JP2015505574A - Cooling and / or lubricating liquid for wafer manufacture - Google Patents

Abstract

The present invention relates to the use of modified polyglycols for cooling and / or the production of lubricating liquids, novel cooling and / or lubricating liquids, and in particular for cutting wafers when scraping the materials of the cooling and / or lubricating liquids. And a wafer manufactured using the cutting liquid.

Description

  The present invention relates to the use of modified polyglycols for the production of cooling and / or lubricating liquids, new cooling and / or lubricating liquids, in the cooling and / or lubricating liquids, in particular when cutting materials. And a wafer manufactured by using the cutting liquid.

  A wafer is a thin disk made of a semiconductor, eg, a semiconductor used in photovoltaic devices. Electronic elements, especially integrated circuits, can be manufactured from the wafer. The wafer is generally made of a brittle material, such as silicon, but also made of gallium arsenide or cadmium telluride. The basis for wafer manufacture is generally cylindrical or cubic single crystals or polycrystals, which are sawed into individual disks, or wafers. Sewing (also called cutting or wrapping) is actually performed by a wire saw, and essentially two methods are used.

  The so-called free abrasive wafer cutting is a separation method using a thin wire as a blade and cutting abrasive grains that are not bonded in a carrier liquid. The wire generally has a diameter of 80-180 μm. The wire is immersed in a slurry composed of a carrier liquid and cutting abrasive grains, and the cutting abrasive grains fixed to the wire surface enter the gap of the saw. The object / silicon block (referred to as an ingot) to be sawed / lapped is cut into a wafer by the cutting abrasive. At that time, particles are scraped from the solid to be cut. The carrier liquid for the cutting abrasive is applied as a slurry together with the cutting abrasive through a dipping bath through which the wire passes and generally through a nozzle. The carrier liquid has, inter alia, the problem of causing the cutting abrasive particles to adhere to the wire and removing the scraped particles from the solid to be cut. Furthermore, the carrier liquid has the role of providing cooling and transporting the wear through the saw slit.

  In the second method, that is, so-called fixed abrasive wafer cutting, a wire on which diamonds are arranged and a coolant are used. In the prior art, a corresponding coolant containing water is mentioned for cost reasons and better exhaust heat. The presence of water is technically a disadvantage as the resulting silicon wear product reacts with water to form silicate, precipitate and agglomerate. In order to avoid this drawback, the corresponding water-containing coolant must contain a high proportion of glycols and additives such as dispersants, silicate inhibitors and wetting agents. Corresponding water-containing coolants and suitable additives are mentioned, for example, in the documents JP 2006111728 A, JP 2004107620 A and JP 2007031502 A.

  The prior art for so-called free abrasive wafer cutting is as follows. EP 1 757 419 A1 is a method for separating a workpiece, for example by means of a wire saw of a wafer, wherein a slurry applied to the wire is used and the water content of at least part of the gaseous medium surrounding the slurry is adjusted Or the method of controlling is known. From EP 1 757 419 A1, it is further known to use glycols as carrier materials.

  From DE 199 83 092 B4 and US 6,383,991 B1, cutting oils comprising polyether compounds a) and silica particles b) are known, and this cutting oil composition is used for cutting ingots using a wire saw. In particular, it is known to be used for cutting silicon ingots.

  From EP 0 131 657 A1 and US Pat. No. 4,828,735, aqueous lubricants based on polyethers are known. From the Chinese patent application CN 101205498 A an aqueous cutting solution is likewise known, in which case the reduction of water absorption is not mentioned. Particularly mentioned compounds are polyalkyleneoxy compounds etherified with alcohols having 1 to 4 carbon atoms. From the above-mentioned documents it is not known that the corresponding formulations show a particularly favorable cooling or lubricating action.

  From EP 686 684 A1, a suspension for sawing consisting of an abrasive in an aqueous phase is known which contains one or more water-soluble polymers as thickeners. From US 2007/0010406 A1, hydroxypolyethers are known as additive substances for aqueous cutting liquids which can be used inter alia for the production of silicon wafers.

  Known cutting fluids for free abrasive wafer cutting and fixed abrasive wafer cutting are generally based on water. However, the presence of water is disadvantageous because it can cause corrosion or hydrogen can be generated by the reaction of water and silicon, for example when cutting silicon wafers. In that case, a further problem arises in that silicates or polysilicates form on the wafers, wires and machines.

  In addition, known water-soluble systems may contain water and draw water based on their hygroscopic properties, which may cause the same drawbacks as aqueous systems.

  The object of the present invention is to provide an improved cooling and / or lubricating liquid, in particular a cooling and / or lubricating liquid which leads to a reduction in water absorption and leads to a reduction in the energy required for sawing. Met. Furthermore, a corresponding cooling and / or lubricating liquid should ensure a particularly high exhaust heat and a particularly good wire saw, in particular a diamond wire saw.

［式中、
Ｒ¹は、１〜１０個の炭素原子を有するｚ価のアルキル基であり、
Ｒ²は、水素および／または１〜１０個の炭素原子を有する一価のアルキル基であり、
ＥＯは、エチレンオキシ基であり、
ＡＯは、３〜１０個の炭素原子を有するアルキレンオキシ基であり、
ｘは、１〜８の数、特に２〜８の数であり、
ｙは、０．５〜６の数、特に１〜４の数であり、
ｚは、１〜６の数、特に１〜３の数である］の化合物を、材料を削るための、特にワイヤソーでのウェハのソーイングのための、吸水性が低減された冷却および／または潤滑液の製造のために用いる使用によって解決される。 Said object is according to the invention the formula I

[Where:
R ¹ is a z-valent alkyl group having 1 to 10 carbon atoms,
R ² is hydrogen and / or a monovalent alkyl group having 1 to 10 carbon atoms,
EO is an ethyleneoxy group,
AO is an alkyleneoxy group having 3 to 10 carbon atoms,
x is a number from 1 to 8, in particular from 2 to 8,
y is a number from 0.5 to 6, in particular from 1 to 4,
z is a number from 1 to 6, especially a number from 1 to 3; cooling and / or lubrication with reduced water absorption for scraping materials, especially for sawing wafers with wire saws Solved by the use used for liquid production.

［式中、
Ｒ¹は、１〜１０個の炭素原子を有するｚ価のアルキル基であり、
Ｒ²は、水素および／または１〜１０個の炭素原子を有する一価のアルキル基であり、
ＥＯは、エチレンオキシ基であり、
ＡＯは、３〜１０個の炭素原子を有するアルキレンオキシ基であり、
ｘは、１〜６の数、特に１〜４の数であり、
ｙは、０．５〜６の数、特に１〜４の数であり、
ｚは、１〜６の数、特に１〜３の数である］の少なくとも１種の化合物を含有する冷却および／または潤滑液であって、該冷却および／または潤滑液は１質量％未満の含水量を有する前記冷却および／または潤滑液に関する。 Furthermore, the present invention provides a compound of general formula I

[Where:
R ¹ is a z-valent alkyl group having 1 to 10 carbon atoms,
R ² is hydrogen and / or a monovalent alkyl group having 1 to 10 carbon atoms,
EO is an ethyleneoxy group,
AO is an alkyleneoxy group having 3 to 10 carbon atoms,
x is a number from 1 to 6, in particular from 1 to 4,
y is a number from 0.5 to 6, in particular from 1 to 4,
z is a number of 1 to 6, particularly a number of 1 to 3], which is a cooling and / or lubricating liquid, wherein the cooling and / or lubricating liquid is less than 1% by mass. It relates to said cooling and / or lubricating liquid having a water content.

  Furthermore, the present invention relates to the use of the cooling and / or lubricating liquid according to the invention for scraping material, in particular for sawing a wafer with a wire saw, in particular with a diamond wire saw, and from the object using a wire saw. A method for cutting a wafer, wherein the object and / or the section in the object can be produced by the method according to the invention, wherein the object is cooled and / or lubricated by the cooling and / or cutting liquid, and the method according to the invention. In particular to manufactured wafers, in particular silicon wafers.

  According to the invention, the cooling and / or lubricating liquid can be used as a cooling liquid or as a lubricating liquid in the method for scraping the material, or a corresponding liquid that can be used as a liquid that fulfills both functions, ie cooling and lubrication. Means.

  The compounds according to the invention generally correspond to the general formula I.

R ¹ is generally a z-valent alkyl group having 1 to 10 carbon atoms, preferably a z-valent alkyl group having 1 to 8 carbon atoms, such as 1, 2, 3, 4, 5, 6, Z-valent alkyl radical having 7 or 8 carbon atoms, in particular pentyl, such as 3-methyl-1-butanol, octyl, such as 2-ethyl-hexanol, methyl or butyl, in particular 1-butyl.

The present invention therefore preferably relates to the use according to the invention, wherein R ¹ represents a z-valent alkyl radical having ¹ to 6 carbon atoms, in particular butyl.

z-valence means, within the scope of the invention, that the radical R ¹ may be substituted at the z positions by z alkylene oxide groups according to formula I. That is, R ¹ is derived from a z-valent alcohol. z in formula I generally means 1 to 6, preferably 1 to 3, particularly preferably 1. According to the invention, preferably monohydric to trihydric alcohols R ^1- (OH) _z are therefore used as the basis for the cooling and / or lubricating liquid according to the invention.

R ² generally means hydrogen and / or a monovalent alkyl group having 1 to 10 carbon atoms, preferably hydrogen. When R ¹ according to the invention is a polyvalent group, hydrogen and a monovalent alkyl group having 1 to 10 carbon atoms can be present simultaneously as group R ² .

EO means a group generally formed in general formula I by the ring-opening addition of an ethyleneoxy group, ie ethylene oxide, to an alcohol, in particular to an alcohol of the formula R ¹ —OH or the corresponding alkoxylate of this alcohol. .

x is generally a number from 1 to 8 in formula I, in particular a number from 2 to 8, for example 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, It means 5.5, 6, 6.5, 7, 7.5 or 8. x may be an integer or a fraction of a rational number according to the present invention. According to the present invention, x describes the average value of the molar amount of ethylene oxide for each 1 mol of alcohol R ¹ —OH. According to the present invention, there can be a corresponding distribution of molecules with various amounts of ethylene oxide, so a rational fraction may be determined for x. The measurement of x is generally performed by methods known to those skilled in the art, such as gel permeation chromatography, HPLC and / or NMR spectroscopy.

  For the cooling and / or lubricating fluids according to the invention, x is generally a number from 1 to 6, preferably a number from 1 to 4, where x may in this case also be an integer, or It may be a rational fraction.

According to the invention, it is possible to use alcohol R ¹ —OH as a basis for the production of the polyglycols used according to the invention. According to the invention, the alcohol R ¹ —OH is already together with 1, 2, 3 or 4 equivalents of ethylene oxide, ie the corresponding monoglycol, diglycol or triglycol of the alcohol R ¹ —OH. It may be the alcohol R ¹ —OH used. Accordingly, the alcohol R ¹ —OH monoglycol or diglycol such as butyl monoglycol (BMG) or butyldiglycol (BDG) is preferably used as the starting alcohol.

AO is generally an alkyleneoxy group having 3 to 10 carbon atoms in formula I, preferably a propyleneoxy group (PO), a butyleneoxy group (BuO) and / or pentyleneoxy (PeO), ie propylene oxide, By butylene oxide and / or pentylene oxide is meant a group formed by ring-opening addition to an alcohol, in particular an alcohol of the formula R ¹ —OH or the corresponding alkoxylate of this alcohol.

According to the invention, the alcohol R ¹ —OH, which has already been reacted with 1, 2, 3 or 4 equivalents of alkylene oxide (AO), ie the corresponding monohydric alcohol R ¹ —OH. Alkylene glycol, dialkylene glycol or trialkylene glycol can be used. Preferably, therefore, alkylalkylene glycols such as methyldipropylene glycol (MDP) can be used as the starting alcohol.

y is generally a number from 0.5 to 6 in formula I, in particular a number from 1 to 4, for example 0.5, 1, 1.5, 2, 2.5, 3, 3.5 or 4. means. y may be an integer or a fraction of a rational number according to the present invention. According to the present invention, y describes the average value of the molar amount of alkylene oxide ^per 1 mol of alcohol R ¹ —OH, respectively. According to the present invention, there can be a corresponding distribution of molecules with various amounts of alkylene oxide, so a rational fraction may be determined for y. The measurement of y is generally performed by methods known to those skilled in the art, such as gel permeation chromatography, HPLC and / or NMR spectroscopy.

In the corresponding compounds of formula I, the repeating units (EO) and (AO) may be present as blocks or statistically distributed (randomly). In a preferred embodiment, the repeating units are present in a statistically distributed manner. When distributed as a block or statistically, one or more (EO) molecules or one or more (AO) molecules may ^first be present bound to the alcohol R ¹ —OH.

  In a preferred embodiment, the cooling and / or lubricating liquid consists of a compound of formula I. The molecular weight of the compound of formula I is preferably 120 to 800 g / mol.

Particularly preferred compounds of the formula I are (3-methyl-1-butanol)-(PO) _1.5- (EO) _5.0 , preferably prepared in its block form, (2-ethyl-hexanol)-(PO ) _1.0 - (EO) _5.0, preferably those produced in the block form, (methyl - diethylene _{glycol) - (PeO) 2.0 - (} EO) 6.0, preferably those produced in the block form, (1-butyl -Monoglycol)-(PO) _3.0- (EO) _2.5 , preferably selected from its random production, (1-butyltriglycol)-(PO) _3.0 and mixtures thereof.

  The stated general and preferred embodiments of the compounds of the formula I apply independently of each other for the use according to the invention and also for the cooling and / or lubricating liquid according to the invention itself.

  The cooling and / or lubricating liquid according to the invention is particularly excellent in that the liquid lubricates particularly well in use when scraping the material. It can be examined, for example, by the amount of wear of stainless steel cylinders when using a lubricating liquid. For this purpose, the wear behavior is measured via mass loss of the cylinder by tribological methods known to the person skilled in the art, for example on a Reagert balance (Waage nach Reichert). The mass loss, expressed in mg, is in direct proportion to the cooling and lubricating fluid lubrication used by the present invention. In accordance with the invention, the wear is preferably less than 60 mg, advantageously less than 50 mg, particularly advantageously less than 45 mg, as measured by a Reichert scale.

  Therefore, the present invention is preferably a use according to the present invention, wherein said wear is measured by a Reichert scale and is measured as a mass loss of the stainless steel cylinder used, advantageously less than 60 mg. Relates to said use, which is less than 50 mg, particularly preferably less than 45 mg.

  Therefore, the present invention is preferably also a cooling and / or lubricating liquid according to the present invention, wherein the wear is measured as a mass loss of the stainless steel cylinder used, measured with a Reichert scale. The cooling and / or lubricating liquid of less than 60 mg, preferably less than 50 mg, particularly preferably less than 45 mg.

  According to the invention, the contact angle after 1 second at 25 ° C. of the cooling and / or lubricating liquid on V2A steel is preferably 10 to 40 °, particularly preferably 10 to 35 °.

  The present invention is therefore a use according to the invention, wherein the contact angle after 1 second at 25 ° C. on the V2A steel of said cooling and / or lubricating liquid is 10-40 °, preferably 10-35. Relates to said use being.

  According to the invention, the viscosity of the cooling and / or lubricating liquid at 20 ° C. is preferably 15 to 120 mPas, particularly preferably 20 to 110 mPa, particularly preferably 38 to 110 mPa.

  The present invention is therefore preferably used according to the invention, wherein the viscosity of the cooling and / or lubricating liquid at 20 ° C. is preferably 15 to 120 mPas, particularly preferably 20 to 110 mPa, particularly preferably 38 to Relates to said use being 110 mPa.

  The cooling and / or lubricating liquid according to the invention may contain not only one compound of formula I but also a mixture of formula I.

  The stated general and preferred properties of the compounds of the general formula I and of the use according to the invention apply independently of one another for the cooling and / or lubricating fluids according to the invention themselves.

  The preparation of the compounds of formula I is known per se. See, for example, Nonionic Surfactants, Martin J. Schick, Volume 2, Chapter 4 (Marcel Dekker, Inc., New York 1967).

  The cooling and / or lubricant according to the invention can generally be used in any method known to those skilled in the art for scraping materials, in particular for sawing a wafer with a wire saw. Preferably, the cooling and / or lubricating liquid according to the invention is used in a so-called free abrasive wafer cutting method or a fixed abrasive wafer cutting method.

  Such loose abrasive wafer cutting methods are known per se to those skilled in the art. In addition to at least one compound of the formula I, it contains abrasive grains and optionally further additives as defined in detail below for sawing.

  Conventional abrasive grains, in particular abrasive grains and / or cutting abrasive grains, may be used, for example metal grains, metal grains or semi-metal grains, carbide grains, nitride grains, oxide grains, boride grains or diamond grains. . Particularly preferred cutting abrasive grains are carbide grains and boride grains, especially silicon carbide (SiC) grains. The cutting abrasive preferably has a conformed shape, depending on the material and the wafer to be cut, with a preferred particle size of 0.5-50 μm. The cutting abrasive may be present in a heterodisperse form or a homodisperse form. The cutting abrasive grains are preferably contained in the cooling and / or lubricating liquid at a concentration of 25 to 60% by mass, particularly at a concentration of 40 to 50% by mass.

  Particularly preferably according to the invention, the cooling and / or lubricating liquid is used in a fixed abrasive wafer cutting method, in particular in a method using a diamond wire saw.

  The present invention therefore preferably relates to the use according to the invention, wherein the cooling and / or lubricating liquid is used in a fixed abrasive wafer cutting method, in particular in a method using a diamond wire saw.

  According to the invention, the wafer to be produced contains a semiconductor material, in particular silicon, GaAs, CdTe or ceramic, particularly preferably the wafer consists of a semiconductor material, in particular silicon, GaAs, CdTe or ceramic, in particular Single crystal silicon and polycrystalline silicon are preferable, and single crystal silicon is particularly preferable.

  The invention therefore preferably relates to the use according to the invention, wherein the wafer comprises a semiconductor material, in particular silicon, in particular consisting of silicon.

  These wafers are manufactured by sawing with a wire saw from cylindrical or prismatic blocks made of a corresponding semiconductor material. According to the invention, these blocks can be present as single crystals or polycrystals.

  In a preferred embodiment according to the present invention in which the cooling and lubricating liquid according to the present invention is used in a fixed abrasive wafer cutting method, the present invention can process single crystal or polycrystalline blocks made of semiconductor materials. In this case, the cooling and / or lubricating liquid contains, in a preferred embodiment, no further content other than one or more compounds of general formula I. That is, in this embodiment, the cooling and / or lubricating liquid according to the invention consists of one or more compounds of general formula I.

  In general, the cooling and / or lubricating liquid used according to the invention may contain 1 to 50% by weight of water. In a preferred embodiment, the cooling and / or lubricating liquid used has a water content of less than 1% by weight, particularly preferably less than 0.5% by weight, particularly preferably less than 0.1% by weight. .

  The present invention therefore preferably uses according to the invention, wherein the cooling and / or lubricating liquid is less than 1% by weight, preferably less than 0.5% by weight, particularly preferably less than 0.1% by weight. Said use having a water content of

  Particularly preferably according to the invention, the cooling and / or lubricating liquid used has a water content of less than 1% by weight, particularly preferably less than 0.5% by weight, particularly preferably less than 0.1% by weight. And a fixed abrasive wafer cutting method, particularly a method using a diamond wire saw.

  The invention is therefore preferably used according to the invention, wherein the cooling and / or lubricating liquid is less than 1% by weight, particularly preferably less than 0.5% by weight, particularly preferably 0.1% by weight. It relates to said use having a water content of less than and used in a fixed abrasive wafer cutting method, in particular in a method using a diamond wire saw.

  Furthermore, the cooling and / or lubricating liquid according to the invention has a reduced water absorption. The water absorption is, for example, 0 to 16% by weight, preferably 0.1 to 12% by weight, particularly preferably 0, as measured by differential weighing after storage for 7 hours at a relative air humidity of 38 ° C. and 78 ° C., respectively. .1 to 11% by mass.

  The water content of the cooling and / or lubricating liquid according to the invention can be measured by methods known to those skilled in the art. The lower limit of the water content is, for example, more than 1 ppm by mass, and more preferably more than 10 ppm by mass.

  The advantage according to the invention that the cooling and / or lubricating liquid is used at the abovementioned particularly low water content is that silicates cannot be formed from worn silicon particles due to the absence of water. The silicate makes post-treatment of the cooling and / or lubricating liquid used difficult and thus makes it difficult to recycle this liquid. In the absence of silicate, recycling of silicon wear, in particular, is clearly facilitated.

  Accordingly, the present invention is preferably a use according to the present invention, wherein the cooling and / or lubricating liquid is used after the material has been shaved, in particular after sawing with a wire saw of the wafer, for the separation of wear products that have occurred. Relates to said use being processed and / or recycled.

  A further advantage of the cooling and / or lubricating liquid according to the invention is that it is not necessary to add an additive, for example to suppress silicate formation or to provide a better lubricating action. This situation also facilitates recycling of the liquid.

  In a preferred embodiment of the method according to the present invention, a polycrystalline wafer having an irregular crystal structure and having a content of, for example, SiC, by means of the cooling and / or lubricating liquid according to the present invention, is preferably a fixed abrasive. Manufactured by grain wafer cutting method. This is possible, inter alia, because the cooling and / or lubricating liquid according to the invention has a greatly improved lubricating action.

  Furthermore, the cooling and / or lubricating liquid according to the invention has the advantage that the liquid is readily water-soluble. That is, after sawing the wafer, the wafer can be easily cleaned by rinsing with water or an aqueous solution.

  With regard to a further possible embodiment according to the invention in which the cooling and / or lubricating liquid according to the invention is used as an aqueous formulation, for example having a water content of 1 to 50% by weight, preferably added to the formulation Agent is added. These additives are known per se to those skilled in the art and are described below.

  In one embodiment of the invention, in addition to the compound of formula I, an alkylene alcohol based on ethylene oxide, propylene oxide or a copolymer of ethylene oxide and propylene oxide, preferably having a molecular weight of 200 to 800 g / mol It is included.

Further possible additives for cooling and / or lubricating liquids according to the invention are, for example, monoalkylene glycols, oligoalkylene glycols or polyalkylene glycols,
Wetting agent,
Dispersant,
Anticorrosive,
Other additives such as complexing agents and / or scale inhibitors.

For example, for 100 parts by weight of compound I, at least one of the following additives is added in the following parts by weight:
Alkylene glycol: 10 to 90 parts by weight, especially 20 to 60 parts by weight Wetting agent: 1 to 100 parts by weight, especially 10 to 40 parts by weight Dispersant: 0.1 to 20 parts by weight, particularly 0.5 to 10 parts by weight : 0.1-10 parts by weight, especially 0.1-3 parts by weight Complexing agent: 0.1-10 parts by weight, especially 1-5 parts by weight Other additives: 0.05-10 parts by weight, especially 0 .1-5 parts by mass.

  Particularly preferred additives are shown below.

Wetting agents In addition to the compounds of the formula I to be used according to the invention, further wetting agents, in particular (1) the following poly (oxyalkylene) derivatives a) to g) a) sorbitan esters, such as poly (oxyethylene) ) Sorbitan monolaurate, poly (oxyethylene) sorbitan monooleate, (poly (oxyethylene) sorbitan trioleate)
b) fatty amines such as tallow aminooxyethylate, soy aminooxyethylate c) castor oil such as castor oil oxyethylate d) alkanolamides such as coconut oil alkanolamidoxyethylate e) fatty acids such as oxyethyl oleate Rate, lauric acid oxyethylate, palmitic acid oxyethylate f) fatty acid alcohol g) linear alcohol oxyethylate, nonylphenol oxyethylate, octylphenol oxyethylate (2) hydrophilic polydimethylsiloxane a) at least one Poly (dimethyl) siloxane poly (dimethylsiloxane) copolymer substituted with two carbonyl end groups c) poly (dimethylsiloxane) -b-poly (propylene oxide) -b-poly (ethylene oxide) copolymer D) polyquaternary (dimethylsiloxane) copolymers (3) fatty imidazolines (4) fatty acid esters of a) to e) below a) phosphate esters b) sorbitan c) glycerol compounds such as glycerol monooleate, glyceryl Dioleate, glyceryl trioleate, dilaurate e) sulfosuccinic acid (5) quaternary compounds such as quaternary ammonium ethosulphate may be used.

Further suitable non-ionic, cationic, wetting agents of the anionic or amphoteric, especially - C ₄ -C ₂₂ are alkoxylated - alcohols, such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. These may be alkoxylated with ethylene oxide, propylene oxide and / or butylene oxide. Usable as wetting agents are in this case all alkoxylated alcohols which contain at least two molecules of the above-mentioned alkylene oxide added. In this case, block polymers of ethylene oxide, propylene oxide and / or butylene oxide are applicable, or addition products containing the above-mentioned alkylene oxides in a statistical distribution or block distribution. Nonionic wetting agents generally contain from 2 to 50 moles, preferably from 3 to 20 moles of at least one alkylene oxide per mole of alcohol. The alcohol preferably has 10 to 18 carbon atoms. Depending on the alkoxylation catalyst used in the preparation, the preparation method and the type of post-treatment, the alkoxylate has a broad or narrow alkylene oxide homolog distribution;
- C ₆ ~C ₁₄ - alkyl chain and 5-30 amino phenol alkoxylates having an alkylene oxide unit, for example, alkyl phenol ethoxylates;
Sorbitan, an alkylpolyglucoside having 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain and generally having 1 to 20, preferably 1.1 to 5 glucoside units Alkanoates, alkoxylated;
N-alkyl glucamides, fatty acid alkoxylates, fatty acid amine alkoxylates, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates, alkoxylated block copolymers from ethylene oxide, propylene oxide and / or butylene oxide, polyisobutene-ethoxylates Polyisobutene-maleic anhydride derivatives, optionally alkoxylated monoglycerides, glycerol monostearate, sorbitan esters and bisglycerides.

  Particularly suitable nonionic wetting agents are alkyl alkoxylates or mixtures of alkyl alkoxylates, for example 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. The wetting agent is an alkoxylation product or a mixture of alkoxylation products obtained by reacting an alkanol and an alkylene oxide in the presence of an alkoxylation catalyst. Particularly suitable starting alcohols are so-called Gerve alcohols, in particular ethylhexanol, propylheptanol and butyloctanol. Particularly preferred is propylheptanol. Preferred alkylene oxides are propylene oxide and ethylene oxide, preferably alkyl alkoxylates in which a short polypropylene oxide block is bonded directly to the starting alcohol, as described, for example, in DE-A 102 43 365 Particularly preferred due to its low residual alcohol content and due to its good biodegradability.

［式中、
Ｒ¹は、少なくとも一分岐型のＣ₄〜Ｃ₂₂−アルキルまたは−アルキルフェノールを意味し、
Ｒ²は、Ｃ₃〜Ｃ₄−アルキルを意味し、
Ｒ⁵は、Ｃ₁〜Ｃ₄−アルキルを意味し、
Ｒ⁶は、メチルもしくはエチルを意味し、
ｎは、１〜５０の平均値を意味し、
ｍは、０〜２０の、好ましくは０．５〜２０の平均値を意味し、
ｒは、０〜５０の平均値を意味し、
ｓは、０〜５０の平均値を意味し、
その際、ｍは、Ｒ⁵がメチルもしくはエチルであるかまたはｒが０の値を有する場合には少なくとも０．５である］のアルコールアルコキシレートである。 A preferred class of suitable nonionic wetting agents is of the general formula (NI)

[Where:
R ¹ means at least one branched C ₄ -C ₂₂ -alkyl or -alkylphenol;
R ² means C ₃ -C ₄ -alkyl,
R ⁵ means C ₁ -C ₄ -alkyl,
R ⁶ means methyl or ethyl,
n means an average value of 1-50,
m means an average value of 0-20, preferably 0.5-20,
r means the average value of 0-50,
s means an average value of 0-50,
Wherein m is an alcohol alkoxylate wherein R ⁵ is methyl or ethyl or is at least 0.5 when r has a value of 0].

Furthermore, 20 to 95% by weight, preferably 30 to 95% by weight of at least one alcohol alkoxylate and 5 to 80% by weight, preferably 5 to 70% by weight, R ¹ have the same carbon number. It may be a mixture of the corresponding alcohol alkoxylates which are unbranched alkyl groups.

［式中、
Ｒ³は、分枝鎖状もしくは非分枝鎖状のＣ₄〜Ｃ₂₂−アルキルもしくは−アルキルフェノールを意味し、
Ｒ⁴は、Ｃ₃〜Ｃ₄−アルキルを意味し、
ｐは、１〜５０の、好ましくは４〜１５の平均値を意味し、
ｑは、０．５〜２０の、好ましくは０．５〜４の、より好ましくは０．５〜２の平均値を意味する］のアルコールアルコキシレートであってよい。 Furthermore, the general formula (NII)

[Where:
R ³ represents a branched or unbranched C ₄ -C ₂₂ -alkyl or -alkylphenol;
R ⁴ means C ₃ -C ₄ -alkyl,
p means an average value of 1-50, preferably 4-15,
q may mean an alcohol alkoxylate of 0.5-20, preferably 0.5-4, more preferably 0.5-2].

  Furthermore, 5 to 95% by weight of at least one branched alcohol alkoxylate (NII) just described and 5 to 95% by weight of unbranched chains instead of branched alkyl groups It may be a mixture of the corresponding alcohol alkoxylates in the form of alkyl groups.

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

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

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

Radicals R ¹ are preferably, C ₈ -C ₁₅ -, particularly preferably C ₈ -C ₁₃ -, in particular C ₈ -C ₁₂ - an alkyl group, an alkyl group of at least one branch. There may also be a plurality of branches.

R ⁵ is preferably methyl or ethyl, in particular methyl. R ⁶ is preferably ethyl.

In the mixture, there is a compound having an unbranched alcohol group R ¹ and a branched alcohol group R ¹ . This is the case, for example, for oxo alcohols with a proportion of linear alcohol chains and a proportion of branched alcohols. For example, C _13/15 oxo alcohols often have about 60% by weight of a completely linear alcohol chain, but also about 40% by weight of α-methyl branched and C _{2 or higher} -branched alcohol chains. Have.

In the alcohol alkoxylate of the general formula (NII), R ³ is preferably a branched or unbranched C ₈ -C ₁₅ -alkyl group, particularly preferably a branched or unbranched chain. A C ₈ -C ₁₃ -alkyl group, especially a branched or unbranched C ₈ -C ₁₂ -alkyl group. R ⁴ is preferably propyl, in particular n-propyl. p preferably has an average value of 4-15, particularly preferably an average value of 6-12, in particular an average value of 7-10. q preferably has an average value of 0.5-4, particularly preferably 0.5-2, in particular 1-2.

  Corresponding to the alcohol alkoxylates of the general formula (NI), the alcohol alkoxylates of the general formula (NII) may also be present as a mixture having unbranched alcohol groups and branched alcohol groups. .

The alcohol component underlying the alcohol alkoxylate is not only a pure alkanol, but also a homologous mixture having a range of carbon atoms. Examples are C _8/10 alkanol, C _10/12 alkanol, C _13/15 alkanol, C _12/15 alkanol. Mixtures of multiple alkanols are also possible.

The alkanol alkoxylates or mixtures according to the invention described above are preferably alcohols of the general formula R ¹ —OH or R ³ —OH or mixtures of the corresponding branched and unbranched alcohols, optionally. By first reacting with a C ₃ -C ₆ -alkylene oxide, then with ethylene oxide, then optionally with a C ₃ -C ₄ -alkylene oxide and then with the corresponding C ₅ -C ₆ -alkylene oxide. Manufactured. The alkoxylation is then preferably carried out in the presence of an alkoxylation catalyst. In particular, basic catalysts such as potassium hydroxide are used. By means of special alkoxylation catalysts such as modified bentonites or hydrotalcites (which are described, for example, in WO 95/04024), the statistical distribution of the amount of alkylene oxide incorporated is strongly narrowed as “narrow” A “Narrow-Range” alkoxylate is obtained.

［式中、
Ａは、エチレンオキシを意味し、
Ｂは、それぞれ独立してＣ₃〜Ｃ₁₀−アルキレンオキシ、好ましくはプロピレンオキシ、ブチレンオキシ、ペンチレンオキシもしくはそれらの混合物を意味し、
その際、基ＡおよびＢは、ブロックの形で示された順序で存在し、
ｐは、０〜１０の数を意味し、
ｎは、０より大きく２０までの数を意味し、
ｍは、０より大きく２０までの数を意味し、
ｑは、０より大きく１０までの数を意味し、
ｐ＋ｎ＋ｍ＋ｑは、少なくとも１を意味し、その際、
Ｃ₅Ｈ₁₁がｎ−Ｃ₅Ｈ₁₁の意味を有するアルコキシレートＡ１を７０〜９９質量％と、Ｃ₅Ｈ₁₁がＣ₂Ｈ₅ＣＨ（ＣＨ₃）ＣＨ₂および／またはＣＨ₃ＣＨ（ＣＨ₃）ＣＨ₂ＣＨ₂を有するアルコキシレートＡ２を１〜３０質量％とが混合物で存在する］のアルコキシレートを含有するアルコキシレート混合物である。 In a specific embodiment of the invention, the compound of the general formula (NIII)

[Where:
A means ethyleneoxy,
B independently represents C ₃ -C ₁₀ -alkyleneoxy, preferably propyleneoxy, butyleneoxy, pentyleneoxy or mixtures thereof;
The groups A and B are then present in the order indicated in the form of blocks,
p means a number from 0 to 10;
n means a number greater than 0 and up to 20;
m means a number from 0 to 20;
q means a number greater than 0 to 10;
p + n + m + q means at least 1, in which case
C ₅ H ₁₁ and a 70 to 99% by weight of alkoxylate A1 having the meaning _{n-C 5 H 11, C} 5 H 11 is _{C 2 H 5 CH (CH 3} ) CH 2 and / or CH ₃ CH (CH ₃ ) 1 to 30% by mass of alkoxylate A2 having CH ₂ CH ₂ is present in the mixture].

In the general formula (NIII), p means a number from 0 to 10, preferably from 0 to 5, in particular from 0 to 3. When block (B) _p is present, p is preferably a number from 0.1 to 10, particularly preferably from 0.5 to 5, in particular from 1 to 3.

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

  q is preferably a number in the range of 1-5, particularly preferably a number in the range of 2-3.

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

  In the alkoxylate there are preferably 3 or 4 alkylene oxide blocks. According to one embodiment, the alcohol group is first followed by ethyleneoxy units, followed by propylene oxide units, followed by ethyleneoxy units. According to a further embodiment, the alcohol group is first followed by propyleneoxy units, then ethyleneoxy units, then propyleneoxy units, and finally ethyleneoxy units. Instead of propyleneoxy units, other mentioned alkyleneoxy units may also be present.

  p, n, m and q then refer to the average value which is provided as the average value for the alkoxylate. Thus, p, n, m, q may also be different from integer values. In the alkoxylation of an alkanol, a distribution of the degree of alkoxylation that can be adjusted to a predetermined size is generally obtained by using various alkoxylation catalysts. By selection of suitable amounts of groups A and B, the characteristic spectrum of the alkoxylate mixture according to the invention can be adapted according to practical requirements.

Said alkoxylate mixture is obtained by alkoxylation of the base alcohol C ₅ H ₁₁ CH (C ₃ H ₇ ) CH ₂ OH. The starting alcohol can be mixed so that the ratio according to the invention is obtained from a plurality of individual components. The alcohol can be produced by aldol condensation of valeraldehyde followed by hydrogenation. The production of valeraldehyde and the corresponding isomer is carried out by hydroformylation of butene. It is described, for example, in US Pat. No. 4,287,370; Beilstein E IV 1, 32 68, Ullmanns Encyclopedia of Industrial Chemistry, 5th edition, Volume A1, pages 323 and 328 and beyond. Subsequent aldol condensation is described, for example, in US 5,434,313 and Roempp Chemie Lexikon, 9th edition, heading “Aldol-Addition”, page 91. Hydrogenation of the aldol condensation product follows general hydrogenation conditions.

  Furthermore, 2-propylheptanol can be prepared by condensation of 1-pentanol (as the corresponding methylbutanol-1 mixture) at elevated temperature in the presence of KOH (eg Marcel Guerbet, CR Acad Sci Paris). 128, 511, 1002 (1899)). In addition, see Roempp Chemie Lexikon, 9th edition, Georg Thieme publication Stuttgart and the publications cited therein and Tetrahedron, Vol. 23, pages 1723 to 1733.

In the general formula (NIII), the group C ₅ H ₁₁ has the meaning n-C ₅ H ₁₁ , C ₂ H ₅ CH (CH ₃ ) CH ₂ or CH ₃ CH (CH ₃ ) CH ₂ CH ₂ . The alkoxylate is a mixture, wherein
- C ₅ H ₁₁ has the alkoxylates A1 having the meaning n-C ₅ H ₁₁ 70~99 wt%, preferably a 85 to 96% by weight,
1 to 30% by weight, preferably 4 to 15% by weight, of alkoxylate A2 in which C ₅ H ₁₁ has C ₂ H ₅ CH (CH ₃ ) CH ₂ and / or CH ₃ CH (CH ₃ ) CH ₂ CH ₂ And exist.

The group C ₃ H ₇ preferably has the meaning n-C ₃ H ₇ .

［式中、
Ｒは、イソトリデシル基を示し、
ｍは、２の数を表し、同時にｎは、３もしくは４の数を表すか、または
ｍは、３もしくは４の数を表し、同時にｎは、２の数を表し、かつ
ｘおよびｙは、互いに独立して、１〜２０の数を意味し、その際、
ｍ＝２／ｎ＝３もしくは４の場合に、変数ｘは、ｙより大きいかまたはｙと同じである］のブロック状のイソトリデカノールアルコキシレートであってもよい。前記のブロック状のイソトリデカノールアルコキシレートは、例えばDE 196 21 843 A1に記載されている。 Furthermore, the general formula (NV)

[Where:
R represents an isotridecyl group,
m represents the number 2 and at the same time n represents the number 3 or 4, or m represents the number 3 or 4, simultaneously n represents the number 2 and x and y are Independently of each other, means a number from 1 to 20,
When m = 2 / n = 3 or 4, the variable x may be greater than or equal to y] in the form of a block isotridecanol alkoxylate. Such block-like isotridecanol alkoxylates are described, for example, in DE 196 21 843 A1.

Another suitable nonionic surfactant class is end-capped alcohol alkoxylates, particularly those capped with the above-described alcohol alkoxylates. In one particular embodiment, it is the corresponding end-capped alcohol alkoxylate of the alcohol alkoxylates of general formula (NI), (NII), (NIII) and (NV). Terminal blocking can be, for example dialkyl sulfates, C ₁ -C ₁₀ - alkyl halides, C ₁ -C ₁₀ - phenyl halides, preferably chlorides, bromides, particularly preferably cyclohexyl chloride, cyclohexyl bromide, phenyl chloride or This can be done with phenyl bromide.

［式中、
Ｒ^Iは、水素またはＣ₁〜Ｃ₂₀−アルキルであり、
Ｒ^IIおよびＲ^IIIは、同一または異なっており、それぞれ互いに独立して、水素、メチルまたはエチルであり、
Ｒ^IVは、Ｃ₁〜Ｃ₁₀−アルキル、好ましくはＣ₁〜Ｃ₄−アルキルまたはシクロヘキシル−もしくはフェニル−であり、
ｍ’およびｎ’は、同一または異なっており、０以上であるが、但し、
ｍ’およびｎ’の合計は、３〜３００である］を有する。 Examples for end-capped alkoxylates are also described in DE-OS 37 26 121, the entire disclosure of which is hereby incorporated by reference in the present invention. In a preferred embodiment, the alcohol alkoxylate has the general structure (NVI)

[Where:
R ^I is hydrogen or C ₁ -C ₂₀ -alkyl;
R ^II and R ^III are the same or different and each independently of one another is hydrogen, methyl or ethyl;
R ^IV is C ₁ -C ₁₀ -alkyl, preferably C ₁ -C ₄ -alkyl or cyclohexyl- or phenyl-
m ′ and n ′ are the same or different and are 0 or more, provided that
The sum of m ′ and n ′ is from 3 to 300].

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

［式中、
Ｒ^Iは、Ｃ₅〜Ｃ₂₁−アルキル基またはアルケニル基を指し、
Ｒ²は、Ｃ₁〜Ｃ₄−アルキル基を意味し、
Ａ^Iは、Ｃ₂〜Ｃ₄−アルキレンを表し、
ｙは、２または３の数を指し、かつ
ｘは、１〜６の値を有する］の末端基封鎖脂肪酸アミドアルコキシレートである。 Further relevant nonionic wetting agents are known from WO-A 95/11225, of the general formula

[Where:
R ^I refers to a C ₅ -C ₂₁ -alkyl or alkenyl group,
R ² represents a C ₁ -C ₄ -alkyl group,
A ^I represents C ₂ -C ₄ -alkylene;
y represents a number of 2 or 3, and x has a value of 1 to 6].

Examples for such compounds are the reaction product of n-butyltriglycolamine of the formula H ₂ N— (CH ₂ —CH ₂ —O) ₃ —C ₄ H ₉ with methyl dodecanoate or the formula H ₂ and ethyl tetra glycol amine _{N- (CH 2 -CH 2 -O)} 4 -C 2 H 5, saturated C ₈ business practices -C ₁₈ - is the reaction product of a mixture of fatty acid methyl esters.

  In addition, nonionic wetting agents may further include 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, particularly end-capped. And fatty acid alkanolamide alkoxylates are suitable.

  Furthermore, as nonionic wetting agents, block copolymers made of ethylene oxide, propylene oxide and / or butylene oxide (BASF SE or BASF Corp.'s Pluronic (registered trademark) and Tetronic (registered trademark)) are also suitable. Yes. In a preferred embodiment, a triblock copolymer having a polyethylene / polypropylene / polyethylene block and having a molecular weight of 4000 to 16000, wherein the weight proportion of polyethylene block is 55 to 90 relative to the triblock copolymer. %. Particular preference is given to triblock copolymers having a molecular weight of greater than 8000, having a polyethylene content of 60 to 85% by weight, based on the triblock copolymer. These preferred triblock copolymers are commercially available from BASF Corp., particularly under the names Pluronic F127, Pluronic F108 and Pluronic F98, respectively, and are described in WO 01/47472 A2, the entire disclosure of which is hereby incorporated by reference It shall be disclosed in

Furthermore, block copolymers consisting of ethylene oxide, propylene oxide and / or butylene oxide, preferably also blocked on one or both sides, may be used. One side of the blockade, for example, alcohols, in particular C ₁ -C ₂₂ as the starting compound for reaction with the alkylene oxide - is achieved by using alkyl alcohols, such as methanol. Furthermore, for example, endcapping of the both sides, the free block copolymers, dialkyl sulfates, C ₁ -C ₁₀ - alkyl halides, C ₁ -C ₁₀ - phenyl halides, preferably chlorides, bromides, particularly preferably cyclohexyl Can be provided by reaction with chloride, cyclohexyl bromide, phenyl chloride or phenyl bromide.

In addition, a single nonionic wetting agent or a combination of various nonionic surfactants can be used. Only may be used alcohol - one only nonionic wetting agent comprising class, C ₄ -C _22, particularly alkoxylated. On the other hand, however, wetting agent mixtures from different classes may be used.

  The concentration of the nonionic wetting agent in the composition according to the invention can vary depending on the alkali treatment conditions, in particular depending on the material to be alkali treated.

Suitable anionic wetting agents include alkane sulfonates such as C ₈ -C _24- , preferably C ₁₀ -C ₁₈ -alkane sulfonates and soaps such as saturated and / or unsaturated C ₈ -C ₂₄ -carboxylic acid Na. Salt and K salt.

Further suitable anionic wetting agents are linear C ₈ -C ₂₀ -alkyl benzene sulfonates (“LAS”), preferably linear C ₉ -C ₁₃ -alkyl benzene sulfonates and -alkyl toluene sulfonates.

Dispersants / scale inhibitors Furthermore, according to the present invention, it is additionally selected from the group consisting of at least one dispersant, for example a salt of naphthalene sulfonic acid, a condensation product of naphthalene sulfonic acid and formaldehyde, and a polycarboxylate. Can be used. Corresponding dispersants 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 can also act as scale inhibitors (Belagsverhinderer) in some cases. This is because the dispersant disperses the calcium carbonate CaCO ₃ formed in the alkaline medium, thus inhibiting, for example, nozzle clogging or scale formation in the conduit. Regardless, the composition according to the invention may additionally contain at least one further scale inhibitor. Suitable scale inhibitors are described, for example, in WO 04/099092, said reference being
(A) a poly (meth) acrylic acid basic skeleton of 50 to 80% by weight, preferably 50 to 75% by weight, particularly preferably 55 to 70% by weight;
(B) 1 to 40% by weight, preferably 5 to 20% by weight, particularly preferably 7 to 15% by weight of one or more bonded to and / or introduced to the basic skeleton Units selected from the group consisting of isobutene units, telelactone units and isopropanol units;
(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 acid;
(Meth) acrylic acid copolymer, wherein the total mass of the units in the (meth) acrylic acid copolymer is 100% by mass, and all mass notations are relative to the (meth) acrylic acid copolymer. Certain (meth) acrylic acid copolymers are described.

The (meth) acrylic acid copolymers envisaged according to WO 04/099092 preferably have a mass average molecular weight of the polymer with sulfonic groups of 1000 to 20000 g / mol and preferably the following process steps:
(1) radical polymerizing (meth) acrylic acid in the presence of isopropanol and optionally water to obtain polymer I;
(2) amidating the polymer (I) derived from process step (1) by reaction with at least one aminoalkanesulfonic acid;
Can be manufactured.

Further suitable scale inhibitors include, for example:
A polycarboxylic acid half amide obtained by reaction of a polymer containing an anhydride group with a compound containing an amino group (according to DE 195 48 318),
-Vinyl lactic acid and / or isopropenyl lactic acid (according to DE 197 195 16),
-Homopolymers of acrylic acid (according to US-A-3 756 257),
A copolymer consisting of acrylic acid and / or (meth) acrylic acid and vinyl lactic acid and / or isopropenyl lactic acid,
A copolymer of styrene and vinyl lactic acid,
A copolymer consisting of maleic acid and acrylic acid,
The following (I) at least one monoethylenically unsaturated monomer:
(II) to a 200-5000 g / mol molar mass polymer of monoethylenically unsaturated dicarboxylic acid or anhydride thereof;
Obtained by radical-initiated graft polymerization,
(III) Water-soluble or water-dispersible graft polymer (DE 195 03 546) in which 5 to 2000 parts by weight of (I) are used per 100 parts by weight of graft base (II)
-Optionally hydrolyzed polymaleic anhydride and its salts (according to US-A-3 810 834, GB-A-1 454 657 and EP-A-0 261 589),
-Iminodisuccinate (according to DE 101 02 209),
A formulation (according to US 5,366,016) comprising a complexing agent, for example ethylenediaminotetraacetic acid (EDTA) and / or diethylenetriaminepentaacetic acid (DTPA),
-Phosphonates,
-Polyacrylates,
-Polyaspartic acid or polyaspartic acid modified with DE-A-44 34 463,
-Polyaspartic imide,
Hydroxamic acid, hydroxamic acid ethers and / or polymers with hydrazide groups (according to DE 44 27 630),
An optionally hydrolyzed maleimide polymer (according to DE 43 42 930),
Naphthylamino polycarboxylate (according to EP 0 538 969),
Oxaalkanepolyphosphonic acid (according to EP 330 075),
-Polyhydroxyalkane-amino-bis-methylenephosphonic acid (according to DE 40 16 753) and-oxidised polyglucosan (according to DE 43 30 339)
Is mentioned.

  Particularly preferred dispersants are polyacrylic acids, for example the Sokalan® type of BASF SE and polyaspartic acid, in particular β-polyaspartic acid having a molecular weight of 2000 to 10000 g / mol. Preference is given to acrylic acid homopolymers described in EP 2 083 067 A1 as the carboxylic acid group-containing compound of the polymer. These polymers preferably have a number average molecular weight in the range 1000 to 50000, particularly preferably in the range 1500 to 20000. A particularly suitable homopolymer of acrylic acid as the carboxylic acid group-containing compound of the polymer is under the trade name Sokalan® PA of BASF SE.

  Suitable polymeric carboxylic acid group-containing compounds are also oligomaleic acids such as those described in EP-A 451 508 and EP-A 396 303.

Further preferred as the carboxylic acid group-containing compound of the polymer is the polymerization introduction of at least one unsaturated mono- or dicarboxylic acid or dicarboxylic anhydride or salt thereof as monomer A) and at least one comonomer B). The copolymer contained. Preferably, the monomer A) is a C ₃ -C ₁₀ -monocarboxylic acid, C ₃ -C ₁₀ -monocarboxylic acid salt, C ₄ -C ₈ -dicarboxylic acid, C ₄ -C ₈ -dicarboxylic acid anhydride. Products, salts of C ₄ -C ₈ -dicarboxylic acids and mixtures thereof. Monomers A) in the form of salts are preferably used in the form of their water-soluble salts, in particular in the form of alkali metal salts, such as potassium salts and in particular sodium or ammonium salts. The monomers A) may each be present completely or partly in anhydrous form. Of course, mixtures of monomers A) can also be used.

  Said monomer (A) is preferably selected from acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, itaconic acid and mixtures thereof. Particularly preferred monomers (A) are acrylic acid, methacrylic acid, maleic acid, maleic anhydride and mixtures thereof. These copolymers preferably have at least one monomer A) in an amount of 5 to 95% by weight, particularly preferably 20 to 80% by weight, based on the total weight of the monomers used for the polymerization. In particular, it is introduced by polymerization in an amount of 30 to 70% by mass.

Anticorrosive Agent As an anticorrosive agent, for example, an agent described in WO 2008/071582 A1, for example, carboxylic acid acts. The carboxylic acid may be linear or branched. Mixtures of various carboxylic acids may be particularly preferred. Caprylic acid, ethylhexanoic acid, isononanoic acid and isodecanoic acid are particularly preferred carboxylic acids. Since anticorrosion emulsions are often neutral to weakly alkaline, it may be preferred to use the carboxylic acid in at least partially neutralized form, ie as a salt. For neutralization, sodium hydroxide solution and / or potassium hydroxide solution, as well as, for example, alkanolamines are particularly suitable. Particular preference is given here to the use of mono- and / or trialkanolamines. The use of dialkanolamine is less preferred due to the risk of nitrosamine formation. Nevertheless, dialkanolamines can also be used for neutralization alone or together with mono- and / or trialkanolamines.

  Suitable anticorrosives are in particular aliphatic carboxylic acid amides having 14 to 36 carbon atoms, such as myristic acid amide, palmitic acid amide and oleic acid amide; alkenyl succinamides having 6 to 36 carbon atoms, such as Octenyl succinamide, dodecenyl succinamide; mercaptobenzothiazole.

  Particularly preferred anticorrosives are particularly preferably alkylenediamine adducts of aliphatic amines, triethanolamine and ethylenediamine adducts with 2-8 mol% of propylene oxide.

Complexing agent A complexing agent is a compound that binds 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 diacetic acid), ASDA (aspartic acid diacetic acid), IDS (iminodisuccinic acid), HEIDA (hydroxyethylimine diacetic acid), EDDS (ethylenediamine disuccinic acid), citric acid, oxodisuccinic acid and butane Tetracarboxylic acids or their fully or partially neutralized alkali metal salts or ammonium salts.

Other Additives A particularly suitable additive is a scale inhibitor for silicates. It is preferably an alkoxylation product of an amine, particularly preferably an alkylene diamine, which is sold under the trade name Tetronic® by BASF Corp. and BASF SE. BASF Corp.'s Tetronic® 90R4 is considered particularly suitable.

［式中、
Ｒは、同一または異なる、直鎖状または分枝鎖状のＣ₂〜Ｃ₆−アルキレン基であり、
Ｂは、分岐を意味し、
Ｅは、式

のアルキレンオキシ単位を意味し、
Ｒ¹は、１，２−プロピレン、１，２−ブチレンおよび／または１，２−イソブチレンを意味し、
Ｒ²は、エチレンを意味し、
Ｒ³は、１，２−プロピレンを意味し、
Ｒ⁴は、同一または異なる基、水素、Ｃ₁〜Ｃ₄−アルキルを意味し、
ｘ、ｙ、ｚは、それぞれ２〜１５０の数を意味し、その際、ｘ＋ｙ＋ｚの合計は、アルコキシル化前のポリアルキレンイミンの３００〜１００００の平均分子量Ｍｗに相当するアルキレンイミン単位の数を意味し、
ｍは、０〜２の有理数を意味し、
ｎは、６〜１８の有理数を意味し、
ｐは、３〜１２の有理数を意味し、その際、０．８≦ｎ／ｐ≦１．０（ｘ＋ｙ＋ｚ）１／２である］の両性の水溶性アルコキシ化ポリアルキレンイミンである。 Further suitable additives are, for example, fixing agents. Suitable fixing agents are, for example, those of the general formula AI described in WO 2006/108856 A2.

[Where:
R is the same or different linear or branched C ₂ -C ₆ -alkylene group;
B means branch,
E is the formula

Means an alkyleneoxy unit of
R ¹ means 1,2-propylene, 1,2-butylene and / or 1,2-isobutylene,
R ² means ethylene,
R ³ means 1,2-propylene,
R ⁴ represents the same or different group, hydrogen, C ₁ -C ₄ -alkyl,
x, y, and z each represent a number of 2 to 150, where the sum of x + y + z represents the number of alkyleneimine units corresponding to an average molecular weight Mw of 300 to 10000 of the polyalkyleneimine before alkoxylation. And
m means a rational number from 0 to 2,
n means a rational number between 6 and 18,
p represents a rational number of 3 to 12, in which case 0.8 ≦ n / p ≦ 1.0 (x + y + z) 1/2] is an amphoteric water-soluble alkoxylated polyalkyleneimine.

［式中、
Ｒ¹は、１〜１０個の炭素原子を有するｚ価のアルキル基であり、
Ｒ²は、水素または１〜１０個の炭素原子を有する一価のアルキル基であり、
ＥＯは、エチレンオキシ基であり、
ＡＯは、３〜１０個の炭素原子を有するアルキレンオキシ基であり、
ｘは、１〜８の数、特に２〜８の数であり、
ｙは、０．５〜６の数、特に１〜４の数であり、
ｚは、１〜６の数、特に１〜３の数である］の少なくとも１種の化合物を含有する冷却および／または潤滑液であって、該冷却および／または潤滑液は１質量％未満の含水量を有する前記冷却および／または潤滑液に関する。 The present invention also relates to general formula I

[Where:
R ¹ is a z-valent alkyl group having 1 to 10 carbon atoms,
R ² is hydrogen or a monovalent alkyl group having 1 to 10 carbon atoms,
EO is an ethyleneoxy group,
AO is an alkyleneoxy group having 3 to 10 carbon atoms,
x is a number from 1 to 8, in particular from 2 to 8,
y is a number from 0.5 to 6, in particular from 1 to 4,
z is a number of 1 to 6, particularly a number of 1 to 3], which is a cooling and / or lubricating liquid, wherein the cooling and / or lubricating liquid is less than 1% by mass. It relates to said cooling and / or lubricating liquid having a water content.

  With regard to the cooling and / or lubricating liquid according to the invention, the above applies correspondingly for the use according to the invention.

Preferably, the present invention relates to a cooling and / or lubricating liquid according to the present invention wherein R ¹ is butyl.

  The invention also relates to the use of the cooling and / or lubricating liquid according to the invention for grinding materials, in particular for sawing wafers with a wire saw, in particular with a diamond wire saw. For this reason, what has been said above for the loose abrasive wafer cutting method or the fixed abrasive wafer cutting method applies accordingly.

  The present invention also cuts a wafer from an object using a wire saw, particularly from a block, ingot or cylinder made of a semiconductor material such as silicon, GaAs, CdTe and ceramic, especially from a silicon block, silicon ingot or silicon cylinder. A method for doing so, wherein the object and / or the section in the object is cooled and / or lubricated with a cooling and / or lubricating liquid according to the invention as defined above.

  The invention also relates to a particularly manufactured wafer, in particular a silicon wafer, which can be produced by the method according to the invention. The wafers produced according to the invention are superior in that they show fewer microcracks than the wafers produced by prior art methods based on the production method according to the invention. This reduces the risk of breakage. Furthermore, the wafer has a more uniform surface than wafers manufactured according to the prior art, based on the manufacturing method according to the invention, and has fewer streaks.

  The cooling and / or lubricating liquid according to the invention and the cutting method according to the invention are particularly suitable for ingots, blocks or cylinders made of monocrystalline or polycrystalline silicon monocrystalline or polycrystalline, GaAs, CdTe and other semiconductors and ceramics (ingots). Suitable for sawing).

  The cooling and / or lubricating liquid according to the invention can be used as an anhydrous formulation, preferably without further additives, and thus reprocessing, for example by chemical engineering wet aftertreatment according to WO 02/40407 A1 and EP 1 390 184 A1 Very suitable for.

Example:
General production instructions for polyethers In an anhydrous, dry 1 L pressure reactor, 1-2 mol each of starting alcohol is charged, and 0.2% by weight (based on the final product) of KOH is added. Add and rinse with nitrogen. The closed reactor is then warmed to 130 ° C. over 30 minutes and adjusted to 1 bar overpressure with nitrogen. Subsequently, the molar amounts of propylene oxide or pentene oxide (hereinafter referred to as PO or PeO) and ethylene oxide (hereinafter referred to as EO) shown in Table 1 in parallel (random work mode) or sequentially (block work mode). Weigh while stirring.

  In the case of a block working mode, PO or PeO is added, after the pressure has reached a constant, it is stirred at 130 ° C. for at least 0.5 hours and the pressure is adjusted to 1 bar before adding EO. During the reaction, the vessel is conditioned to 130 ° C. After the pressure has reached a constant, the mixture is further stirred for about 0.5 hours. After the reaction is complete, cool to 80 ° C., let the reactor release and rinse with nitrogen, add the calculated amount of glacial acetic acid for KOH neutralization and stir for 0.5 h .

  The OH number is measured according to DIN 51562, the residual alcohol is measured by gas chromatography and the color number APHA is measured by EN 1557 (23 ° C.).

Table 1: Examples and analysis

  Examples C1-C5 are examples according to the invention, examples C6 and C7 are comparative examples, n. b. Means not measured.

Properties The properties of the cooling and / or lubricating liquids C1 to C5 according to the invention are summarized in Table 2. For comparison, two examples are given (C6 and C7) that are not industrially used as cutting fluids (market standard) according to the invention. C7 contains 80% by weight propylene glycol, 18% by weight water and 2% by weight of additives not specified or analyzed in detail.

The following properties were measured:
Water absorption The water absorption of the cooling and / or lubricating liquid is measured after 7 hours after storing the liquid in a Heraeus BBD 6220 type CO ₂ incubator at 38 ° C. and a relative air humidity of 78%. For storage, 1 g of each cutting solution is used in a Petri dish with an internal diameter of 60 mm. The average value of each double measurement is obtained. The water absorption is indicated by an increase in mass% with respect to the initial weighing.

Viscosity The viscosity of the cutting fluid is measured at 20 ° C. using a Brookfield LVDV-III Ultra device (spindle V-73). The viscosity is indicated in mPas.

Contact angle The contact angle of the cutting solution is measured at 25 ° C. 1 second after the surface has been rinsed with water and acetone and subsequently dropped onto a steel plate made of V2A steel that has been dried with air. For the measurement, a video-assisted high-speed contact angle measuring device from Dataphysics Instruments GmbH (Filderstadt) is used. The unit of contact angle is indicated in degrees [°].

Wear Wear behavior is a stainless steel cylinder for roller bearings named Needle Bearing ZRO. 12x18 with a load of 300 N and a travel of 110 m on a balance (Hermann Reichert Maschinenbau, Heidenhof Backnang) named MDD2. Measured in minutes. The cylinder is purchased from Timken Company (Canton / Ohio / USA). Duplicate measurements are performed for each, and the average value of cylinder mass loss is measured. Mass loss is shown in mg.

Table 2

Claims (14)

Formula I

[Where:
R ¹ is a z-valent alkyl group having 1 to 10 carbon atoms,
R ² is hydrogen and / or a monovalent alkyl group having 1 to 10 carbon atoms,
EO is an ethyleneoxy group,
AO is an alkyleneoxy group having 3 to 10 carbon atoms,
x is a number from 1 to 8, in particular from 2 to 8,
y is a number from 0.5 to 6, in particular from 1 to 4,
z is a number from 1 to 6, especially a number from 1 to 3; cooling and / or lubrication with reduced water absorption for scraping materials, especially for sawing wafers with wire saws Use to make liquids. Use according to claim 1, characterized in that in formula I R1 represents a z-valent alkyl group having ¹ to 6 carbon atoms, in particular butyl.   Use according to claim 1 or 2, wherein the contact angle after 1 second at 25 ° C of the cooling and / or lubricating liquid on V2A steel is 10-40 °, preferably 10-35 °. Use characterized by being.   Use according to any one of claims 1 to 3, wherein the viscosity of the cooling and / or lubricating liquid at 20 ° C is preferably 15 to 120 mPas, particularly preferably 20 to 110 mPas. Features use.   5. Use according to any one of claims 1 to 4, characterized in that the wafer contains a semiconductor material, in particular silicon, in particular consisting of silicon.   Use according to any one of claims 1 to 5, characterized in that the cooling and / or lubricating liquid is used in a fixed abrasive wafer cutting method, in particular in a method using a diamond wire saw. Use to.   7. Use according to any one of claims 1 to 6, characterized in that the cooling and / or lubricating liquid has a water content of less than 1% by weight.   8. Use according to any one of claims 1 to 7, wherein the cooling and / or lubricating liquid is used to separate the generated wear material after shaving the material, in particular after sawing the wafer with a wire saw. Use characterized by being post-treated and / or recycled.   9. Use according to any one of claims 1 to 8, wherein the wear is measured by a Reichert scale and measured as a weight loss of the stainless steel cylinder used, and less than 60 mg. Use characterized by being. Formula I

[Where:
R ¹ is a z-valent alkyl group having 1 to 10 carbon atoms,
R ² is hydrogen and / or a monovalent alkyl group having 1 to 10 carbon atoms,
EO is an ethyleneoxy group,
AO is an alkyleneoxy group having 3 to 10 carbon atoms,
x is a number from 1 to 6, in particular from 1 to 4,
y is a number from 0.5 to 6, in particular from 1 to 4,
z is a number of 1 to 6, particularly a number of 1 to 3], which is a cooling and / or lubricating liquid, wherein the cooling and / or lubricating liquid is less than 1% by mass. A cooling and / or lubricating liquid characterized by having a water content. The cooling and / or lubricating liquid according to claim 10, wherein R ¹ is butyl.   12. Use of the cooling and / or lubricating liquid according to claim 10 or 11 for sawing a material, in particular for sawing a wafer with a wire saw, in particular with a diamond wire saw.   12. A method of cutting a wafer from an object by means of a wire saw, wherein the object and / or a section in the object is defined in claim 1 or a cooling and / or lubricating liquid according to claim 10 or 11 And cooled and / or lubricated.   14. A particularly manufactured wafer, in particular a silicon wafer, which can be produced by the method according to claim 13.