DE19848611A1 - Surface treatment solution for substrate, especially metal, e.g. for vapor deposition or plasma coating - Google Patents

Abstract

Surface treatment solution contains 0.001-10, preferably 0.5-2 wt.% (chloro)fluoroalkane derivative (I) with a polar or dipolar group, e.g. carboxyl, acyl, carbonyl fluoride, hydroxyalkyl, acyloxy, amide, cyano, urea, sulfo, hydroxyl, mercapto, phosphono, phosphato or acrylyl group. Surface treatment solution contains 0.001-10, preferably 0.5-2 wt.% (chloro)fluoroalkane derivative, with a polar or dipolar group, of formula (I); Rf = a partly or completely fluorinated or chlorofluorinated, linear or branched aliphatic hydrocarbyl group, optionally with oxygen (O), nitrogen (N) or sulfur (S) atom(s) in the chain; V = a polar or dipolar group selected from -COOR, -COR, -COF, -CH2OR, -OCOR, -CONR2, -CN, -CONH-NR2, -CON=C(NH2)2, -CH=NOR, -NRCONR2, -NR2COR, -Nw, -SO3R, -OSO3R, -OH, -SH, B, -OP(OH)2, -OP(ONH4)2, -OPO(ONH4)2 and -CO-CH=CM2; R = hydrogen (H), phenyl or linear or branched alkyl or alkyl ether group, which may be (partly) (chloro)fluorinated and has <= 12, preferably <= 8 carbon (C) atoms, or -Rv-V; w = 2 or 3; or Rv = linear or branched alkylene, which may be (partly) (chloro)fluorinated and has 1-12, preferably <= 8 C. Independent claims are also included for (a) a method for surface treatment of a substrate; and (b) the resultant products.

Description

The invention relates to a surface treatment agent for Treating and changing the surface properties of Surfaces, especially metallic surfaces, and a Process for treating surfaces of substrates, especially of metallic substrates, using the Treatment agent, as well as treated according to the procedure Substrates and their use in particular in a CVD or PVD or PCVD coating processes (chemical, physical or physical / chemical deposition from the ionized Gas phase) or other coating method, in particular Plasma coating process.

CVD or PVD coating processes are state of the art well known. In such procedures, which under others also for the production of semiconductors or devices will be used with hard surface coatings cleaned substrate from an atmosphere a chemical compound of the layer-forming compound or the layer-forming element, for example one Semiconductor element, a chemical or physical Exposed to decomposition treatment, the compound or the element is deposited on the substrate. This will a high purity layer e.g. B. of semiconductor material, such as Silicon, gallium, germanium, or from other compounds, such as titanium nitride or boron compounds, optionally under Addition of dopants such as P, As etc. to harden the Surface etc. built.

However, there were processes known in the art Difficulties caused by separation processes on the Interface of the coating to the substrate. In the state of the art Attempts have been made to address this problem Surface treatment process before coating, such as To oppose etching processes etc. The achieved here  However, results are not satisfactory because of this a sufficiently good adhesion between the layer and the Substrate could not be achieved.

The object is achieved by the invention, a Surface treatment agent and a method for To provide improvement in interface adhesion.

Extensive investigations have been carried out by the inventor about how the liability properties of the adjacent surface layers can be improved can. As a decisive consideration, the Inventor of the train of thought developed the surfaces of the Substrates before the CVD coating in contrast to the state of the Technology not to provide high purity, but on the Surface of the substrate before CVD or PVD treatment Apply a layer of a treatment agent, which according to Art a liability broker a reliable liability between the in the next step applied CVD layer and the substrate enables.

The inventor therefore found out in the course of his investigations that that the surface properties of the substrate after that Pretreatment with a polymeric organofluorine compound can be changed so that the liability of the next Process step in the CVD or PVD coating or other plasma coating layer essential is improved. At the same time, the roughness and the Porosity of the surface is reduced and it can reduce the density of the layer applied in the CVD or PVD process without detaching the layer.

The invention is therefore directed to a surface treatment agent for treating substrates, in particular to change the surface properties of substrates, especially of substrates with metallized or metallic or ceramic surface or one Plastic surface, as well as a method for treating  Substrates, especially of metallic or ceramic Substrates, using the treatment agent, as well as on substrates treated by the process and their use especially in a CVD or PVD coating process.

The surface treatment agent according to the invention is in the form of a solution of 0.001 to 10% by weight, preferably 0.5 to 2% by weight, of an organofluorine compound of the formula R _f -V in a solvent, preferably a halogenated hydrocarbon solvent such as perfluorinated or chlorinated alkanes or cycloalkanes, with up to 12 carbon atoms, or in the form of an aqueous solution of the organofluorine compound of the formula R _f -V with an emulsifier in an amount of up to 5% by weight, based on the total weight of the aqueous solution.

In the formula R _f -V of the abovementioned fluoroorganic compound, R _f stands for an aliphatic hydrocarbon radical which can be partially or completely fluorinated and can be straight-chain, branched-chain or cyclic, the hydrocarbon radical being represented by one or more oxygen, nitrogen or sulfur atoms can be interrupted.

In the formula R _f -V of the above-mentioned organofluorine compound, V represents a polar or dipolar group which is selected from -COOR, -COR, -COF, -CH ₂ OR, -OCOR, -CONR ₂ , -CN, - CONH-NR ₂ , -CON = C (NH ₂ ) ₂ , -CH = NOR, -NRCONR ₂ , -NR ₂ COR, -NR _w , -SO ₃ R, -OSO ₃ R, -OH, -SH, / B, -OP (OH) ₂ , -OPO (OH) ₂ , -OP (ONH ₄ ) ₂ , -OPO (ONH ₄ ) ₂ , -CO-CH = CH ₂ . Therein R in a group V can be the same or different and stands for hydrogen, a phenyl radical or a straight-chain or branched-chain alkyl or alkyl ether radical, which can be partially or completely fluorinated or chlorofluorinated, with up to 12, preferably up to B carbon atoms, where w represents 2 or 3,
or stands for -R _v V-, where V is the polar or dipolar group indicated above and R _{v is} a straight-chain or branched-chain alkylene radical which can be partially or completely fluorinated or chlorofluorinated, with 1 to 12, preferably up to 8, carbon atoms stands.

V preferably represents a member from the group consisting of -COOH, -SO ₃ H, -COOR, -SOR, -COR, -COCF ₃ , -COCF (CF ₃ ) ₂ , -PO (OH) ₂ and -SO ₂ R, in particular -COOH, -SO ₃ H, -COR, and -SO ₂ R, where R is a straight-chain or branched-chain alkyl radical which is partially or completely fluorinated, with up to 12, preferably up to 8 carbon atoms, or represents -R _v V-, where V represents the polar or dipolar group indicated above and R _v denotes a straight-chain or branched-chain alkylene radical, which can be partially or completely fluorinated or chlorofluorinated, with up to 12, preferably up to 8, carbon atoms.

The radical denoted by R _f , which is partially or fully fluorinated, is preferably one with a molecular weight of 1000 to 10,000, preferably 1400 to 10,000. In particular with a molecular weight within this range, molecular chains of favorable length are formed, which on the one hand are not too short and, on the other hand, are not too long in order to be able to form the spiral-like molecular structures to be explained further below.

The radical denoted by R _f is more preferably partially or fully fluorinated alkanes or partially or fully fluorinated alkyl ethers or thioethers with a preferred molecular weight of 1,400 to 10,000.

R _f in the formula R _f -V preferably represents a straight-chain or branched-chain aliphatic hydrocarbon radical having the following schematic formula (1)

RO _x (C _a H _b F _2a-b O) _m (C _a H _b F _2a-b ) _n (1)

wherein
a = 2, 3, 4;
b = 0, 1, 2;
x = 0.1;
20 ≦ n + m ≦ 500;
n ≧ 1 and m ≧ 0, and
R represents a straight-chain or branched-chain alkyl radical which is partially or fully fluorinated, has up to 12, preferably up to 8, carbon atoms or alternatively F if x = 0.

In the formula (1),

RO _x (C _a H _b F _2a-b O) _m (C _a H _b F _2a-b ) _n (1)

a = 2, 3; b = 0.1; x = 0.1; 25 ≦ n + m ≦ 200; n ≧ 1 and m ≧ 0, and R is a straight-chain or branched-chain alkyl radical which is partially or fully fluorinated, with up to 12, preferably up to 8 carbon atoms, or alternatively F means if x = 0.

In the formula (1) very particularly preferably a = 2, 3; b = 0; x = 0.1; 25 ≦ n + m ≦ 200, and n = 1.

Compounds of the general formula R _f1 R _f2 -V can be used as particularly preferred compounds of the formula R _f -V in the treatment agent according to the invention, where V has the meaning given above and the groups R _f1 and R _{f2 have} the following meanings:

R _f1 represents a perfluoroalkyl ether group of the formula C _n F _{2n + 1} O-, where n can be 1 to 8; R _f2 stands for a perfluoroalkyl ether group of the following formulas (I) to (IV):

where n = 8 to 55, m = 0 to 10 and k = 0-1;

(-CF ₂ -CF ₂ O) _n (CF ₂ O) _m CF ₂ - (II)

where n = 5 to 200 and m = 0 to 30;

(-CF ₂ CF ₂ CF ₂ O) _n CF ₂ CF ₂ - (III),

where n = 5 to 50;

(-CH ₂ -CF ₂ -CF ₂ O-) _n CH ₂ CF ₂ - (IV),

where n = 5 to 50.  

In the perfluoroalkyl ether groups of the formulas (I) to (IV) as previously indicated, the indices n, m and k denote the number of indicated unit each in a perfluoroalkyl ether group (I) or (II), but not such that m or k units follow each other directly.

In these compounds of the aforementioned formulas, their Manufacturing is known in the art, so that is only briefly discussed here Partial or complete polymerization products fluorinated alkanes such as ethylene, propylene or butylene, which in Be polymerized in the presence of oxygen. For example Such polymers, starting from perfluoropropylene, -butylene or -ethylene, which are in liquid form and below -30 EC in the presence of oxygen with ionizing radiation are irradiated or at this Temperature treated with a mixture of fluorine and oxygen will be manufactured.

An alternative way of producing these compounds is to react perfluoroethylene with formaldehyde under elevated pressure at 20-60 ° C in the presence of hydrogen fluoride to form the corresponding oxetane and subsequent polymerization in the presence of COF ₂ .KF in an aprotic solvent with ring opening of the oxetane .

It is also possible to start such perfluoropolymers from the epoxy of perfluoroethylene, propylene or butylene or Mixtures of these, with the addition of potassium fluoride or Cesium fluoride in an aprotic solvent in one polymerize anionic polymerization reaction.

In these polymerizations, mixtures of perfluoroalkyl ether polymers with different chain structures are generally formed. With these polymers, complete fluorination of the alkyl chain can be achieved with the aid of conventional fluorinating agents such as SbF ₅ , CoF ₃ or silver fluoride. In the case of the polymers, there is usually a terminal -C (= O) F group which saponifies in a further reaction and then, if appropriate, with a further reaction partner such as an amino, thio, amido compound etc. can be substituted with alkyl radicals, is converted to a carboxylic acid derivative.

The inventor has found that compounds of the general formula R _f -V are applied to the metallic surface to be loaded in the form of a solution in a partially or fully fluorinated hydrocarbon or partially or fully fluorinated chlorinated hydrocarbon in a concentration of 0.001 to 10% by weight and can adhere firmly to the wetted surface, even after knocking off or washing off the excess liquid and drying.

As a result of the fat-dissolving properties of the solvent, the surface of the substrate is completely freed of fat and the attachment of the molecules R _f -V to the surface is made possible accordingly easily. The application can be done by immersing or wetting or brushing the surface, and the solvent evaporates after the excess solution has run off from the surface, so that a loading of the surface with the molecules of the formula R _f -V is ensured.

Fundamental considerations of the inventor regarding the physical and electronic bases of the liability phenomena of the layer to be applied on the substrate led to the Realizing that the liability between the two is the Components forming boundary layers essentially by Interaction with those present on the respective surfaces Dislocation is caused. Such Dislocation sites represent errors in the crystal structure of the Substrates that are present at the places where the smallest ordered crystallite units of the substrate meet or corresponding irregularities in the crystal structure available. Such dislocation points cause metallic substrates that that between the metal atoms basically freely moving electron gas at interfaces  bumps that can only be overcome with additional energy can be.

Since such irregularities in the crystal structure in the Occur inside as well as on the surface of a substrate and those that occur for a split second Selective polarization within the substrate different surface charges are generated with corresponding surface charges on the surface of the other layer of the pair of layers interact, the adhesion of the layers is believed to be due to the caused electromagnetic forces.

The inventor surprisingly found that the adhesion between the layers of the pair of layers produced in a CVD or PVD process can be improved in that the surface of the substrate which is to be coated in the CVD or PVD process, for example with a semiconductor material , is treated with a solution of one or more compounds of the formula R _f -V in a solvent, preferably a perfluorinated solvent such as Frigen, in a concentration of 0.001 to 10% by weight, optionally with the addition of an emulsifier or surfactant, after which then the coating takes place in a PVD, CVD or PCVD chamber.

Although the mechanism for the attachment of the molecules R _f -V could not be fully clarified, the inventor assumes that the molecules R _f- V are present on the surface due to the charge differences between individual areas of the substrate surface formed by the dislocation sites and the hydrophilic ones Group, ie a group with dipolar or polar properties, can be attached and so to speak "freeze" the dislocation state at the attachment point.

The inventor has carried out extensive attempts to test the suitability of compounds with different hydrophilic groups V in the molecule R _f -V. It turned out that such molecules can be readily attached to the surface as long as such a group V with a pronounced dipole property is used. In the context of the invention, dipole property is understood to mean that, owing to the different electronegativities of the atoms present in group V, bonds are polarized and charge differences between the individual atoms, ie small positive or negative potentials, are produced on the atoms involved in the bond. Such interactions can also be caused by the atoms with free electron pairs present in group V.

Due to the length of the molecular chains R _{f of} the compounds R _f -V and the distance between the molecules anchored to the surface R _f - V, the residues R _f tend to form tangled, feather-like or spiral structures.

The inventor also found that since, according to the above, the molecules R _f -V are anchored via the group V to the surface, which the inventor believes is due to the polarization of the group V, in addition to the metallic substrate surfaces such surfaces can be loaded that allow the molecules of the formula R _f -V to attach due to polar structures on the surface.

Thus, it is also possible according to the invention to provide other substrate materials with a loading matrix of compounds of the formula R _f -V in the sense of the invention, which are not to be understood directly as a pair of layers in the sense of the above definitions.

The invention is therefore also directed to a method for treating the surface of a substrate, which preferably comprises the following steps:
Cleaning the surfaces of the substrate with a solvent that may be present to remove impurities;
Drying the surface at a temperature above the evaporation temperature of the solvent; Treating the surface of the substrate with the treatment agent in the form of a solution of 0.001 to 10% by weight of an organofluorine compound of the formula R _f -V in a halogenated hydrocarbon solvent having up to 12 carbon atoms, or in the form of an aqueous solution of 0.001 to 10% by weight. % of the organofluorine compound of the formula R _f -V with an emulsifier in an amount of up to 5% by weight, based on the total weight of the aqueous solution;
and optionally allowing the solution to act for a period of up to 60 minutes, preferably 2 to 30 minutes, and optionally drying the substrate at a temperature above the evaporation temperature of the solvent used for a period sufficient to completely evaporate the solvent. In order to favor the effect of the solution on the substrate, ultrasonic vibrations can be applied or the solution can be brought into the boiling or cavitation state.

The substrate treated in this way can be introduced directly into a vapor deposition chamber and then provided with a coating which, owing to the loading of the surface of the substrate with compounds of the formula R _f -V as adhesion promoter, shows improved adhesion as an untreated substrate.

By means of the coating with compounds of the formula R _f -V, all materials which are to receive hard surface layers can be subjected to a pretreatment before CVD, PVD or plasma post-treatment. This also includes tools, gears, roller bearings, etc.

Alternatively, the organofluorine compound R _f -V, before the start of the CVD, PVD or PCVD vapor deposition process under the working atmosphere and its pressure conditions which are provided for the vapor deposition process, can be introduced into the vacuum chamber in the form of the treatment agent in solution or undiluted, in particular be sprayed or injected and so form a load on the surface of the substrate. It is additionally or alternatively also possible to enter the organofluorine compound after the evaporation process under the evaporation atmosphere and its pressure states in the evaporation atmosphere and thereby to deposit it on the vaporized surface. Surprisingly, the inventor has also found that the organofluorine compound can be deposited alternately with the vapor deposition material used in the vapor deposition process on the previously vapor-deposited surface of the substrate. For this purpose, the process of evaporation with the evaporation material is interrupted for a predetermined period of time and during this period the organofluorine compound according to the invention is deposited on the evaporation surface of the substrate, after which the evaporation process is continued with the evaporation material. In order to interrupt the evaporation process, the evaporation of the evaporation material is interrupted.

Instead of using a CVD or PVD process, others can also Plasma coating processes are used, in particular those that work with an ionized plasma. Particularly suitable substrates to be vaporized are those with metallic, metallized or ceramic surface. As Such materials are suitable for Metal alloys that are based on a vapor deposition process Let the substrate evaporate, especially titanium, chromium, tungsten, Titanium aluminum, magnesium and the like. But others too Evaporation materials such as carbon fractions or boron nitride are suitable.

The invention is further illustrated by the following examples. The corresponding amino products of perfluoropolyoxyalkylenes are prepared, for example, by the reaction of perfluoropolyoxaalkylenes of the above formula R _f1 R _f2 COF, in which R _f1 and R _{f2 have} the meaning given above, in solution with amines, hydrazines, guanidines.

The solution of the amino products of the perfluoropolyoxyalkylenes, the is applied to a solid surface in one Solvent leads to adsorption and subsequent Chemosorption of the molecules on the surface. Generate these  a kind of monomolecular layer (or a the layer-like structure of several mono layers) 40 to 100 angstroms thick.

According to recent investigations by the inventor, the molecules of the active substance R _f adsorbed in this way form molecular chains perpendicular to the surface which, owing to the steric factors (low availability of space and space), form a spiral structure with a kind of anchoring via group V on the coated surface form. The molecules of the formula R _f -V are preferably attached and anchored primarily to the surface dislocations, which are characterized by increased electron density.

The active substance becomes simple in solution at atmospheric Pressure at approx. 20EC on the surface to be coated applied and forms after about 20 to 30 minutes of exposure the tied mono layer described above.

The mono layer thus formed lowers the surface tension a metal (e.g. iron) of 1800-5000 (milli-Newtons) mN / m before layer formation to 2-4 mN / m, the frictional moment of Starting movement is reduced 10 to 10,000 times.

The trained mono-layer is mechanically and chemically stable and can withstand a pressure of 300 kg / mm ² without tearing. The temperature stability of the layer is more than 450EC and under vacuum conditions up to 1000EC and more, and the active substances are non-flammable, non-toxic and easy to handle.

The coefficient of friction one with the active substance coated metallic surface are 0.05 to 0.1, which is approx 10 to 15 times lower than an uncoated one Is aluminum or iron alloy. This can reduce the wear by up to 10 to 15 times less, which is the use of the coating makes it particularly attractive in precision mechanics.

A peculiarity of the with the monolayers formed  coated surfaces, given the small thickness of the Layers has occurred surprisingly, is the increase in Micro hardness of the coated metal surfaces. So is contrary the expectation with a thin layer according to the invention, the is only a few angstroms thick, the microhardness up to approx. 1.0 Fm (Micron) depth below the coated metal surface by 10 up to 30% larger.

example 1

A solution of the compound of the formula

where indexes 55 and 10 represent the number of indexed units in a molecule, at a concentration of 0.05% in the solvent CF ₂ Cl-CFCl ₂ (99.95% by weight) was used to produce a monomolecular layer with a thickness of 50 angstroms as described above on an iron alloy Gx38CrMoV, gas nitrided with a layer thickness of the connection zone of 8-12 µm (homogeneous), layer thickness of the diffusion zone 120 to 300 µm, surface hardness approx. 1100 HV1 and core hardness 520 to 670 HV10 (NHT 650 HV1 = 150 µm).

After layering to a thickness of 50 angstroms, the hardness of the material was increased by 10 HRc. The coefficient of friction was measured at a pressure of 2311 kg force / cm and determined to be 0.09. The value remained constant at this value in a wear test over a test period of 100 hours, and the mean wear was 7.8 × 10 ^-5 grams / hour.

Example 2

A solution of the compound of the formula

where indexes 46 and 14 represent the number of indexed units in a molecule, at a concentration of 0.05% in the solvent perfluorocyclohexane (99.95% by weight) was used to produce a monomolecular layer with a thickness of 60 angstroms as above described on an iron alloy 16MnCrS5, case hardened and tempered to 58 + 4 HRC, applied. After creating the 60 angstroms layer, the hardness of the material was increased to 68 + 4 HRC. The coefficient of friction was measured at a pressure of 2311 kg force / cm and found to be 0.09. The value remained constant at this value during a wear test over a test period of 100 hours, and the mean wear was 8.1 × 10 ^-5 grams / hour.

Example 3

In the same way as described in Example 2 with the same substance an iron alloy 17 CrNiMo6, Case hardened to 60 + 2 HRC, EHT 0.9-1.0, with core strength Max. 1200 N / mm5 (after hardening), coated. This hardness is after creating the 55 angstroms thick layer to about 67 + 2 HRC increased, the wear was reduced by 5 times that The coefficient of friction was approximately 0.09. The burdens (Pressure) in the test are as in the above examples.

Further preferred compounds of the formula R _f -V are given in the attached Table 1 together with the solvents preferably used with this compound.

Examples of the use of the invention Surface treatment agent for CVD- PVD- Coating process with hard materials

The workpieces are pretreated according to the following scheme, to high-performance steels, hard metals and the like to treat:

Example 4

• a. Cleaning the workpiece as usual before coating, in water solution, alkaline or acidic or in one Solvent,
• b. Dry at approx. 100 EC until completely removed  the water residues or the solvent,

Dipping in the treatment agent for about 5 to 10 minutes, Here are among others the following variants for one Similar PVD process possible:

i. the first active substance

CF ₃ O- (CF ₂ CF ₂ O) ₅₀ - (CF ₂ O) ₁₀ CF ₂ ÕCOOH

this is in the concentration of 0.1% by weight in the solvent:

CF ₂ Cl-CFCl ₂

diluted. The workpiece is in the solution for 5-10 minutes immersed and then, possibly even without drying, in the Vacuum chamber transported. The treatment agent can in this Solution also during the steaming process Vacuum conditions are sprayed into the working atmosphere, if additional process support is provided by the Spraying is required or desired.

ii: the second active substance

This active substance is used in a concentration of 0.2% by weight. also diluted in the above solvent. The Workpiece is in this solution for about 1 to 6 minutes dipped and then in the coating process brought in.

iii: the third active substance

This active substance is in a concentration of 0.3 weight % diluted with the above solvent and on the Work piece for approx. 0.5 to 10 minutes.

• c. Inserting the workpieces into the vacuum chamber as usual,
• d. Evacuating the vacuum chamber down to the working pressure depending on the respective evaporation material (e.g. for TiN down to 10 ^-3 to 10 ^B4 pascal),
• e. (alternatively) bombardment with ions to the ion (plasma) Allow cleaning process - about 5 to 10 minutes,
• f. Evaporation of a titanium (alternatively chrome, tungsten, Titanium-aluminum and the like.) Cathode with the help of a Magnetron, arc, electron beam process in ionized atmosphere of nitrogen, oxygen or a carbon-containing gas that a Connection with the cathode material (titanium, chrome, Tungsten, aluminum-titanium and the like the substrate (workpiece) to be coated. The duration of the steaming process is approximately 20 to 120 Minutes depending on layer type and layer thickness.
• G. (Alternatively) the process can be supplemented by spraying the treatment agent during, before or after the coating, that is:
  after the substrate (workpiece) has been plasma-cleaned, the treatment agent is sprayed through an opening in the vacuum chamber, so that it encases the workpiece from all sides; this process can be repeated at a time interval of 1 to 10 minutes at least once in the evaporation process (step f.) after its interruption, so that the layers of evaporation material and fluoroorganic compound according to the invention as a multilayer composite layer on the functional surface of the to be coated Part of the substrate are built.
  The spraying process can additionally or alternatively also be carried out as the last step after the vapor deposition process.

The effects achieved in case i.

The adhesive strength of the TiN layer produced on the Base substrate is significantly increased; the roughness of the TiN layer is reduced by approx. 20 to 40%; the material density of the Layer becomes around 20-40% especially in the border area increased by binding the layer to the workpiece surface is. These effects apply to both the arc and Magnetron PVD processes as well as for CVD processes.

The effects achieved in case ii.

The adhesive strength of the TiCN layer produced on the Base substrate is significantly increased; the roughness of the TiN layer is reduced by about 20 to 30%; the material density of the Layer becomes around 20-30% especially in the border area increased by binding the layer to the workpiece surface is. These effects apply to both arcing and Magnetron PVD processes as well as for CVD processes. Through the generated by subsequent spraying of the treatment agent The friction coefficients of the coating become up to one layer Coefficient of friction reduced by 0.09.

The effects achieved in case iii.

The TiAlN layer created has a significantly higher adhesion to the base substrate; the roughness of the TiN layer is reduced by approx. 30 reduced to 40%; the material density of the layer is reduced by approx. 30% increased especially in the border area in which the layer is bound to the workpiece surface. These effects apply for both the arc and magnetron PVD process as well  for CVD processes. By spraying the The layers produced are the coefficients of friction of the overall coating reduced to a coefficient of friction of 0.08 and the hardness by approx. 5% increased.  

Claims (12)

1. Surface treatment agent in the form of a solution of 0.001 to 10% by weight, preferably 0.5 to 2% by weight, of an organofluorine compound of the formula R _f -V in a solvent, where, in the formula R _f -V, R _{f represents} an aliphatic hydrocarbon radical which can be partially or completely fluorinated or chlorofluorinated and can be straight-chain or branched-chain, the hydrocarbon radical can be interrupted by one or more oxygen, nitrogen or sulfur atoms, and V represents a polar or dipolar group , which is selected from -COOR, -COR, -COF, -CH ₂ OR, -OCOR, -CONR ₂ , -CN, -CONH-NR ₂ , -CON = C (NH ₂ ) ₂ , -CH = NOR, -NRCONR ₂ , -NR ₂ COR, -N _w , -SO ₃ R, -OSO ₃ R, -OH, -SH, / B, -OP (OH) ₂ , -OPO (OH) ₂ , -OP (ONH ₄ ) ₂ , -OPO (ONH ₄ ) ₂ , -CO-CH = CM ₂ , wherein R in a group V may be the same or different and represent hydrogen, a phenyl radical or a straight-chain or branched-chain alkyl or alkyl ether radical, i.e. it can be partially or completely fluorinated or chlorofluorinated, has up to 12, preferably up to 8 carbon atoms, and w is 2 or 3, or represents -R _v V-, where V represents the polar or dipolar group indicated above and R _{v represents} a straight-chain or branched-chain alkylene radical, which can be partially or completely fluorinated or chlorofluorinated, with 1 to 12, preferably up to 8, carbon atoms. 2. Surface treatment agent according to claim 1 in the form of a solution of a compound of formula R _f -V in a solvent selected from a halogenated hydrocarbon solvent, selected from partially or fully fluorinated, chlorofluorinated or chlorinated alkanes or cycloalkanes having up to 12 carbon atoms, or in the form of a aqueous solution with an emulsifier in an amount up to 5 wt .-%, based on the total weight of the aqueous solution. 3. Surface treatment agent according to claim 1 or 2, in which, in the formula R _f -V, R _{f represents} a straight-chain or branched-chain aliphatic hydrocarbon radical having the following schematic formula (1):
RO _x (C _a H _b F _2a-b O) _m (C _a H _b F _2a-b ) _n (1)
wherein:
a = 2, 3, 4,
b = 0, 1, 2;
x = 0.1;
20 ≦ n + m ≦ 500;
n ≧ 1 and m ≧ 0, and
R represents a straight-chain or branched-chain alkyl radical which is partially or fully fluorinated and has up to 12, preferably up to 8, carbon atoms, or alternatively F when x = 0; and
V represents a substituent from the group consisting of -COOH, -SO ₃ H, -COOR, -SO ₃ R, -COR and -SO ₂ R, where R represents a straight-chain or branched-chain alkyl radical which partially or completely fluorinates is with up to 12, preferably up to 8 carbon atoms. 4. Surface treatment agent according to claim 1, 2 or 3, in which, in the formula R _f -V, R _{f represents} a straight-chain or branched-chain aliphatic hydrocarbon radical having the following schematic formula (1):
RO _x (C _a H _b F _2a-b O) _m (C _a H _b F _2a-b ) _n (1)
wherein:
a = 2, 3;
b = 0.1;
x = 0.1;
25 ≦ n + m ≦ 200;
n ≧ 1 and m ≧ 0, and
R represents a straight-chain or branched-chain alkyl radical which is partially or fully fluorinated and has up to 12, preferably up to 8, carbon atoms or alternatively F when x = 0; and V represents a substituent from the group consisting of -COOH, -SO ₃ H, -COR and -SO ₂ R, where R represents a straight-chain or branched-chain alkyl radical which is partially or completely fluorinated, with up to 12, preferably up to 8 carbon atoms, preferably a fully fluorinated hydrocarbon radical with up to 8 carbon atoms. 5. Surface treatment agent according to claim 1, 2, 3 or 4, in which, in the formula R _f -V, R _{f stands} for a straight-chain or branched-chain aliphatic hydrocarbon radical having the following schematic formula (1):
RO _x (C _a H _b F _2a-b O) _m (C _a H _b F _2a-b ) _n (1)
wherein:
a = 2, 3;
b = 0
x = 1;
25 ≦ n + m ≦ 200;
n = 1, and
R represents a straight-chain or branched-chain one is a completely fluorinated hydrocarbon radical having up to 8 carbon atoms or alternatively F if x = 0; and
V represents a substituent from the group consisting of -COOH, -SOH, -COR and -SO ₂ R, where R represents a straight-chain or branched-chain alkyl radical which is partially or completely fluorinated, with up to 12, preferably up to 8 carbon atoms, preferably a fully fluorinated hydrocarbon radical having up to 8 carbon atoms. 6. Surface treatment agent according to claim 1 or 2, wherein, as compounds of the formula R _f -V, compounds of the general formula R _f1 R _f2 -V are used, where V has the meaning given above and the groups R _f1 and R _f2 the following Have meanings:
R _f1 represents a perfluoroalkyl ether group of the formula C _n F _{2n + 1} O-, where n can be 1 to 8;
R _f2 represents a perfluoroalkyl ether group of one of the following formulas (I) to (IV):
where n = 8 to 55, m = 0 to 10 and k = 0-1;
(-CF ₂ -CF ₂ O) _n (CF ₂ O) _m CF ₂ - (II) where n = 5 to 200 and m = 0 to 30;
(-CF ₂ CF ₂ CF ₂ O) _n CF ₂ CF ₂ - (III) where n = 5 to 50;
(-CH ₂ -CF ₂ -CF ₂ O-) _n CH ₂ CF ₂ - (IV) where n = 5 to 50. 7. A method of treating the surface of a substrate comprising the following steps:
Cleaning the surface of the substrate with a solvent that may be present to remove impurities;
Drying the surface at a temperature above the evaporation temperature of the solvent;
Treating the surface of the substrate with the treatment agent according to any one of claims 1 to 6 in the form of a solution of 0.001 to 10 wt .-%, preferably 0.5 to 2 wt .-%, of an organofluorine compound of the formula R _f -V in one Halogenated hydrocarbon solvent with up to 12 carbon atoms, or in the form of an aqueous solution of 0.001 to 10 wt .-% of the fluoroorganic compound of the formula R _f -V with an emulsifier in an amount up to 5 wt .-%, based on the total weight of the aqueous Solution. 8. The method according to claim 7 for treating the surface of a Substrates, characterized in that the solution over a period of up to 60 minutes, preferably 2 to 30 Minutes on the metallic surface, whereby the action with the application of ultrasound or in Boiling or cavitation of the solvent can take place. 9. The method according to claim 7 or 8, characterized in that the surface so treated at a temperature above the evaporation temperature of the used Solvent over a period of time to complete  Evaporation of the solvent is sufficient, dries. 10. Use of the method according to one of the claims 7-9 treated substrates in a CVD, PVD or other Coating process, in particular plasma coating method. 11. A method for vapor deposition of a substrate, in which an evaporation material is evaporated onto the substrate during a vapor deposition process under a predetermined working atmosphere, characterized in that the surface treatment agent according to one of claims 1 to 6 before and / or after the vapor deposition process and / or in a predetermined time interval for which the evaporation process is interrupted, is entered into the working atmosphere with the deposition of the organofluorine compound R _f -V on the substrate. 12. Product manufactured after use or after The method of claim 10 or 11.