₄-Alkylketten und 5 bis 30 Alkylenoxideinheiten;
• Alkylpolyglucoside mit 8 bis 22, vorzugsweise 10 bis 18 Kohlenstoffatomen in der Alkylkette und im allgemeinen 1 bis 20, vorzugsweise 1,1 bis 5 Glucosideinheiten Sorbitanalkanoate, auch alkoxyliert;
• N-Alkylglucamide, Fettsäurealkoxylate, Fettsäureaminalkoxylate, Fettsäureamidalkoxylate, Fettsäurealkanolamidalkoxylate, alkoxyliert, Blockcopolymere aus Ethylenoxid, Propylenoxid und/oder Butylenoxid, Polyisobuten-Ethoxylate, Polyisobuten-Maleinsäureanhydrid-Derivate, gegebenenfalls alkoxylierte Monoglyceride, Glycerinmonostearate, Sorbitanester sowie Bisglyceride.

Other suitable nonionic, cationic, anionic or amphoteric wetting agents are in particular

• alkoxylated C ₄ - to C ₂₂ -alcohols, such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. These may be alkoxylated with ethylene oxide, propylene oxide and / or butylene oxide. Suitable wetting agents here are all alkoxylated alcohols which contain at least two molecules of one of the abovementioned alkylene oxides added. In this context, block polymers of ethylene oxide, propylene oxide and / or butylene oxide are suitable or adducts which contain said alkylene oxides in random or blockwise distribution. The nonionic wetting agents generally contain from 2 to 50, preferably from 3 to 20, moles of at least one alkylene oxide per mole of alcohol. The alcohols preferably have 10 to 18 carbon atoms. Depending on the nature of the alkoxylation catalyst used in the preparation, the preparation process and the workup, the alkoxylates have a broad or narrow alkylene oxide homolog distribution;
• Alkylphenol alkoxylates such as alkylphenol ethoxylates having C ₆ to C ₁₄ alkyl chains and 5 to 30 alkylene oxide units;
• Alkyl polyglucosides having 8 to 22, preferably 10 to 18, carbon atoms in the alkyl chain and generally 1 to 20, preferably 1.1 to 5 glucoside units of sorbitan alkanoates, also alkoxylated;
• N-alkylglucamides, fatty acid alkoxylates, Fettsäureaminalkoxylate, Fettsäureamidalkoxylate, Fettsäurealkanolamidalkoxylate, alkoxylated, block copolymers of ethylene oxide, propylene oxide and / or butylene oxide, polyisobutene ethoxylates, polyisobutene-maleic anhydride derivatives, optionally alkoxylated monoglycerides, glycerol monostearates, sorbitan esters and bisglycerides.

Particularly suitable nonionic wetting agents are alkyl alkoxylates or mixtures of alkyl alkoxylates, as described, for example, in US Pat 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 in DE-A 43 25 237 are described. These are alkoxylation products obtained by reacting alkanols with alkylene oxides in the presence of alkoxylation catalysts or mixtures of alkoxylation products. Particularly suitable starter alcohols are the so-called Guerbet alcohols, in particular ethylhexanol, propylheptanol and butyloctanol. Particularly preferred is propylheptanol. Preferred alkylene oxides are propylene oxide and ethylene oxide, with alkyl alkoxylates with direct attachment of a preferably short Poylypropylenoxidblocks to the starter alcohol, such as in DE-A 102 43 365 are particularly preferred because of their low residual alcohol content and their good biodegradability.

R¹

mindestens einfach verzweigtes C_4-22-Alkyl oder -Alkylphenol,

R²

C_3-4-Alkyl

R⁵

C_1-4-Alkyl

R⁶

Methyl oder Ethyl

n

mittlerer Wert von 1 bis 50

m

mittlerer Wert von 0 bis 20, vorzugsweise 0,5 bis 20

r

mittlerer Wert von 0 bis 50

s

mittlerer Wert von 0 bis 50,

wobei m mindestens 0,5 ist, wenn R⁵ Methyl oder Ethyl ist oder r den Wert 0 hat.A preferred class of suitable nonionic wetting agents are the alcohol alkoxylates of the general formula (NI)

R ^{1 is} -O- (CH ₂ -CHR ⁵ -O-) _r (CH ₂ -CH ₂ -O-) _n (CH ₂ -CHR ⁶ -O-) _s (CH ₂ -CHR ² -O-) _m H (NI)

with the meaning

R ¹

at least mono-branched C _4-22 -alkyl or -alkylphenol,

R ²

C _3-4 alkyl

R ⁵

C _1-4 alkyl

R ⁶

Methyl or ethyl

n

average value from 1 to 50

m

average value from 0 to 20, preferably 0.5 to 20

r

average value from 0 to 50

s

average value from 0 to 50,

where m is at least 0.5 when R ^{5 is} methyl or ethyl or r is 0.

It may also be a mixture of 20 to 95 wt .-%, preferably 30 to 95 wt .-% of at least one above alcohol alkoxylate and 5 to 80 wt .-%, preferably 5 to 70 wt .-%, of a corresponding alcohol alkoxylate, in which R ^1, however, is an unbranched alkyl radical having the same carbon number act.

R³

verzweigtes oder unverzweigtes C_4-22-Alkyl oder -Alkylphenol,

R⁴

C_3-4-Alkyl

p

mittlerer Wert von 1 bis 50, vorzugsweise 4 bis 15

q

mittlerer Wert von 0,5 bis 20, bevorzugt 0,5 bis 4, bevorzugter 0,5 bis 2

handeln.It may also be alcohol alkoxylates of the general formula (NII)

R ^{3 is} -O- (CH ₂ -CH ₂ -O) p (CH ₂ -CHR ⁴ -O-) _q H (NII)

with the meaning

R ³

branched or unbranched C _4-22 -alkyl or -alkylphenol,

R ⁴

C _3-4 alkyl

p

average value of 1 to 50, preferably 4 to 15

q

average value of 0.5 to 20, preferably 0.5 to 4, more preferably 0.5 to 2

act.

It can also be a mixture of 5 to 95 wt .-% of at least one branched alcohol alkoxylate (NII), as described immediately above, and 5 to 95 wt .-% of a corresponding alcohol alkoxylate, in which instead of a branched alkyl but a unbranched alkyl is present.

In the alcohol alkoxylates of general formula (NI), R ^{2 is} preferably propyl, in particular n-propyl.

In the alcohol alkoxylates of the general formula (NII), n preferably has an average value of 4 to 15, particularly preferably 6 to 12, in particular 7 to 10.

Preferably, m has an average value of 0.5 to 4, particularly preferably 0.5 to 2, in particular 1 to 2.

The radical R ¹ is preferably C _8-15 , particularly preferably C _8-13 , in particular C _8-12- alkyl, which is at least mono-branched. There may also be multiple branches.

R ⁵ is preferably methyl or ethyl, especially methyl.

R ⁶ is preferably ethyl.

In the mixtures there are compounds with unbranched and branched alcohol radicals R ¹ . This is the case, for example, with oxo alcohols which have a proportion of linear and a proportion of branched alcohol chains. For example, a C _13/15 -oxo alcohol often about 60 wt .-% of completely linear alcohol chains, but in addition also about 40 wt .-% α-methyl-branched C and _{≥2-branched} alcohol chains.

In the alcohol alkoxylates of the general formula (NII), R ^{3 is} preferably a branched or unbranched C _8-15 -alkyl radical, more preferably a branched or unbranched C _8-13 -alkyl radical and in particular a branched or unbranched C _8-12 -alkyl radical. R ⁴ is preferably propyl, especially n-propyl. p preferably has an average value of 4 to 15, particularly preferably an average value of 6 to 12 and in particular a mean value of 7 to 10. q preferably has an average value of 0.5 to 4, particularly preferably 0.5 to 2, in particular 1 to 2.

According to the alcohol alkoxylates of the general formula (NI), the alcohol alkoxylates of the general formula (NII) may also be present as mixtures with unbranched and branched alcohol radicals.

Alcohol components on which the alcohol alkoxylates are based are not only pure alkanols, but also homologous mixtures having a range of carbon atoms. Examples are C _8/10 alkanols, C _10/12 alkanols, C _13/15 alkanols, C _12/15 alkanols. It is also possible to mix several alkanols.

The above alkanol alkoxylates or mixtures according to the invention are preferably prepared by reacting alcohols of the general formula R ¹ -OH or R ³ -OH or mixtures of corresponding branched and unbranched alcohols, optionally first with C _3-6 alkylene oxide, then with ethylene oxide and optionally subsequently with C _3-4 alkylene oxide and then with a corresponding C _5-6 alkylene oxide. The alkoxylations are preferably carried out in the presence of alkoxylation catalysts. In particular, basic catalysts such as potassium hydroxide are used. By special alkoxylation catalysts such as modified bentonites or hydrotalcites, as described, for example, in US Pat WO 95/04024 described, the statistical distribution of the amounts of incorporated alkylene oxides can be greatly restricted, so that one obtains "narrow-range" alkoxylates.

A

Ethylenoxy

B

jeweils unabhängig C_3-10-Alkylenoxy, vorzugsweise Propylenoxy, Butylenoxy, Pentylenoxy oder Gemische davon,

wobei Gruppen A und B in Form von Blöcken in der angegebenen Reihenfolge vorliegen,

p

Zahl von 0 bis 10

n

Zahl größer 0 bis 20,

m

Zahl größer 0 bis 20

q

Zahl größer 0 bis 10

p + n + m + q

mindestens 1

wobei 70 bis 99 Gew.-% Alkoxylate A1, in denen C₅H₁₁ die Bedeutung n-C₅H₁₁ hat, und 1 bis 30 Gew.-% Alkoxylate A2, in denen C₅H₁₁ die Bedeutung C₂H₅CH(CH₃)CH₂ und/oder CH₃CH(CH₃)CH₂CH₂ hat, im Gemisch vorliegen.In a particular embodiment of the present invention, alkoxylate mixtures containing alkoxylates of the general formula (NIII)

C ₅ H ₁₁ CH (C ₃ H ₇ ) CH ₂ O (B) _p (A) _n (B) _m (A) _q H (NIII)

with the meaning

A

ethyleneoxy

B

each independently C _3-10 alkyleneoxy, preferably propyleneoxy, butyleneoxy, pentyleneoxy or mixtures thereof,

where groups A and B are in the form of blocks in the order given,

p

Number from 0 to 10

n

Number greater 0 to 20,

m

Number greater 0 to 20

q

Number greater 0 to 10

p + n + m + q

at least 1

in which 70 to 99% by weight Alkoxylates A1, in which C ₅ H _{11 has} the meaning nC ₅ H ₁₁ , and 1 to 30% by weight Alkoxylates A2, in which C ₅ H _{11 has} the meaning C ₂ H ₅ CH (CH ₃ ) CH ₂ and / or CH ₃ CH (CH ₃ ) CH ₂ CH ₂ , present in the mixture.

In the general formula (NIII), p is a number from 0 to 10, preferably 0 to 5, in particular 0 to 3. If blocks (B) _p are present, p is preferably a number from 0.1 to 10, particularly preferably 0, 5 to 5, in particular 1 to 3.

In the general formula (NIII), n is preferably a number in the range of 0.25 to 10, especially 0.5 to 7, m is preferably a number in the range of 2 to 10, especially 3 to 6. B is preferably propyleneoxy and / or butyleneoxy, especially propyleneoxy at both positions.

q is preferably a number in the range of 1 to 5, more preferably in the range of 2 to 3.

The sum p + n + m + q is at least 1, preferably 3 to 25, particularly preferably 5 to 15, in particular 7 to 13.

The alkoxylates preferably contain 3 or 4 alkylene oxide blocks. According to one embodiment, the alcohol residue is then initially followed by ethyleneoxy units, followed by propylene oxide units and subsequently ethyleneoxy units. According to a further embodiment, the alcohol radical is then initially followed by propyleneoxy units, then ethyleneoxy units, then propyleneoxy units and finally ethyleneoxy units. Instead of the propyleneoxy units, the other indicated alkyleneoxy units may also be present.

p, n, m and q denote an average value, which results as an average for the alkoxylates. Therefore, p, n, m, q can also differ from integer values. In the alkoxylation of alkanols, a distribution of the degree of alkoxylation is generally obtained, which can be adjusted to some extent by using different alkoxylation catalysts. By choosing suitable Quantities of groups A and B, the property spectrum of the alkoxylate mixtures according to the invention can be adjusted depending on the practical requirements.

The alkoxylate mixtures are obtained by alkoxylation of the underlying alcohols C ₅ H ₁₁ CH (C ₃ H ₇ ) CH ₂ OH. The starting alcohols can be mixed from the individual components, resulting in 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 by hydroformylation of butene, such as in US 4,287,370 ; Beilstein E IV 1, 32 68, Ullmanns Encyclopedia of Industrial Chemistry, 5th edition, volume A1, pages 323 and 328 f described. The subsequent aldol condensation is described, for example, in US Pat US 5,434,313 and Römpp, Chemie Lexikon, 9th edition, keyword "Aldol addition" page 91 , The hydrogenation of the aldol condensation product follows general hydrogenation conditions.

Furthermore, 2-propylheptanol can be prepared by condensation of 1-pentanol (as a mixture of the corresponding methylbutanols-1) in the presence of KOH at elevated temperatures, see eg Marcel Guerbet, CR Acad Sci Paris 128, 511, 1002 (1899 ). Furthermore, it is up Römpp, Chemie Lexikon, 9th edition, Georg Thieme Verlag Stuttgart , and the quotes mentioned there as well Tetrahedron, Vol. 23, pages 1723 to 1733 to point out.

• 70 bis 99 Gew.-%, vorzugsweise 85 bis 96 Gew.-% Alkoxylate A1 vorliegen, in denen C₅H₁₁ die Bedeutung n-C₅H₁₁ hat, und
• 1 bis 30 Gew.-%, vorzugsweise 4 bis 15 Gew.-% Alkoxylate A2, in denen C₅H₁₁ die Bedeutung C₂H₅CH(CH₃)CH₂ und/oder CH₃CH(CH₃)CH₂CH₂ hat.

In the general formula (NIII), the radical C ₅ H ₁₁ may be nC ₅ H ₁₁ , C ₂ H ₅ CH (CH ₃ ) CH ₂ or CH ₃ CH (CH ₃ ) CH ₂ CH ₂ . The alkoxylates are mixtures, where

• 70 to 99 wt .-%, preferably 85 to 96 wt .-% alkoxylates A1 are present, in which C ₅ H _{11 is} nC ₅ H ₁₁ , and
• 1 to 30 wt .-%, preferably 4 to 15 wt .-% alkoxylates A2, in which C ₅ H _{11 is} C ₂ H ₅ CH (CH ₃ ) CH ₂ and / or CH ₃ CH (CH ₃ ) CH ₂ CH ₂ has.

The radical C ₃ H ₇ preferably has the meaning nC ₃ H ₇ .

It may also be block-shaped iso Tridecanolalkoxylate the general formula (NV)

RO- (C _m H _2m O) _x (C _n H _2n O) _y H (NV)

in the
R denotes an iso-tridecyl radical,
m is the number 2 and at the same time n is the number 3 or 4 or
m stands for the number 3 or 4 and at the same time n stands for the number 2 and
x and y independently of one another represent numbers from 1 to 20,
where, in the case m = 2 / n = 3 or 4, the variable x is greater than or equal to y.

These block-shaped iso-Tridecanolalkoxylate are for example in the DE 196 21 843 A1 described.

Another suitable nonionic surfactant class is end-capped alcohol alkoxylates, especially of the aforementioned alcohol alkoxylates. In a particular embodiment, they are the corresponding end-capped alcohol alkoxylates of the alcohol alkoxylates of the general formulas (NI), (NII), (NIII) and (NV). The end-capping can be carried out, for example, with dialkyl sulfate, C _1-10 alkyl halides, C _1-10 phenyl halides, preferably chlorides, bromides, particularly preferably cyclohexyl chloride, cyclohexyl bromide, phenyl chloride or phenyl bromide.

R^I

Wasserstoff oder C₁-C₂₀-Alkyl,

R^II und R^III

gleich oder verschieden sind und jeweils unabhängig voneinander Wasserstoff, Methyl oder Ethyl,

R^IV

C₁-C₁₀-Alkyl, vorzugsweise C₁-C₄-Alkyl, oder Cyclohexyl- oder Phenyl-,

m' und n'

gleich oder verschieden und größer oder gleich 0 sind,

mit der Maßgabe, dass die Summe von m' und n' 3 bis 300 beträgtExamples of end-capped alkoxylates are also in DE-OS 37 26 121 the entire disclosure of which in the present invention is incorporated by reference. In a preferred embodiment, these alcohol alkoxylates have the general structure (NVI),

R ^I -O- (CH ₂ -CHR ^II -O) _{m '(CH 2} -CHR ^III O) _n' R ^IV (NVI)

on, in the

R ^I

Hydrogen or C ₁ -C ₂₀ -alkyl,

R ^II and R ^III

are identical or different and each independently of one another hydrogen, methyl or ethyl,

R ^IV

C ₁ -C ₁₀ -alkyl, preferably C ₁ -C ₄ -alkyl, or cyclohexyl- or phenyl-,

m 'and n'

are the same or different and greater than or equal to 0,

with the proviso that the sum of m 'and n' is 3 to 300

Another class of nonionic surfactants are alkyl polyglucosides having preferably 6 to 22, more preferably 10 to 18, carbon atoms in the alkyl chain. These compounds generally contain 1 to 20, preferably 1.1 to 5, glucoside units.

R¹

einen C₅- bis C₂₁-Alkyl- oder Alkenylrest bezeichnet,

R²

eine C₁- bis C₄-Alkylgruppe bedeutet,

A¹

für C₂- bis C₄-Alkylen steht,

y

die Zahl 2 oder 3 bezeichnet und

x

einen Wert von 1 bis 6 hat.

Other suitable nonionic wetting agents are those from the WO-A 95/11225 known endgruppenverschlossenen Fettsäureamidalkoxylate the general formula

R ^{I is} -CO-NH- (CH ₂ ) _y -O- (A ¹ O) _x -R ²

in the

R ¹

denotes a C ₅ - to C ₂₁ -alkyl or alkenyl radical,

R ²

a C ₁ - to C ₄ -alkyl group,

A ¹

is C ₂ - to C ₄ -alkylene,

y

the number 2 or 3 denotes and

x

has a value of 1 to 6.

Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H ₂ N- (CH ₂ -CH ₂ -O) ₃ -C ₄ H ₉ with dodecanoic acid methyl ester or the reaction products of ethyltetraglycolamine of the formula H ₂ N- (CH ₂ -CH ₂ -O) ₄ -C ₂ H ₅ with a commercially available mixture of saturated C ₈ - to C ₁₈ fatty acid methyl esters.

Also suitable as nonionic wetting agents are polyhydroxy or polyalkoxy fatty acid derivatives such as polyhydroxy fatty acid amides, N-alkoxy or N-aryloxypolyhydroxy fatty acid amides, fatty acid amide ethoxylates, in particular end-capped fatty acid alkanolamide alkoxylates.

Still further, the block copolymers suitable for use as nonionic surfactants of ethylene oxide, propylene oxide and / or butylene oxide (Pluronic ^® - and Tetronic ^® BASF SE BASF Corp. or grades). In a preferred embodiment, triblock copolymers having polyethylene / polypropylene / polyethylene blocks and a molecular weight of 4,000 to 16,000, wherein the weight fraction of the polyethylene blocks is 55 to 90%, based on the triblock copolymer. Particular preference is given to triblock copolymers having a molecular weight of more than 8,000 and a polyethylene content of from 60 to 85% by weight, based on the triblock copolymer. These preferred triblock copolymers are particularly commercially available under the designations Pluronic F127, Pluronic F108 and Pluronic F98, each from BASF Corp., and in US Pat WO 01/47472 A2 the entire disclosure of which is incorporated by reference into the present invention.

In addition, block copolymers of ethylene oxide, propylene oxide and / or butylene oxide, which are closed on one or two sides, can preferably also be used. A one-sided closure can be achieved, for example, by using as starting compound for the reaction with an alkylene oxide an alcohol, in particular a C _1-22 alkyl alcohol, for example methanol. Moreover, one can - for example, the second endcapping - by reacting the free block copolymer with dialkyl sulfate, C _1-10 -alkyl halides, C _1-10 -Phenylhalogenide, preferably chlorides, bromides, particularly preferably cyclohexyl, cyclohexyl bromide, phenyl chloride or phenyl effect.

It is additionally possible to use individual nonionic wetting agents or a combination of different nonionic surfactants. It is possible to use nonionic wetting agents of only one class, in particular only alkoxylated C ₄ - to C ₂₂ -alcohols. Alternatively, one can also use wetting agent mixtures from different classes.

The concentration of nonionic wetting agent in the composition of the invention may vary depending on the conditions of leaching, in particular depending on the material to be leached.

Suitable anionic wetting agents are alkanesulfonates such as C ₈ - to C ₂₄ -, preferably C ₁₀ - to C ₁₈ -alkanesulfonates and soaps such as the Na and K salts of saturated and / or unsaturated C ₈ - to C ₂₄ carboxylic acids.

Further suitable anionic wetting agents are linear C ₈ - to C ₂₀ -alkylbenzenesulfonates ("LAS"), preferably linear C ₉ - to C ₁₃ -alkylbenzenesulfonates and -alkyltoluenesulfonates.

thickener

Thickeners are compounds that increase the viscosity of the chemical composition. Non-limiting examples are for. B. in the WO 2009/090169 A1 indicated: polyacrylates and hydrophobically modified polyacrylates. The advantage of using thickeners is that higher viscosity fluids on inclined or vertical surfaces have a longer residence time than lower viscosity fluids. This increases the interaction time between composition and surface.

Further particularly suitable thickeners are, for example, bentonite, 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

1. (a) 50 bis 80 Gew.-%, vorzugsweise 50 bis 75 Gew.-%, besonders bevorzugt 55 bis 70 Gew.-%, eines Poly(meth)acrylsäure-Grundgerüsts,
2. (b) 1 bis 40 Gew.-%, vorzugsweise 5 bis 20 Gew.-%, besonders bevorzugt 7 bis 15 Gew.-%, mindestens einer an das Grundgerüst gebundenen und/oder in das Grundgerüst eingebundenen (bzw. eingebundener) Einheit ausgewählt aus der Gruppe, bestehend aus Isobuteneinheiten, Terelactoneinheiten und Isopropanoleinheiten und
3. (c) 5 bis 50 Gew.-%, vorzugsweise 5 bis 40 Gew.-%, besonders bevorzugt 10 bis 30 Gew.-%, Amideinheiten auf Basis von Aminoalkylsulfonsäuren umfassen,

wobei das Gesamtgewicht der Einheiten in dem (Meth)acrylsäurecopolymer 100 Gew.-% beträgt und alle Gewichtsangaben auf das (Meth)acrylsäurecopolymer bezogen sind.In addition, according to the invention, at least one dispersing agent, for example selected from the group consisting of salts of naphthalenesulfonic acids, condensation products of naphthalenesulfonic acids and formaldehyde and also polycarboxylates, can additionally be used. Appropriate dispersing agents are commercially available for example under the trade name Tamol ^®, Sokalan ^® and Nekal ^® from BASF SE as well as under the trade name Solsperse ^® from Lubrizol. If appropriate, these dispersants can also act as scaling inhibitors (coating inhibitors), since they disperse the calcium carbonate CaCO ₃ forming in the alkaline medium and thus prevent, for example, clogging of nozzles or deposit formation in pipelines. Independently of this, the composition according to the invention may additionally contain at least one further scaling inhibitor. Suitable scaling inhibitors are for example in WO 04/099092 which describes (meth) acrylic acid copolymers which

1. (a) 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,
2. (b) from 1 to 40% by weight, preferably from 5 to 20% by weight, more preferably from 7 to 15% by weight, of at least one unit bonded to the backbone and / or incorporated into the backbone from the group consisting of isobutene units, terelactone units and isopropanol units and
3. (c) 5 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight, of amide units based on aminoalkylsulfonic acids,

wherein the total weight of units in the (meth) acrylic acid copolymer is 100% by weight and all weights are based on the (meth) acrylic acid copolymer.

1. (1) radikalische Polymerisation von (Meth)acrylsäure in Gegenwart von Isopropanol und gegebenenfalls Wasser, wobei ein Polymer I resultiert, und
2. (2) Amidierung des aus Verfahrensschritt (1) stammenden Polymers I durch Umsetzung mit mindestens einer Aminoalkansulfonsäure.

The according to WO 04/099092 (meth) acrylic acid copolymers preferably have a weight-average molecular weight of the sulfone-containing polymer of from 1,000 to 20,000 g / mol and can preferably be prepared by the following process steps:

1. (1) free radical polymerization of (meth) acrylic acid in the presence of isopropanol and optionally water, resulting in a polymer I, and
2. (2) amidation of the polymer I from process step (1) by reaction with at least one aminoalkanesulfonic acid.

• Polycarbonsäurehalbamide, die durch Umsetzung von Anhydridgruppen enthaltenden Polymerisaten und Aminogruppen enthaltenden Verbindungen erhältlich sind (gemäß DE 195 48 318 ),
• Vinylmilchsäure und/oder Isopropenylmilchsäure (gemäß DE 197 195 16 ),
• Homopolymerisaten der Acrylsäure (gemäß US-A-3 756 257 ),
• Copolymerisate aus Acrylsäure und/oder (Meth)acrylsäure und Vinylmilchsäure und/oder Isopropenylmilchsäure,
• Copolymerisate aus Styrol und Vinylmilchsäure,
• Copolymerisate aus Maleinsäure und Acrylsäure,
• Wasserlösliche oder wasserdispergierbare Pfropfpolymerisate, erhältlich durch radikalisch initiierte Pfropfpolymerisation von
  1. (I) mindestens eines monoethylenisch ungesättigten Monomeren auf
  2. (II) Polymerisaten einer Molmasse von 200 bis 5000 g/mol von monoethylenisch ungesättigten Dicarbonsäuren oder ihren Anhydriden,
  3. (III) wobei man auf 100 Gewichtsteile der Pfropfgrundlage (II) 5 bis 2000 Gewichtsteile (I) einsetzt ( DE 195 03 546 ),
• gegebenenfalls hydrolysierte Polymaleinsäureanhydride und ihre Salze (gemäß US-A-3 810 834 , GB-A-1 454 657 und EP-A-0 261 589 ),
• Iminodisuccinate (gemäß DE 101 02 209 ),
• Formulierungen, enthaltend Komplexbildner wie Ethylendiamintetraessigsäure (EDTA) und/oder Diethylentriaminpentaessigsäure (DTPA) (gemäß US 5,366,016 ),
• Phosphonate,
• Polyacrylate,
• Polyasparaginsäuren bzw. gemäß DE-A-44 34 463 modifizierte Polyasparaginsäuren,
• Polyasparaginsäureimide,
• Hydroxamsäure-, Hydroxamsäureether- und/oder Hydrazidgruppen enthaltende Polymere (gemäß DE 44 27 630 ),
• gegebenenfalls hydrolysierte Polymerisate des Maleinimids (gemäß DE 43 42 930 ),
• Naphtylaminpolycarboxylate (gemäß EP 0 538 969 ),
• Oxaalkanpolyphosphonsäuren (gemäß EP 330 075 ),
• Polyhydroxyalkan-amino-bis-methylenphosphonsäuren (gemäß DE 40 16 753 ) und
• oxidierte Polyglucosane (gemäß DE 43 30 339 ).

Further suitable scaling inhibitors are, for example:

• Polycarbonsäurehalbamide, which are obtainable by reaction of anhydride-containing polymers and amino-containing compounds (according to DE 195 48 318 )
• Vinyllactic acid and / or isopropenyllactic acid (according to DE 197 195 16 )
• Homopolymers of acrylic acid (according to U.S.-A-3,756,257 )
• Copolymers of acrylic acid and / or (meth) acrylic acid and vinyl lactic acid and / or isopropenyl lactic acid,
• Copolymers of styrene and vinyl lactic acid,
• Copolymers of maleic acid and acrylic acid,
• Water-soluble or water-dispersible graft polymers obtainable by free-radically initiated graft polymerization of
  1. (I) at least one monoethylenically unsaturated monomer
  2. (II) polymers having a molecular weight of from 200 to 5000 g / mol of monoethylenically unsaturated dicarboxylic acids or their anhydrides,
  3. (III) wherein 5 to 2000 parts by weight of (I) are used per 100 parts by weight of the graft base (II) ( DE 195 03 546 )
• optionally hydrolyzed polymaleic anhydrides and their salts (according to U.S. Patent 3,810,834 . GB-A-1 454 657 and EP-A-0 261 589 )
• Iminodisuccinate (according to DE 101 02 209 )
• Formulations containing complexing agents such as ethylenediaminetetraacetic acid (EDTA) and / or diethylenetriaminepentaacetic acid (DTPA) (according to US Pat US 5,366,016 )
• phosphonates,
• polyacrylates,
• Polyaspartic acids or according to DE-A-44 34 463 modified polyaspartic acids,
• polyaspartimides,
• Hydroxamic acid, hydroxamic acid and / or hydrazide group-containing polymers (according to DE 44 27 630 )
• optionally hydrolyzed polymers of maleimide (according to DE 43 42 930 )
• Naphthylamine polycarboxylates (according to EP 0 538 969 )
• Oxaalkane polyphosphonic acids (according to EP 330,075 )
• Polyhydroxyalkane-amino-bis-methylenephosphonic acids (according to DE 40 16 753 ) and
• oxidized polyglucosans (according to DE 43 30 339 ).

Particularly preferred dispersants are polyacrylic acid, such as Sokalan from BASF SE ^® types and polyaspartic acids, in particular β-polyaspartic acids with a molecular weight of 2,000 to 10,000 g / mol. Preferred as polymeric carboxylic acid group-containing compounds are those in the EP 2 083 067 A1 specified acrylic acid homopolymers. These preferably have a number-average molecular weight in the range from 1000 to 50,000, more preferably from 1,500 to 20,000. Homopolymers of acrylic acid which are particularly suitable as polymeric compounds containing carboxylic acid groups are the Sokalan® PA grades from BASF SE.

Suitable polymeric compounds containing carboxylic acid groups are also oligomaleic acids, as used, for example, in US Pat EP-A 451 508 and EP-A 396 303 are described.

Preference as polymeric carboxylic acid group-containing compounds are further copolymers which contain in copolymerized form as monomer A) at least one unsaturated mono- or dicarboxylic acid or a dicarboxylic anhydride or a salt thereof and at least one comonomer B). Preferably, the monomer A) is selected from C ₃ -C ₁₀ monocarboxylic acids, salts of C ₃ -C ₁₀ monocarboxylic acids, C ₄ -C ₈ dicarboxylic acids, anhydrides of C ₄ -C ₈ dicarboxylic acids, salts of C ₄ -C _8- 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 metal salts, such as potassium and especially sodium salts or ammonium salts. The monomers A) may each be wholly or partially in anhydride form. Of course, it is also possible to use mixtures of the monomers A).

The monomers (A) are preferably selected from acrylic, methacrylic, crotonic, vinylacetic, maleic, maleic, fumaric, citraconic, citraconic, itaconic and mixtures thereof. Particularly 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 95% by weight, particularly preferably from 20 to 80% by weight, in particular from 30 to 70% by weight, based on the total weight of the monomers used for the polymerization, in copolymerized form.

corrosion inhibitors

As corrosion inhibitors z. B. in the WO 2008/071582 A1 indicated agent, z. B. carboxylic acids. These can be straight-chain or branched. mixtures various carboxylic acids may be particularly preferred. Caprylic acid, ethylhexanoic acid, isononanoic acid and isodecanoic acid are particularly preferred carboxylic acids. Since anticorrosive emulsions are often neutral to slightly alkaline, it may be advantageous to use the carboxylic acids at least partially in neutralized form, ie as a salt. Particularly suitable for neutralization are sodium and / or potassium hydroxide, as well as alkanolamines. Particularly preferred is the use of mono- and / or trialkanolamines. The use of dialkanolamines is less preferred because of the danger of formation of nitrosamines. However, dialkanolamines alone or together with mono- and / or trialkanolamines can also be used for neutralization.

• aliphatische Carbonsäureamide mit 14 bis 36 C-Atomen, beispielsweise Myristinsäureamid, Palmetinsäureamid und Oleinsäureamid; Alkenylsuccinamide mit 6 bis 36 C-Atomen, beispielsweise Octenylsuccinamid, Dodecenylsuccinamid; Mercatobenzothiazole.

Suitable corrosion inhibitors are in particular:

• aliphatic carboxylic acid amides having 14 to 36 carbon atoms, for example myristic acid amide, palmitic acid amide and oleic acid amide; Alkenylsuccinamides having 6 to 36 carbon atoms, for example octenylsuccinamide, dodecenylsuccinamide; Mercatobenzothiazole.

Particularly preferred corrosion inhibitors are alkylene oxide adducts with aliphatic amines, particularly triethanolamine and ethylenediamine adducts with 2 to 8 mol% of propylene oxide.

complexing

Complexing agents are compounds that bind cations. Typical examples are: EDTA (N, N, N ', N'-ethylenediaminetetraacetic acid), NTA (N, N, N-nitrilotriacetic acid), MGDA (2-methyl-glycine-N, N-diacetic acid), GLDA (glutamic acid diacetate), ASDA (aspartic acid diacetate), IDS (iminodisuccinate), HEIDA (hydroxyethylimine diacetate), EDDS (ethylenediaminedisuccinate), citric acid, oxo-disuccinic acid and butanetetracarboxylic acid or their completely or partially neutralized alkali metal or ammonium salts.

Other additives

in der die Variablen folgende Bedeutung haben:

R

gleiche oder verschiedene, lineare oder verzweigte C2-C6-Alkylenreste;

B

eine Verzweigung;

E

eine Alkylenoxyeinheit der Formel

R1

1,2-Propylen, 1,2-Butylen und/oder 1,2-Isobutylen;

R2

Ethylen;

R3

1,2-Propylen;

R4

gleiche oder verschiedene Reste: Wasserstoff; C1-C4-Alkyl;

x, y, z

jeweils eine Zahl von 2 bis 150, wobei die Summe x+y+z eine Zahl von Alkylenimineinheiten bedeutet, die einem mittleren Molekulargewicht Mw des Polyalkylenimins vor der Alkoxylierung von 300 bis 10 000 entspricht;

m

eine rationale Zahl von 0 bis 2;

n

eine rationale Zahl von 6 bis 18;

p

eine rationale Zahl von 3 bis 12, wobei 0,8 ≤ n/p ≤ 1,0 (x+y+z)1/2 ist.

Further suitable additives are, for example, adhesion promoters. Suitable adhesion promoters are, for example, in the WO 2006/108856 A2 specified amphiphilic water-soluble alkoxylated polyalkyleneimines of the general formula AI

in which the variables have the following meaning:

R

identical or different, linear or branched C 2 -C 6 -alkylene radicals;

B

a branch;

e

an alkyleneoxy unit of the formula

R1

1,2-propylene, 1,2-butylene and / or 1,2-isobutylene;

R2

ethylene;

R3

1,2-propylene;

R4

identical or different radicals: hydrogen; C1-C4 alkyl;

x, y, z

each number from 2 to 150, wherein the sum of x + y + z represents a number of Alkylenimineinheiten corresponding to an average molecular weight Mw of the polyalkyleneimine before the alkoxylation of 300 to 10,000;

m

a rational number from 0 to 2;

n

a rational number from 6 to 18;

p

a rational number of 3 to 12, wherein 0.8 ≦ n / p ≦ 1.0 (x + y + z) is 1/2.

The invention further relates to a slurry of the carrier liquid, in particular cutting fluid, abrasives, in particular grinding and / or cutting grains, and optionally additives.

The usual abrasives, in particular grinding and / or cutting grains, can be used, for example metal, metal or semimetal, carbide, nitride, oxide, boride or diamond grains. Particularly preferred cutting grains are carbide and boride, in particular silicon carbide (SiC) grains. The cutting grains preferably have an adapted geometry depending on the materials and the wafers to be cut, a preferred particle size is between 0.5 and 50 μm. The cutting grains may be in heterodisperse or homodisperse form. The cutting grains are preferably contained in the cutting fluid composition in a concentration of 25 to 60% by weight, especially 40 to 50% by weight.

In a particularly preferred embodiment, the carrier liquid, in particular cutting fluid, a contact angle against V2A steel 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, the surface was rinsed with water and acetone.

In a further preferred embodiment, the carrier fluids according to the invention, in particular cutting fluids, on a scale of the designation MDD2, Hermann Reichert Maschinenbau, Heidenhof Backnang, at a load of 300 N and a running distance of 110 m and two times trial repetition lead on average to a decrease in weight of a maximum 20 to 60 mg in one minute on a stainless steel cylinder of the designation M1M6 / 05R, Torrington with a diameter of 12 mm.

In a further preferred embodiment, the carrier liquids according to the invention, in particular cutting fluids, after storage in a Heraeus BBD 6220 CO 2 incubator at 38 ° C. and 78% relative humidity take a maximum of 30, preferably a maximum of 15%, water after a time of 10 hours on. For storage, 1 g of carrier liquid, in particular cutting fluid, are used in petri dishes of an inner diameter of 60 mm. In each case, the mean value of a double determination is determined. In a very particularly preferred embodiment, this water absorption no longer increases even with further exposure.

A slurry of a carrier liquid according to the invention, in particular cutting fluid, and of 40 wt .-% of Abrasiva specified below, in particular grinding and / or cutting grains, preferably has a viscosity, measured at 30 ° C with a Brookfield LVDV-III Ultravorrichtung (Spindle V-73), from 140 to 200 mPas, in particular from 150 to 190 mPas, being used as Carborex BWF 800 PV silicon carbide grains from Washington Mills.

The invention further relates to a method for cutting wafers of in particular inorganic semiconductors, such as silicon ingots or silicon ingots, with a wire saw using a slurry based on the cutting fluid according to the invention and of cutting grains.

The invention further relates to a method for grinding or polishing materials such as silicon ingots or ingots by, for example, chemical mechanical polishing (CMP) or for grinding plastics, in particular for lenses, using abrasives dispersed in a carrier liquid to be used in accordance with the invention.

advantages

The carrier liquid according to the invention, in particular cutting fluid and the method according to the invention for cutting is particularly suitable for sawing ingots, ingots or cylinders (ingots) of monocrystalline or polycrystalline silicon single crystals or polycrystals, GaAs, CdTe and other semiconductors and ceramics.

The carrier liquid according to the invention, in particular cutting fluid, is characterized in that it is low or non-foaming, requires no additives, is pH-neutral and is not toxic. In addition, it contains no volatile organic components. Furthermore, the carrier liquid according to the invention, in particular cutting fluid, excellent for reprocessing by chemical-technical wet processing, for example according to the WO 02/40407 A1 and the EP 1 390 184 A1 ,

Examples: General preparation for polyethers

In an anhydrous, dry 1 l pressure reactor in each case 1-2 mol of the starter alcohol were initially charged and mixed with 0.2Gew% (based on the final product) of KOH and purged with nitrogen. The closed reactor was then heated to 130 ° C. for 30 minutes and an excess pressure of 1 bar was set with nitrogen. Subsequently, the molar amounts of propylene oxide (hereinafter PO) and ethylene oxide (hereinafter EO) indicated in Table 1 were added in parallel (random mode) or in succession (block mode) with stirring. In the block procedure, after PO addition and reaching the constant pressure before the EO addition, the mixture was stirred at 130 ° C. for at least half an hour and the pressure was adjusted to 1 bar. During the reaction, the container was thermostated at 130 ° C. After reaching the constant pressure was stirred for about ½ hour. After the reaction was cooled to 80 ° C, the reactor was depressurized and rinsed with nitrogen, added to the neutralization of the KOH calculated amount of glacial acetic acid and stirred for ½ hour.

The OH number was determined according to DIN 51562, the residual alcohol by gas chromatography and the color number APHA according to EN 1557 (at 23 ° C.). Table 1: Examples and analytical characterization product Chem. Composition (PO here means propyleneoxy, EO here means ethyleneoxy) OH number Residual alcohol% color number Pluriol® E 200 Polyethylene glycol 200 560 DEG 3 max30 C1 (3-methyl-butan-1-ol) + 1.6 PO + 8.3 EO block driving 98.3 0.2 70 C2 (3-methyl-butan-1-ol) + 5.5 PO + 5.5 EO Random driving 87.0 <0.1 25 C3 (3-methyl-butan-1-ol) + 6.0 PO + 5.0EO Random driving 85.7 <0.1 20 C4 n-Butan-1-ol + 5.5 PO + 5.5 EO Random Driving 90.4 <0.1 30 C5 Methyl diglycol + 8.8EO / (3-methyl-butan-1-ol) + 1.5 PO + 7.0 EO in a weight ratio of 6/4 block mode 106.6 / 112.4 0.2 / <0.1 60/50 C6 Pluronic® PE 6200 / n-pentanol +1.5 PO + 6 EO in a weight ratio of 18/82 block mode 112.4 0.1 30 C7 Plurafac® LF 401 / n-pentanol + 1.5 PO + 6 EO in a weight ratio of 3/7 block operation 126.2 0.1 25 C8 n-hexanol + 5.5 PO + 5.5 EO Random driving 84.0 <0.1 20 II.1 2-Methylbutan-1-ol + 5.5 PO + 5.5 EO Random Driving 85.2 <0.1 20 II.2 2-Methylbutan-1-ol + 6.0 PO + 5.0 EO Random Driving 86.1 <0.1 15

The wetting agents or alkylene glycols Pluronic® PE 6200 or Plurafac® LF 401 added in Examples C6 and C7 are commercial products of BASF SE, Ludwigshafen. The analytical data given refer to the component of the invention pentanol + 1.5 PO + 6EO, block mode.

Properties / Determination of the characteristic values

• Wasseraufnahme
  Die Wasseraufnahme der Schneidflüssigkeiten wurde nach ihrer Lagerung in einem CO2-Inkubator des Typs Heraeus BBD 6220, bei 38 °C und 78 % relativer Luftfeuchtigkeit nach einer Zeit von 10 Stunden bzw. 24 Stunden bestimmt. Zur Lagerung wurde jeweils 1g Schneidflüssigkeit in Petrischalen eines inneren Durchmessers von 60mm eingesetzt. Es wurde jeweils der Mittelwert einer Doppelbestimmung ermittelt. Die Wasseraufnahme wird jeweils in Gewichtsprozent Zunahme bezogen auf Einwaage angegeben.
• Slurry-Viskosität
  Zur Bestimmung der Slurry-Viskosität wurde eine Mischung aus 60 Gwichtsprozent der Sägeflüssigkeit und 40 Gewichtsprozent SiC des Typs Carborex BW F 800 PV der Firma Washington Mills hergestellt und die Viskosität bei 30°C und ggf. 50°C mit einem Viskosimeter der Firma Brookfield, Modell LVDV-III Ultra (Spindel V-73) bestimmt. Die Slurry-Viskosität wird in mPas angegeben.
• Kontaktwinkel
  Der Kontaktwinkel der Schneidflüssigkeiten wurde bei 25 °C eine Sekunde nach Tropfenaufgabe auf einer Stahlplatte aus V2A-Stahl bestimmt, dessen Oberfläche mit Wasser und Aceton gespült und anschließend an der Luft 1 h getrocknet wurde. Zur Bestimmung wurde ein videogestütztes Hochgeschwindigkeits- Kontaktwinkelmessgerät der Firma Dataphysics Instruments GmbH, Raiffeisenstraße 34, Filderstadt eingesetzt. Die Einheit des Kontaktwinkels wird in ° angegeben.
• Abrieb
  Das Abriebverhalten wurde auf einer Rebverschleißwaage der Bezeichnung MDD2, Firma Hermann Reichert Maschinenbau, Heidenhof Backnang, bei einer Belastung von 300 N und einer Laufstrecke von 100 m in 54,5 sec. an einem Edelstahlzylinder der Bezeichnung M1M6/05R, Torrington mit einem Durchmesser von 12 mm bestimmt. Es wurde jeweils eine Doppelbestimmung durchgeführt und der Mittelwert der Gewichtsabnahme des Zylinders bestimmt. Die Gewichtsabnahme wird in mg angegeben.

Tabelle 2 Produkt H2O-Aufnahme 10h (24h) [%] Viskosität [mPas] 30°C (50°C) Kontaktwinkel [°] Abrieb [mg] Pluriol® E 200 203 (94) 41 70 C1 17,2 (18,2) 181 (85) 30 25 C2 5,7 (5,9) 160 (89) 23 32 C3 5,3 (5,3) 185 (161) 21 22 C4 6,6 (6,6) 155 (93) 23 28 C5 16,3 (24,3) 164 (77) 29 35 C6 5,5 (8,3) 175 (84) 28 29 C7 6,3 (8,2) 167 (84) 36 33 C8 5,3 (5,3) 198 (176) 34 38 The properties of the cutting fluids according to the invention are summarized in Table 2. The following properties were determined:

• water absorption
  The water uptake of the cutting fluids was determined after storage in a Heraeus BBD 6220 CO2 incubator at 38 ° C. and 78% relative humidity after 10 hours and 24 hours, respectively. For storage, 1 g of cutting fluid was used in Petri dishes of an inner diameter of 60 mm. In each case, the mean value of a duplicate determination was determined. The water absorption is given in percent by weight increase based on weight.
• Slurry viscosity
  To determine the slurry viscosity, a mixture of 60% by weight of the sawing liquid and 40% by weight of Carborex BW F 800 PV SiC manufactured by Washington Mills and the viscosity at 30 ° C and optionally 50 ° C with a viscometer from Brookfield, Model LVDV-III Ultra (Spindle V-73). The slurry viscosity is given in mPas.
• contact angle
  The contact angle of the cutting fluids was determined at 25 ° C. one second after drop application on a steel plate made of V2A steel, the surface of which was rinsed with water and acetone and then dried in air for 1 h. For the determination, a video-assisted high-speed contact angle measuring device from Dataphysics Instruments GmbH, Raiffeisenstrasse 34, Filderstadt was used. The unit of the contact angle is given in °.
• abrasion
  The abrasion behavior was on a Rebverschleißwaage the designation MDD2, Hermann Reichert Maschinenbau, Heidenhof Backnang, at a load of 300 N and a running distance of 100 m in 54.5 sec. At a stainless steel cylinder of the designation M1M6 / 05R, Torrington with a diameter of 12 mm determined. A double determination was carried out in each case and the mean value of the weight decrease of the cylinder was determined. The weight loss is given in mg.

Table 2 product H2O recording 10h (24h) [%] Viscosity [mPas] 30 ° C (50 ° C) Contact angle [°] Abrasion [mg] Pluriol® E 200 203 (94) 41 70 C1 17.2 (18.2) 181 (85) 30 25 C2 5.7 (5.9) 160 (89) 23 32 C3 5.3 (5,3) 185 (161) 21 22 C4 6,6 (6,6) 155 (93) 23 28 C5 16.3 (24.3) 164 (77) 29 35 C6 5.5 (8.3) 175 (84) 28 29 C7 6.3 (8.2) 167 (84) 36 33 C8 5.3 (5,3) 198 (176) 34 38

Pluriol® E 200 is a medium molecular weight polyethylene glycol 200 from BASF SE, Ludwigshafen. The example represents the prior art and is not according to the invention. Compounds II.1 and II.2 gave comparable results to compounds C2 and C3.

field trial

• Abmessungen der Wafer: 5"x 5", 150 µm
• SiC Qualität: F 88, ds50 = 6,5 µm
• Vorschubgeschwindigkeit: 0,6 mm/s
• Drahtgeschwindigkeit: 14 m/s
• Drahtdurchmesser: 120 µm
• Drahtspannung: 20 N
• Slurry Temperatur: 22°C
• Zusammensetzung der Slurry: 60Gew.% Sägeflüssigkeit, 40Gew.% SiC

On a wire saw DS 265 from Meyer Burger AG, Allmendstrasse 86, CH 3600 Thun sawing tests were carried out on polycrystalline silicon blocks using the sawing liquids C1 and C3. The experimental conditions were:

• Dimensions of the wafers: 5 "x 5", 150 μm
• SiC quality: F 88, ds50 = 6.5 μm
• Feed rate: 0.6 mm / s
• Wire speed: 14 m / s
• Wire diameter: 120 μm
• Wire tension: 20 N
• Slurry temperature: 22 ° C
• Composition of the slurry: 60% by weight of sawing fluid, 40% by weight of SiC

In comparison with the PEG 200 (Pluriol® E 200) commonly used in practice, the following improvements were found for the cutting fluids according to the invention: Pluriol® E 200 C1 C3 Water absorption, [% by weight] 3 <0.5 <0.5 Force per wire in feed direction, [N] 0.62 0.57 0.58 Force per wire in wire direction, [N] 1.62 1.51 1.55 Power consumption per wire, [W] (without machine part) 29.5 24.0 26.5 TTV, 5 point edition, [%] (total thickness variation of wafers) 12.5 11.8 10.5 Critical breaking stress, [N / mm2] 158 163 178

Similar improvements have also been found using the other products of the invention indicated in Table 1.

Claims (11)

1. The use of compounds of the formula I
   
           R¹ [O (EO, (AO)_y H]_z
   
   where

   R¹ 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

   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, having a water content of less than 1% by weight.
2. The use according to claim 1, wherein, in the formula I,
   R¹ is a z-valent alkyl radical having from 5 to 10 carbons, in particular pentyl.
3. The use according to at least one of the preceding claims, wherein the carrier fluid, in particular cutting 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.
4. A carrier fluid, in particular cutting fluid, consisting of at least one compound of the formula I
   
           R¹ [O (EO)_x (AO)_y H]_Z
   
   where

   R¹ is a z-valent alkyl radical having from 5 to 10 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

   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, having a water content of less than 1% by weight.
5. The carrier fluid, in particular cutting fluid, according to claim 4, wherein R¹ is pentyl.
6. The carrier fluid, in particular cutting fluid, according to claim 4, wherein the contact angle of the carrier fluid, in particular cutting fluid, on V2A steel at 25°C is from 25 to 50°.
7. 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 silicon carbide grains.
8. 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.
9. 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, α-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.
10. 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.
11. A compound of the formula II
    
            R¹ O (EO)_x (AO)_y H
    
    where

    R¹ is 2-methylbutyl or 3-methylbutyl
    and

    (EO), (AO), x and y are as defined in claim 4.