Covering substance with high scratch resistance and resistance to atmospheric impact

FIELD: chemistry.

SUBSTANCE: invention relates to thermally solidificated covering substances based on aprotic solvent. Claimed is covering substance, which contains at least one compound (A), containing hydroxyl groups, at least one compound (B), containing isocyanate groups, and at least one phosphorus-containing catalyst (D) for cross-linking silane groups, with one or several components of covering substance containing between 2.5 and 97.5 mole %, counted for totality of structural units -N(X-SiR"x(OR')3-x)n(X'-SiR"y(OR')3-y)m (II) and -Z-(X-SiR"x(OR')3-x) (III), at least one structural unit of formula (II), where R'=hydrogen, alkyl or cycloalkyl, carbon chain can be interrupted by means of non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, X,X'=linear and/or branched alkylene pr cycloalkylene residue with from 1 to 20 carbon atoms, R" =alkyl, cycloalkyl, aryl or aralkyl, and carbon chain can be interrupted by means of non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, preferably R"=alkyl residue, n=0 to 2, m=0 to 2, m+n=2, x,y=0 to 2; and between 2.5 and 97.5 mole %, counted per totality of structural units (II) and (III), at least one structural unit of formula (III), where Z=-NH-, -NR-, -O-, R=alkyl, cycloalkyl, aryl or aralkyl, and carbon chain can be interrupted by means of non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, x=0 to 2, and X, R', R" have value, given above, and covering substance can be finally solidificated before covering, which has statistically distributed regions of lattice Si-O-Si. Also claimed are multi-step method of applying coating with application of claimed covering substance, as well as application of claimed method and versions of claimed coating application.

EFFECT: possibility to obtain transparent varnish coating with high resistance to formation of cracks under atmospheric impact and perfect resistance to scratching.

18 cl, 4 tbl, 7 ex

 

The present invention relates to thermally curable media coverage on the basis of the aprotic solvent containing polyols and polyisocyanates with hydrolyzable wilanowie groups, which provide coatings with high resistance to scratching with high gloss and high resistance to weathering.

In WO-A-01/98393 described 2K-top products containing polyol as a film-forming component, and as a component transverse relationship with the polyisocyanate, which is partially functionalized with alkoxysilane groups. These top tools used as primer and provide adhesion to metal substrates, especially aluminum substrates. These top funds within the serial coating OEM or repair coating can be applied to the compositions of the main lacquer clear lacquer. In terms of resistance to scratching and weathering coating means according to WO 01/98393 are not optimal.

In EP-A-0994117 describes moisture curing mixture containing polyol as one component and a polyisocyanate component, which may in part be subjected to interaction with monoalkanolamines came into the reaction it is preferable to obtain aspartate. Coverage under the service mixes though and have a certain hardness, however, with respect to resistance to atmospheric influences and in particular with regard to their resistance to scratching for OEM applications are suitable only conditionally.

US-A-2006/0217472 describes the covering means, which may contain hydroxyquinoline acrylate, low-molecular-weight polyol as one component, a polyisocyanate, and amidofunctional alkoxysilyl component, preferably bichlkashvlly. Such cover means is used as a clear varnish in the compositions of the main lacquer clear lacquer and provide a scratch resistant coating. However, such cover means are suitable for storage only very conditionally, and the resulting coatings have a low resistance to weathering, particularly with respect to UV radiation in a cycle of wet-dry.

In WO 2006/042585 describes transparent varnishes suitable for OEM serial coating, which as the main film-forming component containing a polyisocyanate, isocyanate groups which predominantly on more than 90 mol.% interact with bezalkogolnymi. Transparent varnish of this kind have excellent resistance to scratching with high chemical resistance and resistance to weathering. However, there is still a need to galinasillaste resistance to weathering, especially against crack formation by UV rays in the cycle of wet and dry, when receiving a high level of resistance to scratching.

EP-A-1273640 describes 2K-cover means consisting of a polyol as one component and a component transverse relationship consisting of aliphatic and/or cycloaliphatic polyisocyanates, and from 0.1 to 95 mol.% initially available free isocyanate groups are interacting with bezalkogoljnogo. These top funds can be used for OEM serial varnishing and after full curing possess good resistance to scratching while resistance to environmental influences. However, these top tools are particularly prone to subsequent stitching that is directly after the heat final curing is punishable only insufficient resistance to scratch coatings. Equally strong subsequent stitching a negative impact on resistance to atmospheric influences, so how is the increased risk of cracking due to internal stresses.

In the not yet published German patent application R described coating means, which contain surface-active modified selectabase connection. These top tools provide, of course, the cured coating is, who in the surface region of the coating is based on the accumulation of surface-active modified selectarray connections before thermal curing - have a high density of Si atoms mesh Si-O-Si than in the whole volume. This enrichment mesh Si-O-Si on the surface of the coatings according to the invention as times, by contrast, is absent, and the grid area of the Si-O-Si finally cured coating according to the invention are distributed statistically.

Problem and solution

The present invention was to provide covering means, in particular for coating a transparent varnish with OEM serial varnishing and finishing varnishing of vehicles that provide extremely resistant to weathering the grid, and the undesirable formation of hydrolytically unstable and atmosferostojki groups strongly suppressed in order to guarantee a high acid resistance. Along with these top tools must provide coverage that is already directly after thermal curing are highly resistant to scratching and in particular maintain high quality gloss after exposure tarpanam. In addition, coating and varnishing, especially coating of transparent varnish should also be receiving the s layer thickness of > 40 μm, without the occurrence of cracks from internal stresses. This is an important prerequisite for the application of coatings and lacquer coatings, particularly coatings transparent varnish, in the technologically and esthetically particularly demanding field of serial finishing paint cars (OEM).

In particular, should be made available to the transparent lacquer coating with a high resistance, especially to the formation of cracks at atmospheric UV radiation in a cycle of wet-dry with excellent resistance to scratching.

Moreover, new top funds must be received in a simple way and very well played and during the coating does not cause environmental problems.

The solution of the problem

In light of the above formulation of the problem were found covering products containing

(a) at least one containing the hydroxyl group of the compound (A)

(b) at least one connection (In) free and/or blocked isocyanate groups,

(c) at least one catalyst (D) for stitching Milanovich groups,

and

(i) one or more components of the coating liquids contain gidrolizuemye silane group and

(ii) the covering means can be permanently overiden to cover, which is statistically distributed in the s region of the grid Si-O-Si,

characterized in that the catalyst (D) or catalysts (D) are phosphorus.

Whereas the prior art, it was surprising and not obvious to a person skilled in the art that the tasks that lay at the basis of the present invention could be solved by using coating means according to the invention.

Components according to the invention can be produced particularly easily and with very good reproducibility, and when the varnish does not cause significant Toxicological and environmental problems.

Tools of the coating according to the invention provide a new coating and varnish coatings, especially transparent lacquer coatings which are highly resistant to scratching and, in contrast to the common longevity highly crosslinked resistant to scratching systems are acid-fast. Further, it is possible to obtain coatings and lacquer coating according to the invention, especially a transparent lacquer coating, with a thickness of >40 μm, without the occurrence of cracks from internal stresses. And therefore, coating and lacquer coating according to the invention, in particular a transparent lacquer coating, can be used in the technologically and esthetically particularly demanding field of serial finishing paint cars (OEM). However, they differ especially the high resistance at an automatic car wash and resistance to scratching. In particular, high resistance to scratch coatings is given after the final curing of the coating, so that the coating can easily apply directly after final curing. In addition, an excellent resistance of the coatings according to the invention against crack formation by UV rays and changes in the wet-dry in SAM-test (according to DIN EN ISO 11341 Feb 98 and DIN EN ISO 4892-2 Nov 00) in combination with high resistance to scratching.

Description of the invention

According to the invention the covering means can be prepared with the necessary setting very high resistance to scratching relatively high parts of the silane crosslinking, which is based on the purposeful selection of catalysts (D) for silane crosslinking does not have the disadvantages normally associated with a high content of silane crosslinking. In particular, thanks to the specific choice of catalyst (D) is able to provide top funds, which have a good resistance of the coatings according to the invention against crack formation by UV rays and cycle wet-dry in SUM test (according to DIN EN ISO 11341 Feb 98 and DIN EN ISO 4892-2 Nov 00) in combination with high resistance to scratching, high gloss and high conservation gloss after weathering.

The catalyst (D) for sshi the project Milanovich groups

Essential for the invention is that as the catalyst (D) use of phosphate, especially fosforo - and nitrogen-containing catalysts. This can also be used mixtures of two or more different catalysts (D).

Examples of suitable phosphate catalysts (D) are replaced by complex diesters of phosphonic acids and complex diesters diphosphonic acids, mainly from the group consisting of acyclic phosphonic diesters of acids, cyclic diesters of phosphonic acid, acyclic diphosphonic diesters of acids and cyclic diphosphonic diesters of acid.

So, can for example be used acyclic phosphonic diesters of acids of General formula (V)

or cyclic diesters of phosphonic acids of General formula (VI)

In the General formulas (V) and (VI) residues R10and R11are the same or different from each other; mostly they are the same and have the meaning set forth under formula (IV).

In the General formula (VI) variable L' means

- covalent bond between an atom of the residue R10and atom of residue R11;

is a divalent linking group selected from the group consisting of oxygen atom, substituted, in particular the replacement of the military oxygen, and unsubstituted sulfur atom, substituted, in particular substituted with alkyl, a nitrogen atom, substituted, in particular oxygen-substituted, phosphorus atom and substituted, especially alkyl and alkoxy substituted silicon atom, especially oxygen atom; or

is a divalent linking group selected from the group consisting of substituted and unsubstituted alkyl, containing at least one heteroatom selected from the group consisting of oxygen atom, sulfur atom, nitrogen atom, phosphorus atom, and silicon atom, especially oxygen atom, sulfur atom and nitrogen atom, or alkyl not containing heteroatoms of 1 to 10, mostly from 1 to 6 and especially from 1 to 4 carbon atoms, cycloalkyl with from 3 to 10, mainly from 3 to 6 and in particular 6 carbon atoms and aryl with from 5 to 10 and especially 6 carbon atoms.

Next can also be used, for example, acyclic complex diesters diphosphonic acid (D) General formula (VII):

;

in which the variables have the above value.

Such catalysts are described, for example, in German patent application DE-A-102005045228.

However, in particular the use of substituted complex monetary phosphoric acid and complex diesters of phosphoric acid, mainly from the group consisting of acyclic word is different diesters of phosphoric acid and cyclic complex of diesters of phosphoric acid, especially preferably the amine addition products of complex monoamino and diesters of phosphoric acid. Thus acyclic complex diesters of phosphoric acid (D), in particular selected from the group consisting of acyclic complex of diesters of phosphoric acid (D) General formula (IV):

moreover, the residues R10and R11selected from the group consisting of:

substituted and unsubstituted alkyl with from 1 to 20, mostly from 2 to 16 and particularly from 2 to 10 carbon atoms, cycloalkyl with from 3 to 20, mainly from 3 to 16 and in particular from 3 to 10 carbon atoms and aryl with from 5 to 20, mainly from 6 to 14 and in particular from 6 to 10 carbon atoms,

substituted and unsubstituted alkylaryl, arylalkyl, alkylsilanes, cycloalkenyl, aristically, cycloalkenyl, alkylcyclohexanes, alkylarylsulfonates, arylcyclohexylamine, killkillkill, cycloalkylcarbonyl and cycloalkylcarbonyl-and related alkyl-, cycloalkyl - and aryl group each time contain the above number of carbon atoms, and

substituted and unsubstituted residue of the above type containing at least one, particularly one, heteroatom selected from the group consisting of oxygen atom, sulfur atom, nitrogen atom, phosphorus atom, and silicon atom, in the person of the surface oxygen atom, the sulfur atom and nitrogen atom,

and additionally can also represent hydrogen (partial etherification).

Very particularly preferred as catalyst (D) use appropriate aminoketone esters of phosphoric acid, and here in particular aminocarbonyl ethylhexylamine esters of phosphoric acid and aminocarbonyl phenyl esters of phosphoric acid, very particularly preferably aminocarbonyl bis(2-ethylhexyl)new esters of phosphoric acid.

As examples of amines which are blocked esters of phosphoric acid, in particular, should be called tertiary amines, such as triethylamine. Especially it is preferable to block esters of phosphoric acid used tertiary amines, which provide a good effect of the catalyst under the conditions of curing at 140°C.

Certain blocked amine catalysts are phosphoric acids are also commercially available (for example, products Nacure King Industries). For example, under the name Nacure 4167 King Industries as a particularly suitable catalyst based on the amine should be called blocked partial ester of phosphoric acid.

The catalysts used mainly with a content of from 0.01 to 20 wt.%, particularly preferably with a content of from 0.1 to 10 wt.%, in terms of non-volatile component of the coating means according to the invention. Minor activity of the catalyst can be partially offset by a commensurate higher quantities of feed material.

Structural units with gidrolizuemye wilanowie groups

For the invention it is important that one or more components of the coating liquids contain gidrolizuemye silane group. These gidrolizuemye silane groups lead to the structure of Si-O-Si grid, which are statistically distributed in the cured coating. This means that it does not lead to directed enrichment or depletion of Si-O-Si grid in certain areas of the coating, and does not described in the not yet published German patent application N enrichment in the surface coverage.

In particular in this context are taken cover means, in which one or more components of cover means at least partially have one or more identical or different structural units of the formula (I)

with

G = identical or different gidrolizuemye group,

X = organic residue, in particular linear and/or branched alkalinity or cycloalkenyl residue with 1 to 20 carbon atoms, very particularly preferably X = alkalinity residue with from 1 to 4 atoms in the of Lerida,

R” = alkyl, cycloalkyl, aryl, or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with Ra = alkyl, cycloalkyl, aryl or aralkyl, preferably R” = alkyl residue, in particular with 1 to 6 C-atoms,

x = from 0 to 2, preferably from 0 to 1, particularly preferably x=0.

The structure of these Milanovich residues affects their reactivity. Regarding compatibility and reactivity of the silanes are preferably used silanes with 3 gidrolizuemye groups, i.e. x=0.

Gidrolizuemye group G can be selected from the group of halogen, in particular chlorine and bromine, group alkoxygroup, from the group alkylcarboxylic groups and group acyloxy. Especially preferred alkoxygroup (OR').

The corresponding preferred alkoxy residues (OR') may be the same or different, however, decisive for the structure of residues is the extent to which they influence the reactivity gidrolizatami Milanovich groups. Preferred R' is alkyl residue, in particular with 1 to 6 C-atoms. Especially preferred residues R', which increase the reactivity Milanovich groups, that is a good leaving group. In this regard, the preferred methoxy-balance compared to ethoxy residue and which, in turn, pre is respectful propoxy-balance. And so it is especially preferred R' = ethyl and/or methyl, in particular methyl.

Then you can also have a significant influence on the reactivity organofunctional silanes through the length of the spacers X between the functionality of the silane and the organic functional group that serves to react with the modified component. Examples thereof should be called "alpha - silanes, which are commercially available from Wacker and have a methylene group instead of the existing gamma - silanes propylene group between the Si atom and the functional group. For clarity, preferably used methacryloxypropyltrimethoxysilane (alpha - silane, for example, trading product GENIOSIL® XL 33 Wacker) compared with methacryloxypropyltrimethoxysilane (gamma - silane, for example, trading product GENIOSIL® GF 31 Wacker)to enter gidrolizuemye silane groups in the coating agent.

In General, the preferred Spencers, which increase the reactivity of silane, compared with spacers that reduce the reactivity of silanes.

Along with this functionality silanes also has influence on the properties of the obtained final cured coating. Under the functionality it is understood the number of residues of the formula (I) in the molecule. Therefore, under the monofunctional silane on kautsa silanes, which molecule of silane every time enter a residue of the formula (I) in the modified component. Under bifunctional silane refers to silanes which the molecule of the silane every time introduce two residue of the formula (I) in the component.

Especially preferred according to the invention the covering means, whose components are modified with a mixture of monofunctional and bifunctional silane. At the same time as bifunctional silanes in particular use described below amidofunctional disilane formula (IIa) as a monofunctional silanes described below silanes of the formula (IIIa).

Generally speaking, now with the same content silenzione with an increasing share of monofunctional silane increases the resistance to weathering of course the cured coating, but also reduces the resistance to scratching. In General, moreover, with the increasing share of bifunctional silane reduces the resistance to weathering of course the cured coating, but at the same time increases the resistance to scratching. Therefore, when a high percentage content of the bifunctional silane, respectively, should take other measures to increase resistance to weathering, to provide cover means coz the ACLs to the invention. For example, can be lowered degree of silanization in General, i.e. when the following modification of the polyisocyanate component (b) with (bis-silyl)with the amine of formula (IIa), the share of interacting with the silane isocyanate groups respectively can be chosen low.

In addition, with increasing degree of silanization (hence, increasing the total share content, interact with the compounds (IIa) and (IIIa) isocyanate groups) and the increasing share of bifunctional silane (IIa) increases the influence of the catalyst on the properties of the coating, so then in particular begin to act aminocarbonyl catalysts based on phosphoric acid.

In conclusion, non-functional substituents organofunctional silane, which is used to introduce the structural units (I), respectively (II), (III), can influence the reactivity gidroliticheski a silanol group. For example, this can be explained on the example of voluminous, bulky substituents of aminophenol, which can reduce the reactivity amidofunctional silanes. On this background N-(n-butyl)-3-aminopropyltrimethoxysilane preferable N-cyclohexyl-3-aminopropyltrimethoxysilane for the introduction of the structural units (III).

In General, residues, which increase the reactivity of the si the ANOVA, are preferred in comparison with the remnants of that reactivity of silanes reduce.

Structural units of the formula (I) can be introduced into the components of the top tools in a variety of ways. However, common to the various methods is that the introduction of the structural units occurs through the reaction of functional groups of modified components with additional functional groups of the silane. For example, so in the future should lead to different opportunities for the introduction of the structural units (I) having hydroxyl and optionally other reactive groups of the compound (a) and/or having the isocyanate group of the compound (In).

To use, especially within accessions Michael is suitable, for example, primary aminosilane, such as 3-aminopropyltriethoxysilane (commercially available under the trade name Geniosil® GF 93 Wacker Chemie), 3-aminopropyltrimethoxysilane (commercially available under the trade name Geniosil® GF 96 Wacker Chemie), N-(2-amino-ethyl)-3-aminopropyltrimethoxysilane (commercially available under the trade name Geniosil® GF 9 and Geniosil® GF 91 from Wacker Chemie), N-(2-amino-ethyl)-3-aminopropyltrimethoxysilane (commercially available under the trade name Geniosil® GF 95 Wacker Chemie), etc.

In particular, in the framework of accessions to the isocyanate functional compounds used in the t, for example, the secondary aminosilane, such as, for example, bis-(2-trimethoxysilylmethyl)amine, bis-(2-triethoxysilyl)amine, bis-(3-triethoxysilylpropyl)amine (commercially available under the trade name Dynasylan® 1122 the company Degussa), bis-(3-triethoxysilylpropyl)amine (commercially available under the trade name Dynasylan® 1124 the company Degussa), bis-(4-triethoxysilylpropyl)amine, N-(n-butyl)-3-aminopropyltrimethoxysilane (commercially available under the trade the name Dynasylan® 1189 the company Degussa), N-(n-butyl)-3-aminopropyltriethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane (commercially available under the trade name Geniosil® GF 92 Wacker Chemie), N-cyclohexyl-3-aminopropyltriethoxysilane, N-cyclohexyldiazeniumdioxy (commercially Wacker Chemie under the trade name Geniosil® XL 924), N-cyclohexylbenzothiazole (commercially Wacker Chemie under the trade name Geniosil® XL 926), N-phenylaminopyrimidine (commercially Wacker Chemie under the trade name Geniosil® XL 973) etc.

Epoxy-functional silanes in particular can be used to attach to compounds with carboxylic acid functionality or anhydrite functionality. Examples of suitable epoxy-functional silanes are 3-glycidylmethacrylate (commercially available from the company Degussa under the trade name Dynasylan® GLYMO), 3-glitzy roxypalacecasino (commercially available from the company Degussa under the trade name Dynasylan® GLYEO), etc.

The anhydride-functional silanes can in particular be used for joining the epoxy-functional compounds. For example, silane with anhydrite functionality should be called the anhydride of 3-(triethoxysilyl)propriatary acid (commercially Wacker Chemie under the trade name Geniosil® GF 20).

Such silanes can be used in the framework of the reactions or Michael also within metalcatalyzed reactions. For example, are called 3-methacryloxypropyltrimethoxysilane (commercially available, for example, by the company Degussa under the trade name Dynasilan® MEMO or from Wacker Chemie under the trade name Geniosil® GF 31), 3-methacryloxypropyltrimethoxysilane, VINYLTRIMETHOXYSILANE (commercially available, in particular, from Wacker Chemie under the trade name Geniosil® XL 10), vinylidenechloride (commercially available, in particular, from Wacker Chemie under the trade name Geniosil® XL 12), vinyltriethoxysilane (commercially available, in particular, from Wacker Chemie under the trade name Geniosil® GF 56), (methacryloxyethyl)metaldimension (commercially available, in particular, from Wacker Chemie under the trade name Geniosil® XL 32), methacryloxypropyltrimethoxysilane (commercially available, in particular, from Wacker Chemie under the trade name Geniosil® XL 33), (methacryloxyethyl)metildigoxin (commercially available, in particular, from Wacker Chemie under trgovinasloga Geniosil® XL 34), methacryloxypropyltrimethoxysilane (commercially available, in particular, from Wacker Chemie under the trade name Geniosil® XL 36).

Silanes with isocyanatobenzene or urethane function in particular are used in the framework of the reactions with hydroxy-functional compounds. Examples of silanes with isocyanatobenzene described in WO07/037857.

Suitable isocyanatopropyltrimethoxysilane are, for example, isocyanatopropyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltrimethoxysilane and isocyanatopropyltrimethoxysilane. Most isocyanatoacetate - and di-alkoxysilane available commercially, for example under the name SILQUEST® by OSi Specialties, Inc., the company Witco Corporation.

Applied isocyanatopropyltrimethoxysilane preferably who meet high degree of purity, in particular at least 95%, and preferably is free from additives such as catalysts for the transesterification, which can lead to undesirable side reactions.

In particular, using (isocyanatomethyl)metaldimension (commercially available from Wacker Chemie under the trade name Geniosil® XL 42), 3-isocyanatopropyltrimethoxysilane (commercially available from Wacker Chemie under the trademark Geniosi®I XL 40) and N-dimethoxy(methyl)millimeter-O-methyl-carbamate (commercially available from Wacker Chemie under the trade name Geniosil® XL 65).

According to the invention particularly preferred coating agent containing at least one containing the hydroxyl group of the compound (A)and at least one containing isocyanate group of the compound (B), which differ in that one or more components of the coating tool as an additional functional components are between 2.5 and 97.5 mol%, in terms of the totality of the structural units (II) and (III)at least one structural unit of formula (II)

and

R' = hydrogen, alkyl or cycloalkyl, and the carbon chain may be interrupted not adjacent groups of oxygen, sulfur or NRa, with Ra = alkyl, cycloalkyl, aryl or aralkyl,

preferably R' = ethyl and/or methyl,

X,X ' = linear and/or R is sweetlenny alkalinity or cycloalkenyl residue with 1 to 20 carbon atoms, preferably X, X' = alkalinity residue with 1 to 4 carbon atoms,

R” = alkyl, cycloalkyl, aryl, or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with Ra = alkyl, cycloalkyl, aryl or aralkyl, preferably R” = alkyl residue, in particular with 1 to 6 C-atoms,

n=0 to 2, m=0 to 2, m+n=2, and x, y=0 to 2,

and

between 2.5 and 97.5 mol%, in terms of the totality of the structural units (II) and (III)at least one structural unit of formula (III)

and

Z=-NH-, -NR-, -O-,

with R = alkyl, cycloalkyl, aryl or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with Ra = alkyl, cycloalkyl, aryl or aralkyl,

x=0 to 2,

X, R', R” have the meanings given in the formula (II).

A particularly preferred coating means, in which one or more components of the coating means are between 5 and 95 mol.%, in particular between 10 and 90 mol.%, especially preferably between 20 and 80 mol.%, and very particularly between 30 and 70 mol.%, each time calculated on the sum of structural units (II) and (III)at least one structural unit of formula (II) and between 5 and 95 mol.%, in particular between 10 and 90 mol.%, especially preferably between 20 and 80 mol.%, and very particularly between 30 and 70 mol.%, ka is every time in terms of the totality of the structural units (II) and (III), at least one structural unit of formula (III).

Containing the hydroxyl group of the compound (A)

As containing the hydroxyl group of the compound (A) is mainly used as low molecular weight polyols, and oligo - and/or polymeric polyols.

As low molecular weight polyols are used, for example, diols, such as preferably ethylene glycol, neopentylglycol, 1,2-propandiol,2,2,-dimethyl-1,3-propandiol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol,2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and 1,2-cyclohexanedimethanol, and also polyols, such as preferably trimethylated, trimethylolpropane, trimethylhexane, 1,2,4-butanetriol, pentaerythritol and dipentaerythritol.

Preferably, such low molecular weight polyols admixed in minor fractions of oligo - and/or polymer polianovich component (A).

Preferred oligo - and/or polymeric polyols (A) are srednesemennyh molecular weight Mw>500 daltons, as measured by GPC (helpanimals chromatography), preferably between 800 and 100,000 daltons, in particular between 1,000 and 50,000 daltons. Particularly preferred polyether polyols poliuretanoviy, polisiloksanovoy and especially polyacrylonitrile and/or polymethacrylates, as well as their copolymers, hereinafter called the " polyacrylonitrile. The polyols preferably have IT-a number from 30 to 400 mg KOH/g, in particular between 100 and 300 KOH/g transition Temperature in the glassy state, measured by DSC (differential thermal analysis), polyols are preferably between -150 and 100°C., particularly preferably between -120°C and 80°C.

Suitable polyether polyols are, for example, described in EP-A-0994117 and EP-A-1273640. Poliuretanoviy mainly produced by the interaction polyetherpolyols fluoropolymers with a suitable di - or polyisocyanates and are described, for example, in EP-A-1273640. Suitable polisiloksanovye are for example described in WO-A-01/09260, and given there polisiloksanovoy preferably can be used in combination with other polyols, in particular having a higher junction temperature in the glassy state.

According to the invention very particularly preferred polyacrylonitrile are generally copolymers and mostly srednegalechny molecular weight Mw between 1.000 and 20,000 daltons, in particular between 1.500 and 10,000 daltons, each time measured by means of gel chromatography (GPC) versus polystyrene standards. The temperature of transition to the glassy state of the copolymers is generally between -100 and 100°C, especially IU the DN -50 and 80°C (measured by DSC measurements). Polyacrylonitrile are preferably IT is in the range from 60 to 250 mg KOH/g, in particular between 70 and 200 KOH/g and an acid number of between 0 and 30 mg KOH/g

Hydroxyl number (OH-number) specifies the number of mg of potassium hydroxide equivalent to the amount of acetic acid which, when acetylation is related to 1 g of substance. When determining the sample is boiled with acetic anhydride-pyridine, and the resulting acid is titrated with potassium hydroxide solution (DIN 53240-2).

When this acid number indicates the number of mg of potassium hydroxide, which is consumed to neutralize 1 g of the corresponding compounds of the component (b) (DIN EN ISO 2114).

Also by selecting containing hydroxyl groups binders it is possible to influence the properties of the final cured coating. In General, it increased IT-the number of the component (A) can reduce the degree of silanization, i.e. the number of structural units of the formula (I), respectively (II), (III)that, on the contrary, has a positive effect on the weather resistance of the final cured coating.

As containing the hydroxyl group of the monomer unit is preferably used hydroxyethylacrylate and/or hydroxyethylmethacrylate, such as especially 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate, 2-hydroxypropylmethacrylate, 2-hydroxypropyl kilat, 3-hydroxypropylamino, 3-hydroxypropylmethacrylate, 3-hydroxyethylacrylate, 3-hydroxyethylmethacrylate, and in particular 4-hydroxyethylacrylate and/or 4-hydroxyethylmethacrylate.

As the other monomer unit for polyacrylonitriles preferably used alkyl methacrylates and/or alkyl methacrylates, such as predominantly acrylate, ethyl methacrylate, propylacetate, propylbetaine, isopropylacetate, isopropylacetate, butyl acrylate, butylmethacrylate, isobutylacetate, isobutylacetate, tert-butyl acrylate, tert-butylmethacrylate, amylacetate, amylmetacresol, hexidecimal, vexillarius, hexyl acrylate, ethylhexylacrylate, 3,3,5-trimethylhexanoyl, 3,3,5-trimethylhexamethylene, stearylamine, sterilisability, laurelcrest or laurenmarie, cycloalkylcarbonyl and/or cycloalkylation, such as cyclopentylamine, cyclopentylmethyl, isobutylacetate, isobornylacrylat or especially cyclohexylacetate and/or cyclohexylmethyl.

As the other monomer unit for polyacrylonitriles can be used vinylaromatic hydrocarbons, such as vinyltoluene, alpha methylsterol or in particular styrene, amides or NITRILES of acrylic or methacrylic acid, a complex of vinyl esters or simple vinyl ether is, and also in small quantities in particular acrylic or methacrylic acid.

In another form of the invention containing the hydroxyl group of the compound along with a hydroxyl group has a structural unit of the formula (I)and/or formula (II)and/or formula (III).

Structural units of the formula (II) can be introduced into the compound (A) by incorporating the Monomeric units with similar units or by reacting polyols, which have other functional groups, with a compound of formula (IIa)

moreover, the substituents have the above significance. To interact polyol with compound (IIa) polyol, respectively, has other functional groups that react with secondary amino group of the compound (IIa), such as in particular acid or epoxy group. According to the invention preferred compounds (IIa) are bis(2-ethyltrimethoxysilane)amine, bis(3-propyltrimethoxysilane)amine, bis(4-butyldimethylsilyl)amine, bis(2-ethyltriethoxysilane)amine, bis(3-propyltriethoxysilane)amine and/or bis(4-butyldimethylsilyl)amine. Quite especially preferred is bis(3-propyltrimethoxysilane)amine. This aminosilane available, for example, under the brand name DYNASILAN® company DEGUSSA, with the NGOs Silquest® by OSI.

Monomer units which contain structural elements (II)primarily represents the interaction products of acrylic and/or methacrylic acid or containing epoxy groups alkylacrylate and/or alkyl methacrylates with the above compounds (IIa).

Structural units of the formula (III) can be introduced into the compound (A) by incorporating the Monomeric units with similar units or by reacting polyols, which have other functional groups, with a compound of formula (IIIa)

moreover, the substituents have the above significance. To interact polyol with compound (IIIa) polyol, respectively, has other functional groups that react with the functional group-ZH compounds (IIIa), such as in particular an acid, epoxy or ester groups. According to the invention preferred compounds (IIIa) are omega-aminoalkyl - or omega-hydroxycorticosterone, such as a predominantly 2-AMINOETHYLPIPERAZINE, 2-aminoethylthiomethyl, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyraldehyde, 4-aminoethylthiomethyl, 2-hydroxyethylaminomethyl, 2-hydroxyethylrutoside, 3-hydroxypropylmethacrylate, 3-hydroxypropylamino the silane, 4-hydroxymethylimidazole, 4-hydroxymethylimidazole. Particularly preferred compounds (IIIa) are N-(2-(trimethoxysilyl)ethyl)bonds alkylamines, N-(3-(trimethoxysilyl)propyl)bonds alkylamines, N-(4-(trimethoxysilyl)butyl)bonds alkylamines, N-(2-(triethoxysilyl)ethyl)bonds alkylamines, N-(3-(triethoxysilyl)propyl)bonds alkylamines and/or N-(4-(triethoxysilyl) butyl)alkylamines followed. A particularly preferred N-(3-(trimethoxysilyl)propyl)butylamine. This aminosilane available, for example, under the brand name DYNASILAN® company DEGUSSA, respectively Silquest® by OSI.

Monomer units which contain structural elements (III)primarily represents the interaction products of acrylic and/or methacrylic acid or containing epoxy groups alkylacrylate and/or alkyl methacrylates, and also in case hydroxyquinoline alkoxysilyl compounds are products of the interaction of alkylacrylate and/or alkyl methacrylates, in particular with the above hydroxy - and/or amidofunctional alkoxysilane compounds (IIIa).

Containing isocyanate groups of the compound (In)

As component (C) cover means according to the invention contain one or more compounds with the free, i.e. non-blocking, and/or blocked isocyanate groups. Preferably the coating creditbalance to the invention contain compounds (B) with the free isocyanate groups. Isocyanate group-containing isocyanate groups of the compounds may also be used in blocked form. It is preferable in the case when the coating means according to the invention is used as one-component system.

Serve as the primary substance preferably used according to the invention containing isocyanate groups of the compounds (B) di - and/or polyisocyanates preferably represent a known substituted or unsubstituted aromatic, aliphatic, cycloaliphatic and/or heterocyclic polyisocyanates. Examples of preferred polyisocyanates are 2,4-colorvision, 2,6-colorvision, difenilmetana-4,4'-diisocyanate, difenilmetana-2,4'-diisocyanate, p-delete the entry, biphenyldiol, 3,3'-dimethyl-4,4'-diphenyldiisocyanate, tetramethylene 1,4-diisocyanate, hexamethylene-1,6-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, isophoronediisocyanate, atlantaatlanta, 1,12-dodecanesulfonate, CYCLOBUTANE-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, methylcyclohexylamine-tianity, exagerately-2,4-diisocyanate, exagerately-2,6-diisocyanate, hexahydrofuro-1,3-diisocyanate, hexahydrofuro-1,4-diisocyanate, perheravintolan-2,4'-diisocyanate, 4,4'-methylendysiclogecsyldiizosyonat (for example, Dsmodur® W from Bayer AG), tetramethyldisilane (for example, TMXDI® company American Cyanamid) and mixtures of the aforementioned polyisocyanates. Next, the preferred polyisocyanates are the biuret dimers and isocyanurate trimers of the above diisocyanates.

Particularly preferred polyisocyanates PI are hexamethylene-1,6-diisocyanate, isophoronediisocyanate and 4,4'-methylendysiclogecsyldiizosyonat, biuret dimers and/or isocyanurate trimers.

In another form of the invention presents the polyisocyanates, the polyisocyanate-prepolymers with urethane structural units, which are obtained by interaction of polyols with a stoichiometric excess of the above polyisocyanates. Such a polyisocyanate prepolymers are described, for example, in US-A-4,598,131.

According to the invention very particularly preferred, functionalityand structural units (II) and (III) containing isocyanate groups of the compound (C) receive, preferably by reacting the above di - and/or polyisocyanates with the above compounds (IIa) and (IIIa), that is subjected to interaction

between 2.5 and 90 mol.%, preferably from 5 to 85 mol.%, particularly preferably from 7.5 to 80 mol.%, isocyanate groups in the polyisocyanate main substance with at least one compound (IIa) and between 2.5 and 90 mol.%, prefer the Ino from 5 to 85 mol.%, particularly preferably from 7.5 to 80 mol.%, isocyanate groups in the polyisocyanate main substance with at least one compound (IIIa).

The total share of interacting with the compounds (IIa) and/or (IIIa) isocyanate groups in the polyisocyanate compound (C) is between 5 and 95 mol.%, preferably between 10 and 90 mol.%, especially preferably between 15 and 85 mol.% isocyanate groups in the polyisocyanate primary substance. Especially when a high degree of silanization, i.e. if a high proportion of isocyanate groups, in particular at least 50 mol.%, was browseinterval with the compounds (IIa)and(IIIa), isocyanate groups are beneficial interaction with a mixture of the compounds (IIa) and (IIIa).

Particularly preferred compounds (IIa) are bis(2-ethyltrimethoxysilane)amine, bis(3-propyltrimethoxysilane)amine, bis(4-butyldimethylsilyl)amine, bis(2-ethyltriethoxysilane)amine, bis(3-propyltriethoxysilane)amine and/or bis(4-butyldimethylsilyl)amine. Quite especially preferred is bis(3-propyltrimethoxysilane)amine. This aminosilane available, for example, under the brand name DYNASILAN® company DEGUSSA, respectively Silquest® by OSI.

Preferred compounds (IIIa) are 2-AMINOETHYLPIPERAZINE, 2-aminoethylthiomethyl, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4 am is nonutilitarian, 4-aminoethylthiomethyl, 2-hydroxyethylaminomethyl, 2-hydroxyethylrutoside, 3-hydroxypropylmethacrylate, 3-hydroxypropylmethacrylate, 4-hydroxymethylimidazole, 4-hydroxymethylimidazole.

Particularly preferred compounds (IIIa) are N-(2-(trimethoxysilyl) ethyl)bonds alkylamines, N-(3-(trimethoxysilyl) propyl)bonds alkylamines, N-(4-(trimethoxysilyl) butyl)bonds alkylamines, N-(2-(triethoxysilyl) ethyl)bonds alkylamines, N-(3-(triethoxysilyl) propyl)bonds alkylamines and/or N-(4-(triethoxysilyl)butyl)alkylamines followed. Quite especially preferred is N-(3-(trimethoxysilyl)propyl)butylamine. This aminosilane available, for example, under the brand name DYNASILAN® company DEGUSSA, respectively Silquest® by OSI.

Very particularly preferred containing isocyanate groups with compounds (B) are the products of interactions between hexamethylene-1,6-diisocyanate and/or isophorondiisocyanate, and/or their isocyanurate trimers with bis(3-propyltrimethoxysilane)amine and N-(3-(trimethoxysilyl)propyl)butylamine.

Interaction containing isocyanate groups of the compounds (V) with compounds (IIa) and (IIIa) occurs mainly in the atmosphere of inert gas at temperatures as high as 100°C., most preferably 60°C.

Free isocyanate group-containing isocyanate groups soybean is ineni In can also be used in blocked form. It is preferable in the case when the coating means according to the invention is used as one-component systems. In principle, for blocking can be used each used for blocking polyisocyanates blocking means with a low enough deblokiruyuschee temperature. Such locking means are well known to the person skilled in the art. Preferably use a blocking means, as they are described in EP-A-0626888 and EP-A-0692007.

The combination of components a and b, as well as other components of the integumentary tools

Weight fraction used containing hydroxyl group of compounds And, in terms of weight fraction containing isocyanate groups of the compounds depends on the hydroxy equivalent weight polyol and from the equivalent weight of free isocyanate groups MDI Century

It is preferable that the coating media according to the invention one or more components are between 2.5 to 97.5 mol.%, in terms of the amount of the structural units (II) and (III)at least one structural unit (II) and between 2.5 to 97.5 mol.%, in terms of the amount of the structural units (II) and (III)at least one structural unit (III).

Cover means according to the invention contain preferably between 2.5 and 97.5 wt.%, especially preferably between 5 and 95 wt.%, absolutely about obinna preferably between 10 and 90 wt.%, in particular between 20 and 80 wt.%, in terms of the content of nonvolatile substances in the coating vehicle containing hydroxyl group of the compounds (a) and preferably between 2.5 and 97.5 wt.%, especially preferably between 5 and 95 wt.%, very particularly preferably between 10 and 90 wt.%, in particular between 20 and 80 wt.%, in terms of the content of nonvolatile substances in the coating vehicle containing isocyanate groups of the compounds (B).

In terms of the amount essential for crosslinking in the coating media according to the invention the functional groups formed from parts of hydroxyl and isocyanate groups, as well as parts of the structural elements (I) or (II) and (III), structural elements (I) or (II) and (III) are preferably with a content of from 2.5 to 97.5 mol.%, especially preferably between 5 and 95 mol.% and very particularly preferably between 10 and 90 mol.%.

In order to further ensure the stability of the coatings according to the invention against crack formation by UV rays and cycle wet-dry in SAM-test (according to DIN EN ISO 11341 Feb 98 and DIN EN ISO 4892-2 Nov 00) in combination with high resistance to scratching directly after thermal final curing, high gloss and high gloss retention after weathering, in addition, it is preferable content of the structural units (I), is/or (II), and/or (III) to choose the most so high that the coating means according to the invention contain less than 6.5 wt.% SI structural units (I)and/or (II) and/or (III), particularly preferably a maximum of 6.0 wt.% Si structural units (I)and/or (II) and/or (III), each time calculated on the solids content of a coating means. The content of the silane wt.% Si calculated from the quantities of compounds with the structural unit (I), respectively, compounds (IIa), (IIIa).

In another form of the invention, the structural elements (I), (II) and/or (III) can optionally be part of one or more, different from components (a) and (b), other components (C)and apply the above criteria. For example, as components (C) apply To oligomers or polymers with alkoxysilane groups, such as, for example, described in patents and patent applications US-A-4,499,150, US-A-4,499,151 or EP-A-0 571 073 poly(meth)acrylates as carriers of structural elements (III) or listed in WO-A-2006/042585 compounds as carriers of structural elements (II). As a rule, use the following components (C) with a share of up to 40 wt.%, preferably up to 30 wt.%, particularly preferably up to 25 wt.%, in terms of non-volatile components of a coating means.

Weights is olila and MDI In predominantly chosen so that what is the molar euqivalent the ratio of unreacted isocyanate groups isocyanatomethyl compounds (B) to hydroxyl groups containing hydroxyl group of compound (A) is between 0.9:1 and 1:1,1, preferably between from 0.95:1 and 1.05:1, particularly preferably between to 0.98:1 to 1.02:1.

If we are talking about one-component coating tools, then select containing isocyanate groups of the compound (In)free isocyanate groups are blocked described above, the blocking means.

In a preferred according to the invention 2-component (2K) coating means shortly before application of a coating means are mixed in a known manner component lacquer, which contains involving the hydroxyl group of the compound (A), as well as others described in further components, with other lacquer component, including containing isocyanate groups of the compound (C) and optionally other components is described further in, and, as a rule, lacquer component containing compound (A)contains a catalyst, and solvent.

As solvents for the coating means according to the invention particularly suitable those in top tool are chemically inert in relation to compounds (a) and (b) and also during the curing of the coating means is not su upaut reaction with (a) and (B). Examples of such solvents are aliphatic and/or aromatic hydrocarbons, such as toluene, xylene, solvent-naphtha, Solvesso 100 or Hydrosol® (ARAL), ketones, such as acetone, methyl ethyl ketone or methylmercaptan, esters such as ethyl acetate, butyl acetate, pentalateral or teleconversation, ethers, or mixtures of the above solvents. Preferably aprotic solvents or solvent mixtures have a water content of at most 1 wt.%, particularly preferably a maximum of 0.5 wt.%, in terms of solvent.

Along with the compounds (A), (b) and (C) can be used still other binders, which primarily react with hydroxyl groups of the compound (a) and/or with the free isocyanate groups of the compound (b) and/or alkoxysilyl groups of compounds (A), (b) and/or (C), and can form a net structure.

For example, as component (E) used aminoplastic resin and/or apoximately. Suitable are conventional and known aminoplastic resin, methylol and/or methoxymethyl group partially using urethane or allophanate groups can be defunctionalization. Crosslinking agents of this type are described in patent descriptions US-A-4710542 and ER-IN-0245700, as well as in article C. Singh and coworkers, "Carbamylmethylated Melamines, Novel rosslinkers for the Coatings Industry" in Advanced Organic Coatings Science and Technology Series, 1991, volume 13, cc.193 to 207.

As a rule, use the following components (E) with a share of up to 40 wt.%, preferably up to 30 wt.%, particularly preferably up to 25 wt.%, in terms of non-volatile components of a coating means. Over this coating tool according to the invention may contain at least one customary and known lacquer additive in effective amounts, i.e. in amounts mostly to 30 wt.%, particularly preferably up to 25 wt.% and in particular up to 20 wt.%, every time in terms of non-volatile components of a coating means.

Examples of suitable lacquer additives are:

especially UV absorbers;

in particular, the light stabilizers such as HALS-compounds, benzotriazole or oxalanilide;

- acceptors of free radicals;

- additives for improving the slip;

inhibitors of polymerization;

- antispyware;

- reactive diluents, as they, in General, are known from the prior art, which preferably are inert in respect of the-Si(OR)3 groups;

- wetting agents such as siloxanes, fluorine compounds, monoether carboxylic acids, phosphoric esters, polyacrylic acids and their copolymers, or polyurethanes;

- adhesion promoters, such as tricyclopentadiene;

- to contribute to spreading;

- film-forming functional the Chairman tools, such as derivatives of cellulose;

- fillers such as, for example, nanoparticles based on silicon dioxide, aluminum oxide or zirconium oxide; an additional reference is made to Römpp Lexikon Lacke and Druckfarben", Georg Thieme Verlag, Stuttgart, 1998, cc.250 to 252;

- additives that control the rheology, such as is known from the patent descriptions WO 94/22968, EP-A-0276501, EP-A-0249201 or WO 97/12945; crosslinked polymeric microparticles, such as they are, for example, disclosed in EP-A-0008127; inorganic layered silicates, such as aluminum-magnesium silicates, sodium-magnesium and sodium-magnesium-fluorine-lithium layered silicates of the type montmorillonite; silicic acid, such as aerosol; or synthetic polymers with ionic and/or associative existing groups, such as polyvinyl alcohol, poly(meth)acrylamide, poly(meth)acrylic acid, polyvinylpyrrolidone, styrene-maleic anhydrite copolymers or ethylene-maleic anhydrite copolymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates;

and/or fire retardant means.

In another form of the invention, the coating tool according to the invention may also contain other pigments and/or fillers and serve to produce pigmented top layer. Used to do this, pigments and/or fillers known to the specialist in this region the STI technique.

As obtained from the coating means according to the invention the coating according to the invention also exclusively linked to already otverzhdennye electrophoretic lakirovanie, liquid lakirovanie, basic lakirovanie or the usual and well-known transparent lakirovanie, along with the use in the automotive serial varnishing (OEM) they are remarkably suitable for repair lacquering or modular, resistant to scratching, finish already painted automobile bodies.

The application of the coating means according to the invention may be carried out by all of the usual application methods, such as, for example, sputtering, relevane, promazyvanie, color filling, dipping, soaking, dripping or rolling. While covering the substrate itself may be stationary, and the equipment or installation for applying moves. Meanwhile, the coated substrate, in particular a roll, may also move, and equipment for applying relative to the substrate is stationary or is moving properly. Mostly used methods of spray application, such as, for example, air spray, airless spray, high-speed rotation, electrostatic spray coating (ESTA), optionally combined with what neseniem hot spray, as for example, spraying hot air.

Curing the applied coating means according to the invention may be carried out after a certain period of rest. The rest period is used, for example, for spreading and for degassing lacquer layers or for the evaporation of volatile components such as solvent. The rest period may be reinforced and/or reduced by the application of elevated temperatures and/or low humidity, because in this case there is no damage or changes lacquer layers, such as premature complete crosslinking.

Thermal curing of the coating means has no methodological features, and occurs according to standard and well known methods such as heating in a drying oven with air circulation or irradiation with IR lamps. In this case thermal curing may also occur gradually. Another preferred method of curing is the curing in the near infrared spectrum (NIR radiation). Preferably thermal curing occurs at a temperature of from 30 to 200°C., particularly preferably 40 to 190°C. and in particular 50 to 180°C. over a period of time from 1 minute to 10 hours, particularly preferably from 2 min to 5 h and in particular from 3 min to 3 h, and when repair coating applied temperature is, which are preferably between 30 and 90°C, can also be used for a longer time to cure.

Cover means according to the invention provide a new cured coatings, particularly coatings that are particularly transparent lacquer coating, fittings, especially optical fittings, and svobodnaia films that are resistant to scratching and particularly resistant to chemicals and weather. In particular, according to the invention it is possible to obtain coatings and lacquer coating, especially a transparent coating with a thickness of >40 μm, without the occurrence of cracks due to internal stresses.

Therefore, the coating means according to the invention especially suitable as a decorative, protective and/or giving effect, highly resistant to scratch coatings and coating of vehicle bodies (especially vehicles with an engine, such as motorcycles, buses, trucks or automobiles) or their parts; internal and external areas of the buildings; furniture, Windows and doors; mouldings made of synthetic materials, in particular CDs and Windows; industrial small parts, coils, containers, and packaging; products white; films; optical, electrotechnical and mechanical parts, and the same hollow glass products and consumer goods.

In particular, the coating means according to the invention and of the lacquer coating, in particular a transparent varnish used in the technologically and esthetically particularly demanding field of coating hire repetitive manufacturing (OEM), and also repair coating. Especially preferably the coating means according to the invention is used in multi-step method of applying coatings, in particular in the way in which optionally pre-coated substrate is first applied pigment master lacquer layer and then layer with the coating agent according to the invention.

Can be used as water-based base lacquers, and the basic lacquers based on organic solvents. Suitable base lacquers are, for example, described in EP-A-0692007 and there in the in column 3, line 50 and the following documents. Preferably the applied base lacquer is first dried, that is, from the core of the lacquer film during the evaporation phase is removed, at least one organic solvent, water respectively. Drying occurs mainly at temperatures from room temperature to 80°C. After drying of the applied coating agent according to the invention. Then burn dual-layer coating preferably under conditions that are common what's the varnishing of vehicles series production at temperatures from 30 to 200°C. particularly preferably 40 to 190°C. and in particular from 50 to 180°C. over a period of time from 1 minute to 10 hours, particularly preferably from 2 min to 5 h and in particular from 3 min to 3 h, and when repair coating applied temperature, which preferably are between 30 and 90°C, can also be used for a longer time to cure.

The layers obtained by means of a coating tool according to the invention is primarily distinguished by its especially high resistance to chemicals and weathering, as well as very good resistance at an automatic car wash and resistance to scratching, especially thanks to the exceptional combination of resistance to scratching and weathering against UV radiation in a cycle of wet-dry.

In another preferred form of the invention, the coating tool according to the invention is used as a light, transparent lacquer for coating a polymeric substrate, especially a transparent polymer substrates. In this case, the covering means comprise UV absorbers, based on the number and type are also designed for effective UV protection polymer substrates. In this context, the covering means is different thanks to the exceptional combination of resistance to scratching and services is oisiveto weatherproof against UV radiation in the wet-dry period. Covered in a similar manner polymeric substrates are mainly used to replace the glass components in the automotive industry, and polymer substrates preferably comprise polymethylmethacrylate or polycarbonate.

Examples

The receiving component In accordance with the invention

Example obtain B1 - receiving partially silanizing MDI (HDI with 100 mol.% IIIa: the degree of interaction between the C=30 mol.%)

In a three-neck flask, equipped with reflux condenser and thermometer, is placed 57,3 weight parts trimensional of hexamethylenediisocyanate (HDI) (Basonat HI 100 BASF AG) and 88,0 weight parts of the solvent-naphtha. When cooled reflux condenser, cover with nitrogen and stirring at 21.8 parts by weight of N-[3-(trimethoxysilyl)propyl]-butylamine (IIIa) (Dynasilan® 1189 company Degussa) are added in such a way that does not exceed 50 to 60°C. after dosing the reaction temperature kept at 50 to 60°C until determined using the titration mass fraction of isocyanate is theoretically calculated 70 mol.%.

The solution is partially silanizing MDI has a solids content in 47,1 wt.%.

Example obtain B2 - receiving partially silanizing MDI (HDI 70 mol.% IIIa and 30 mol.% IIa: the degree of interaction between the C=30 mol.%)

In a three-neck flask, reflux x is Hladilnika and thermometer, place of 57.3 parts by weight of trimensional of hexamethylenediisocyanate (HDI) (Basonat HI 100 BASF AG) and to 69.7 parts by weight of the solvent-naphtha. When cooled reflux condenser, cover with nitrogen and stirring the mixture of 14.8 parts by weight of N-[3-(trimethoxysilyl)propyl]-butylamine (Dynasilan® 1189 company Degussa) (IIIa) and 9.2 parts by weight of bis-[3-(trimethoxysilyl)propyl]-amine (IIa) (Dynasilan® 1124 company Degussa) in such a way that does not exceed 50 to 60°C. after dosing the reaction temperature kept at 50 to 60°C until determined using the titration mass fraction of isocyanate is theoretically designed 70 mol.%. The solution is partially silanizing MDI has a solids content in 53,9 wt.%.

An example of obtaining B3 - receiving partially silanizing MDI (HDI with 30 mol.% IIIa and 70 mol.% IIa: the degree of interaction between the C=30 mol.%)

In a three-neck flask, equipped with reflux condenser and thermometer, is placed 57,3 weight parts trimensional of hexamethylenediisocyanate (HDI) (Basonat HI 100 BASF AG) and to 69.7 parts by weight of the solvent-naphtha. When cooled reflux condenser, cover with nitrogen and stirring the mixture of 6.4 parts by weight of N-[3-(trimethoxysilyl)propyl]-butylamine (Dynasilan® 1189 company Degussa) (IIIa) and 21.5 parts by weight of bis-[3-(trimethoxysilyl)propyl]-amine (IIa) (Dynasilan® 1124 company Deguss) thus, not exceed 50 to 60°C. after dosing the reaction temperature kept at 50 to 60°C until determined using the titration mass fraction of isocyanate is theoretically calculated 70 mol.%. The solution is partially silanizing MDI has a solids content in 55,0 wt.%.

An example of obtaining B4 - receiving partially silanizing MDI (HDI with 100 mol.% IIa: the degree of interaction between the C=30 mol.%)

In a three-neck flask, equipped with reflux condenser and thermometer, is placed 57,3 weight parts trimensional of hexamethylenediisocyanate (HDI) (Basonat HI 100 BASF AG) and 88,0 weight parts of the solvent-naphtha. When cooled reflux condenser, cover with nitrogen and stirring of 30.7 parts by weight of parts by weight of bis-[3-(trimethoxysilyl)propyl]-amine (IIa) (Dynasilan® 1124 company Degussa) in such a way that does not exceed 50 to 60°C. after dosing the reaction temperature kept at 50 to 60°C until determined using the titration mass fraction of isocyanate is theoretically calculated 70 mol.%.

The solution is partially silanizing MDI has a solids content in 63,0 wt.%.

An example of obtaining B5 - receiving partially silanizing MDI (HDI with 100 mol.% IIIa: the degree of interaction with=70 mol.%)

In a three-neck flask, about nashenas reflux condenser and a thermometer, place of 57.3 parts by weight of trimensional of hexamethylenediisocyanate (HDI) (Basonat HI 100 BASF AG) and 88,0 weight parts of the solvent-naphtha. When cooled reflux condenser, cover with nitrogen and stirring of 49.4 parts by weight of N-[3-(trimethoxysilyl)propyl]-butylamine (IIIa) (Dynasilan® 1189 company Degussa) in such a way that does not exceed 50 to 60°C. after dosing the reaction temperature kept at 50 to 60°C until determined using the titration mass fraction of isocyanate is theoretically calculated 30 mol.%.

The solution is partially silanizing MDI has a solids content in of 54.8 wt.%.

Example of getting a B6 - receiving partially silanizing MDI (HDI 70 mol.% IIIa and 30 mol.% IIa: the degree of interaction with=70 mol.%)

In a three-neck flask, equipped with reflux condenser and thermometer, is placed 57,3 weight parts trimensional hexamethylenediisocyanate (HDI) (Basonat HI 100 BASF AG) and to 69.7 parts by weight of the solvent-naphtha. When cooled reflux condenser, cover with nitrogen and stirring the mixture of 34.6 parts by weight of N-[3-(trimethoxysilyl)propyl]-butylamine (Dynasilan® 1189 company Degussa) (IIIa) and 21.5 parts by weight of bis-[3-(trimethoxysilyl)propyl]-amine (IIa) (Dynasilan® 1124 company Degussa) in such a way that does not exceed 50 to 60°C. Upon completion of the dispensing temperature of the reaction is kept at 50 to 60°C, while determined using the titration mass fraction of isocyanate is theoretically calculated 30 mol.%. The solution is partially silanizing MDI has a solids content in 61,9 wt.%.

An example of obtaining V7 - receiving partially silanizing MDI (HDI with 30 mol.% IIIa and 70 mol.% IIa: the degree of interaction with=70 mol.%)

In a three-neck flask, equipped with reflux condenser and thermometer, is placed 57,3 weight parts trimensional hexamethylene-diisocyanate (HDI) (Basonat H1100 BASF AG) and 88,0 weight parts of the solvent-naphtha. When cooled reflux condenser, cover with nitrogen and stirring the mixture of 14.8 parts by weight of N-[3-(trimethoxysilyl)propyl]-butylamine (Dynasilan® 1189 company Degussa) (IIIa) and 50.2 parts by weight of bis-[3-(trimethoxysilyl)propyl]-amine (IIa) (Dynasilan® 1124 company Degussa) in such a way that does not exceed 50 to 60°C. after dosing the reaction temperature kept at 50 to 60°C until determined using the titration mass fraction of isocyanate is theoretically designed 70 mol.%.

The solution is partially silanizing MDI has a solids content in 58,2 wt.%.

Getting polyacrylonitrile And

In the steel hull reactor, equipped with a Monomeric flow, initiating flow, thermometer, heating the liquid fuel is reflux heated to 140°C 29,08 weight parts of a standard aromatic solvent mixture (Solventnaphtha® company DHC Solvent Chemie GmbH). Then add the mixture from A1 3,39 weight parts of the solvent-naphtha 2.24 parts by weight of tert.-butyl peroxy-2-ethylhexanoate with such speed under stirring, the mixture A1 ends of 6.75 hours Later, 15 minutes after the start of addition of the mixture A1 add a mixture of A2 consisting of equal to 4.97 weight parts of styrene, 16,91 parts by weight of tert.-of butyl acrylate, 19,89 weight parts of 2-hydroxypropylmethacrylate, 7,45 weight parts of n-butyl methacrylate, and of 0.58 parts by weight of acrylic acid with such speed that the addition of a mixture of A2 is completed within 6 hours After addition of the mixture A1, the reaction mixture is kept for another 2 h to 140°C and then cooled to below 100°C. Then the reaction mixture is still diluted with a mixture of A3 3,70 weight parts of 1-methoxypropylacetate-2, 3,06 weight parts of butylchloroformate and 6,36 weight parts of butyl acetate 98/100. The resulting solution polyacrylonitrile And has a solids content in 52,4% (1 h, 130°C, drying oven with air circulation), the viscosity of 3.6 dPas (ICI-viscometer with cone and plate, 23°C), hydroxyl number 155 mg KOH/g and an acid number of 10-13 mg KOH/g

The coating composition tools

Top tools were prepared as follows:

Component 1 containing component a (polyol) and standard additives and catalyst and solvent, shortly before application combined with componenta, contains component (modified polyisocyanate) and stir until then, until a homogeneous mixture is formed. Application is done pneumatically at 2.5 bar in three passes.

The coating for 5 minutes at room temperature undergoes evaporation and then at 140°C for 22 minutes to burn.

Table 1 lists all the top tools on the content of the components:

Table 1
Composition of a coating means according to the invention
ExampleB1B2B3B4B5B6V7
ComponentB1B2B3B4B5B6V7
weight part polyacrylonitrile And according to the example45,045,045,045,0 45,045,045,0
the weight of the component52,0to 47.248,343,7144,9133,0153,0
weight part of catalyst1(Nacure 4167, King Industries) non-volatile fraction of 25%2,12,22,32,46,97,27,8
weight parts BYK 301 (a means of facilitating spreading, Byk Chemie)0,20,20,20,20,20,20,2
weight parts of Tinuvin 384.2 (Ciba)0,90,90,90,90,90,90,9
weight parts of Tinuvin 292 (Ciba)0,8 0,80,80,80,80,80,8
weight parts of the solvent-naphtha (DHC Solvent Chemie GmbH)20,020,020,020,020,020,020,0
The equivalent ratio of free isocyanate groups in the component to hydroxyl groups in polyacrylonitrile And1,00:1,001,00:1,001,00:1,001,00:1,001,00:1,001,00:1,001,00:1,00
the Si content in wt-%2)1,51,82,52,9a 3.94,55,9
1) a catalyst based on aminocarbonyl complex partial esters of phosphoric acid
2) calculated content Si used quantities (IIa)and(IIIa), in terms of the solid content of a coating funds

The resistance to scratching of the surfaces of the obtained coatings was tested using tests on abrasion (Crockmeter) (following EN ISO 105-X12 with 10 double moves and 9N applied force when using 9 micron polishing paper (3M 281 Q wetordry™production™), followed by determination of residual gloss at 20° with a standard gloss meter), and the test raskovka (Hammertest) (10 or 100 double passages with steel wool (RAKSO®00 (thin)and applied weighing 1 kg, carried out with the assistance of a hammer. Then again determined residual gloss at 20° standard meter gloss, resistance to weathering was investigated using SEM-test (according to DIN EN ISO 11341 Feb 98 and DIN EN ISO 4892-2Nov00). The results are shown in table 2.

Table 2
Properties of layers of transparent varnish obtained by using coating means according to the invention
ExampleB1B2B3B4B5B6V7
Test istian is e (residual gloss in %) 41535863758895
Test raskovka 10 DH (residual gloss in %)38496064798893
Test raskovka 100 DH (residual gloss in %)011828658192
Glitter82858585868686
HIMSELF 180 test (h) prior to the occurrence of cracks5500525050004500525050004000

The table is and 2 shows the properties of the coatings of examples B1 to B7, obtained from the coating means according to the invention, containing isocyanurate product joining In on the basis of interaction HDI-isocyanurate in each case with a mixture of component and component IIIa (examples B2, B3, B6 and B7) compared to the cover means containing isocyanurate product joining In on the basis of interaction with HDI-isocyanurate, hereinafter abbreviated as HDI, and only the component IIa (example B4) respectively IIIa (examples B1 and B5).

When the degree of interaction of the isocyanate groups of HDI 30 mol.% shows B1 (containing only structural units (III) compared to B4 (containing only structural units (II) is clearly a longer period of time in SAM test prior to the initiation of cracks. Accordingly, when the degree of interaction of the isocyanate groups of HDI 70 mol.% example B5 (containing only structural units (III) compared to V7 (containing 70 mol.% structural units (II) shows clearly a longer period of time in SAM test prior to the initiation of cracks. Differently than with weather resistance, is the case with scratch resistance: the extent of interaction of the isocyanate groups of HDI 30 mol.% B1 (containing only structural units (III) compared to B4 (containing only structural units (II) shows clearly weaker scratch resistance in various tests Zara is aniem. Accordingly, when the degree of interaction of the isocyanate groups of HDI 70 mol.% example B5 (containing only structural units (III) compared to V7 (containing 70 mol.% the structural unit (II) shows clearly weaker scratch resistance in various tests tarpanam. As the relative share of structure II is responsible for the scratch resistance and the share structure III for weather resistance, thorough mixing of both siloxane respectively IIIa can be fine-tuned between the time of atmospheric exposure and resistance to scratching. For example, in this context, B1 and B4 must be opposed B2 and B3 in the group with 30 mol.% the degree of interaction of the isocyanate functions. B1 reaches high values in weather resistance, but the resistance to scratching is mediocre. B4 has a strong resistance to scratching, but is weaker when weather resistance. Both examples B2 and B3 compared to B1 possess better resistance to scratching and compared to B4 of the best periods of atmospheric exposure. Similar applies to B5 compared to B6 and B7 in the group with 70 mol.% the degree of interaction of the isocyanate, but here as resistance to scratching, and resistance to weathering due to the high relative proportion of siloxane functions are under even more forces is the major influence. Also it is clear that with a high degree of interaction isocyanate functions relative share structure III has significantly stronger effect on the weather resistance than the structure II resistance to scratching that can be easily installed when comparing values B6 and B7. In General, the value of the resistance to scratching is correlated with the interaction of the isocyanate groups with compounds II and III, and to obtain very high resistance to scratching also requires increased interaction isocyanate groups.

Comparative examples 1 to 7

Examples 1 through 7 were repeated, but with the only difference that instead of the catalyst based on aminocarbonyl complex partial esters of phosphoric acid as a catalyst was used blocked a pair of toluensulfonate.

Table 3 lists all the top tools of comparative examples relative proportion of components:

Table 3
The coating composition of funds comparative examples
ExampleVB1VB2VB3VB4VB5 VB6VB7
ComponentB1B2B3B4B5B6V7
weight part polyacrylonitrile And according to the example45,045,045,045,045,045,045,0
weight part Component52,0to 47.248,343,7144,9133,0153,0
weight part of catalyst3(Dynapol 1203, Degussa) non-volatile fraction of 50%1,11,11,21,23,53,6a 3.9
weight parts BYK 301 (a means of facilitating spreading, wook Chemie)0,2 0,20,20,20,20,2
weight parts of Tinuvin 384.2 (Ciba)0,90,90,90,90,90,90,9
weight parts of Tinuvin 292 (Ciba)0,80,80,80,80,80,80,8
weight parts of the solvent-naphtha (DHC Solvent Chemie GmbH)20,020,020,020,020,020,020,0
The equivalent ratio of free isocyanate groups in the component to hydroxyl groups in polyacrylonitrile And1,00:1,001,00:1,001,00:1,001,00:1,001,00:1,001,00:1,0 1,00:1,00
The Si content in wt-%4)1,51,82,52,9a 3.94,55,9
3) a catalyst based on blocked p-toluenesulfonic acid
4) the content of Si calculated from the quantities used (IIa)and(IIIa), calculated on the solids content of a coating funds

Table 4
Properties of layers of transparent varnish obtained by coating funds comparative examples
ExampleVB1VB2VB3VB4VB5VB6VB7
Test abrasion (residual gloss in %)14671335 5678
Test raskovka 10 DM (residual
Shine in %)
16233236446779
Test raskovka 100 DH (residual gloss in %)0007205358
Glitter82858484848585

Comparison of examples according to the invention from 1 to 7 with comparative examples VB1 to VB7 shows that the coatings according to the invention of examples B1 to B7 after the final curing in 20 min at 140°C possess good resistance to scratching, while the corresponding coatings of comparative examples VB1 to VB7 all after the final curing in 20 min 140°C have significantly lower resistance to scratching. Wherefore, in particular coatings of comparative examples VB1 VB4 after curing should be additionally processed thermally, so in the field of OEM coating to achieve good resistance to scratching, which, however, is very expensive and therefore is nepraktichen. Without this additional processing of the coating due to its low resistance to scratching directly after thermal curing are convenient to use only conditionally, because the danger of damage. Besides, you need to repair on-line polishing properties of the obtained coatings attached to the coatings of comparative examples only tentatively.

With increasing content of the silane coating according to the invention, in particular examples B3 through B7, also demonstrate a better Shine than the coatings of the respective comparative examples.

In addition, the coatings of comparative examples VB1 to VB7 is disadvantageous that - on the basis of a strong subsequent crosslinking of the coatings after thermal curing is the final hardness of the obtained coating - if at all - is much more difficult to install. This subsequent stitching this increases the increasing degree of silanization and increasing share of bifunctional silane (IIa). Subsequent stitching, in General, also leads to maloosmyslennym properties of the obtained coatings and risk of cracks due to internal stresses in coatings compare the additional examples.

1. The covering means on the basis of the aprotic solvent containing
(a) at least one containing the hydroxyl group of the compound (A),
(b) at least one connection (In) free and/or blocked isocyanate groups,
(c) at least one catalyst (D) for stitching Milanovich groups, and
(i) one or more components of the coating liquids contain gidrolizuemye silane groups and
(ii) the covering means can be permanently overiden to cover, which is statistically distributed grid area of the Si-O-Si,
characterized in that
(III) catalyst (D) or catalysts (D) are phosphorus, and
(IV) one or more components of the coating means are between 2.5 and 97.5 mol%, in terms of the totality of the structural units (II) and (III)at least one structural unit of formula (II)

and
R' = hydrogen, alkyl or cycloalkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with Ra = alkyl, cycloalkyl, aryl or aralkyl, preferably R' = ethyl and/or methyl X,X' = linear and/or branched alkalinity or cycloalkenyl residue with 1 to 20 carbon atoms, preferably X, X' = alkalinity residue with 1 to 4 carbon atoms,
R” = alkyl, cycloalkyl, aryl, or Aral is Il, moreover, the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with Ra = alkyl, cycloalkyl, aryl or aralkyl, preferably R” = alkyl residue, in particular with 1 to 6 C-atoms,
n=0 to 2, m=0 to 2, m+n=2, and
x,y=0 to 2, and
between 2.5 and 97.5 mol%, in terms of the totality of the structural units (II) and (III)at least one structural unit of formula (III)

and
Z=-NH-, -NR-, -O -,
R = alkyl, cycloalkyl, aryl or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with Ra = alkyl, cycloalkyl, aryl or aralkyl,
x=0 to 2, and
X, R', R” have the meaning given in formula (II).

2. Coating tool according to claim 1, characterized in that the catalyst (D) is a phosphorus-containing and nitrogen.

3. Coating tool according to claim 1, characterized in that the catalyst (D) or catalysts (D) are selected respectively selected from the group of substituted complex diesters of phosphonic acid and/or complex diesters diphosphonic acid, substituted complex monoamino phosphoric acid and/or complex diesters of phosphoric acid, mainly from the group consisting of acyclic complex of diesters of phosphoric acid and/or cyclic complex of diesters of phosphoric acid, and/or relevant aminocarbonyl esters of phosphoric KIS is the notes.

4. Coating tool according to claim 2, characterized in that the catalyst (D) blocked tertiary amine.

5. Coating tool according to claim 1, characterized in that the catalyst (D) is selected from the group aminocarbonyl ethylhexyloxy partial esters of phosphoric acid and aminocarbonyl phenyl partial esters of phosphoric acid, particularly aminocarbonyl bis(ethylhexyl)new esters of phosphoric acid.

6. Coating tool according to claim 1, characterized in that one or more components of cover means at least partially has one or more similar or different structural units of the formula (I)

with
G = identical or different gidrolizuemye group, in particular G = alkoxygroup (OR'),
X = organic residue, in particular linear and/or branched alkalinity or cycloalkenyl residue with 1 to 20 carbon atoms, very particularly preferably X = alkalinity residue with 1 to 4 carbon atoms,
R” = alkyl, cycloalkyl, aryl, or aralkyl, and the carbon chain may be interrupted by non-contiguous groups of oxygen, sulfur or NRa, with Ra = alkyl, cycloalkyl, aryl or aralkyl, preferably R” = alkyl residue, in particular with 1 to 6 C-atoms,
x=0 to 2, preferably from 0 to 1, particularly preferably x=0.

7. Coating tool according to claim 1, trichomania fact, that one or more components of the coating means are between 5 and 95 mol.%, in particular between 10 and 90 mol.%, especially preferably between 20 and 80 mol.%, and very particularly between 30 and 70 mol.%, each time calculated on the sum of structural units (II) and (III)at least one structural unit of formula (II) and between 5 and 95 mol.%, in particular between 10 and 90 mol.%, especially preferably between 20 and 80 mol.%, and very particularly between 30 and 70 mol.%, each time calculated on the sum of structural units (II) and (III)at least one structural unit of formula (III).

8. Coating tool according to claim 1, characterized in that the structural elements (II) and (III) are in fractions of from 2.5 to 97.5 mol.%, preferably from 5 to 95 mol.%, especially preferably between 10 and 90 mol.%, every once in terms of the amount of badly needed to stitch in top tool functional groups, formed from parts of hydroxyl and isocyanate groups, as well as parts of the structural elements (II) and (III).

9. Coating tool according to claim 6, characterized in that the coating agent contains less than 6.5 wt.% Si structural units (I)and/or (II) and/or (III), preferably a maximum of 6.0 wt.% Si structural units (I) and/or (II) and/or (III), each time calculated on the solids content of a coating means.

10. Coating tool according to claim 6, characterized in that the polyisocyanate (A) has structural units (I) (II) (III).

11. Top tool of claim 10, characterized in that the polyisocyanate (B)
between 2.5 and 90 mol.% isocyanate groups in the polyisocyanate main substance of the subject interaction to obtain the structural units (II) and
between 2.5 and 90 mol.% isocyanate groups in the polyisocyanate main substance of the subject interaction to obtain the structural units (III)
and/or the total share of which came in the reaction of isocyanate groups to obtain structural units (II) and/or (III) in the polyisocyanate main ingredient is between 5 and 95 mol.%.

12. Top tool of claim 10, wherein the polyisocyanate base material selected from the group 1,6-hexamethylenediisocyanate, isophoronediisocyanate, and 4,4'-methylendysiclogecsyldiizosyonat, biuret dimers of the above polyisocyanates and/or isocyanurate of trimers of the above polyisocyanates.

13. Coating tool according to claim 1, characterized in that the polyol (A) contains at least one poly(meth)acrylation.

14. Multistage method of coating, characterized in that optionally pre-coated substrate is applied pigmented layer of base paint and then a layer of the coating tool according to one of claims 1 to 13.

15. Multistage method of coating according to 14, characterized in that by the primary varnish pigmentaria the aqueous base lacquer is dried at temperatures from room temperature up to 80°C, and the damage on the main lacquer coating tool according to one of claims 1 to 13 utverjdayut at temperatures from 30 to 200°C over a period of time from 1 minute to 10 hours

16. Application of the method according to 14 or 15 for varnishing series production automobiles and auto repair coating.

17. The application of a coating tool according to one of claims 1 to 13 as a transparent lacquer for coating cars mass production and for repair lacquering.

18. The application of a coating tool according to one of claims 1 to 13 as a light, transparent lacquer for coating polymeric substrates.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to thermally solidificated covering substances based on aprotic solvent. Claimed is covering substance, which contains at least one compound (A), containing hydroxyl groups, and at least one compound (B), containing isocyanate groups, and one or several components of covering substance have between 2.5 and 97.5 mole % counted per totality of structural units (I) and (II), at least one structural unit of formula (I), where R'=hydrogen, alkyl or cycloalkyl, and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, X,X'=linear and/or branched alkylene or cycloalkylene residue with from 1 to 20 carbon atoms; R"= alkyl, cycloalkyl, aryl or aralkyl, and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, n=0 to 2, m=0 to 2, m+n=2, x,y=0 to 2; and between 2.5 and 97.5 mole % counted per totality of structural units (I) and (II), at least one structural unit of formula (II), where Z=-NH-, -NR-, -O-; R=hydrogen, alkyl, cycloalkyl, aryl or aralkyl and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, x=0 to 2, and X, R', R" have value, given above; and polyol (A) contains at least one poly(meth)acrylate polyol. Also claimed are multi-step method of applying coating with application of said covering substance, method application and versions of coating application.

EFFECT: possibility of simple obtaining of transparent varnish coatings with high resistance to crack formation under atmospheric impact and perfect resistance to scratching, which do not cause any ecological problems.

15 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: polyurethane coating is made from a composition which contains refined castor oil, an ester, an antifoaming additive BYK-066 based on fluorine-modified polysiloxanes, aluminium oxide, titanium oxide, aerosil, a water adsorbent, an additive BYK-410 - urea in an organic solvent N-methylpyrrolidone, a curing agent isocyanate SUPRASEK 5025, which is 4,4'-diphenylmethane diisocyanate and additionally as filler - dolomite or zeolite or a mixture of dolomite and zeolite in ratio 3.25:1.

EFFECT: coating has high breaking strength and modulus of elasticity in tension, while providing sufficiently high deformation characteristics, particularly tensile elongation.

2 tbl

FIELD: construction.

SUBSTANCE: method to manufacture a coating includes preparation of a mixture by means of mixing of a filler from rubber crumb and a binder based on polyurethane. Simultaneously and separately from each other mixtures are produced for basic and upper layers, at the same time in the mixture for the basic layer they use a filler from rubber crumb with fraction of 2-12 mm, and in the mixture for the upper layer they use a filler from rubber crumb with fraction of 1-3 mm and a pigment dye. In process of mixture mixing for its upper layer it is compacted, afterwards the mixture for the upper layer is serially discharged into a die mould, then the mixture for the basic layer is discharged, and pressed under pressure with the help of a press, then maintained until full hardening, and the produced coating is discharged from the die mould.

EFFECT: high efficiency of coating manufacturing, higher reliability and durability of a coating, possibility to manufacture a double-layer coating with damping properties.

8 cl

FIELD: chemistry.

SUBSTANCE: formulation composition contains: A) 5-95 wt % at least one radiation-curable resin, B) 5-25 wt % silicic acid, C) 0.1-10 wt % at least one adhesion promoter, D) 5-90 wt % at least one radiation-curable reactive diluent, E) 0.5-5 wt % at least one dispersant. The adhesion promoter is selected form phosphoric acid and/or phosphonic acid and/or products of reaction thereof with functionalised acrylates. The composition can additionally contain photoinitiators, pigments and additives, selected from diffusion promoting agents, delustering agents and degassing agents. The compositions are used as a primer, an intermediate layer, coating varnish and/or clear varnish, as well as for making coatings via a coil coating technique.

EFFECT: coatings have flexibility, thereby providing excellent protection of metal substrates from corrosion.

18 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a self-crosslinking binder for coating compositions containing an aqueously dispersed polymer component A having at least one carbonyl group of the ketone or aldehyde type per molecule, and a component B having at least two hydrazine or hydrazide groups per molecule, and at least one structural unit -NR1-NR2-CHR3-CHR4-NH-R5 (I), where the radicals R1, R2, R3 and R4 are each individually selected from a group consisting of a hydrogen radical and a linear or branched alkyl radical having from 1 to 10 carbon atoms, R3 and R4 may additionally be selected from a group consisting of aryl and alkylaryl radicals having from 6 to 15 carbon atoms, and from oxyalkyl radicals with 1 to 10 carbon atoms, where oxy groups may be inserted into the alkyl chain or at the end of an alkyl chain, and R5 is selected from a group consisting of a hydrogen radical, alkyl radicals which may be linear, branched or cyclic and may have from 1 to 10 carbon atoms, and residues of formula -(CH2)n-CO-O-X, where n is an integer of from 1 to 6, and X is a residue of a polyatomic alcohol or phenol. A method of producing such a binder is also described.

EFFECT: producing a coating binder which is self-crosslinking when drying, having fast drying properties and improved chemical resistance and weather resistance.

17 cl, 5 ex, 5 tbl

FIELD: construction.

SUBSTANCE: invention represents an emulsion, in which oligomers with terminal isocyanate groups are a dispersion medium, and a disperse phase is a solution or a dispersion produced as a result of mixing a lime solution with calcium hydroxide content of 10-70 wt % with glycerine in the amount of 1-250 wt parts per 100 wt parts of calcium hydroxide, besides, the disperse phase content in the composition makes 1-55 wt %.

EFFECT: development of a cheap and easy to apply composition, coatings from which have high adhesion to moist metal or concrete surfaces, have proper adhesion to concrete applied onto them, are hardened with specified speed at temperature from zero and above, inhibit processes of metal corrosion and have low elasticity module.

1 tbl

FIELD: chemistry.

SUBSTANCE: coating has surface tension less than 20 mN/m, wherein the coating material used is hydrolysis-resistance lacquers, and where the hydrolysis-resistant lacquers are selected from a group consisting of polyurethanes, acryl and silicones, where the coating has a random topography with roughness of less than 500 nm, preferably less than 300 nm.

EFFECT: coating prevents deposit of bacteria and improves thermal conduction of the coated material.

19 cl, 4 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to aldimines of formula (I)

where A does not contain active hydrogen and a primary amine group, or together with R7 denotes a (n+2)-valent hydrocarbon radical containing 3-20 carbon atoms and, if necessary, at least one heteroatom in form of oxygen of an ether group or nitrogen or a tertiary amine group; n equals 1, 2, 3 or 4; m equals 0,1, 2, 3 or 4; R1 and R2 each denotes a univalent hydrocarbon residue with 1-12 carbon atoms or together denote a divalent hydrocarbon radical which is part of a carbocyclic ring with 5-8 carbon atoms; R3 denotes H or alkyl; R4 and R5 independently denote CH3 or a univalent aliphatic radical containing 2-12 carbon atoms and optionally hydroxy groups; X denotes O, S, N-R6, or N-R7, where R6 denotes a univalent hydrocarbon radical containing 1-20 carbon atoms and having at least one hydroxy group; as well as curable compositions containing such aldimines and use of said compositions.

EFFECT: obtaining novel aldimines which can be used as curing agents in curable compositions.

22 cl, 18 ex, 6 tbl

FIELD: chemistry.

SUBSTANCE: powder coating is obtained from a composition containing at least one binding material (A) from polyester resin with a hydroxyl functional group and at least one polyurethane resin (B) as a cross-linking agent containing blocked isocyanate groups. At least one binding material from the polyester resin (A) with a hydroxyl functional group and at least one polyurethane resin (B) have melting point of 60-180°C, specifically 60-160°C. The powder composition is deposited on a substrate and cured. The substrate can be metal, plastic, wood, paper or glass.

EFFECT: obtaining coatings with the required processing properties, specifically obtaining thin films and high flexibility combined with excellent mechanical coating properties.

11 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: paint with thermo-, fire-protective properties contains (wt %): binder based on acrylic (co)polymers and/or silicone resins and organosoluble polyurethanes - (20-40), filler in form of a mineral component - (10-30), antipyrene additive - (10-20), modifying additive in form of ceramic and/or glass microspheres with diameter of 20-150 mcm -(10-30) and an organic solvent - the rest. The paint composition additionally contains bentonite powder, intercalated with cobalt Co2+ ions and/or cerium Ce3+ ions in amount of 3-7 wt %.

EFFECT: invention increases stability of the formed protective paint coating to thermal-oxidative reactions, improves environmental safety, fire-resistance of the protective coating and endows said coating with bactericidal properties.

7 cl, 2 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to thermally solidificated covering substances based on aprotic solvent. Claimed is covering substance, which contains at least one compound (A), containing hydroxyl groups, and at least one compound (B), containing isocyanate groups, and one or several components of covering substance have between 2.5 and 97.5 mole % counted per totality of structural units (I) and (II), at least one structural unit of formula (I), where R'=hydrogen, alkyl or cycloalkyl, and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, X,X'=linear and/or branched alkylene or cycloalkylene residue with from 1 to 20 carbon atoms; R"= alkyl, cycloalkyl, aryl or aralkyl, and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, n=0 to 2, m=0 to 2, m+n=2, x,y=0 to 2; and between 2.5 and 97.5 mole % counted per totality of structural units (I) and (II), at least one structural unit of formula (II), where Z=-NH-, -NR-, -O-; R=hydrogen, alkyl, cycloalkyl, aryl or aralkyl and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, x=0 to 2, and X, R', R" have value, given above; and polyol (A) contains at least one poly(meth)acrylate polyol. Also claimed are multi-step method of applying coating with application of said covering substance, method application and versions of coating application.

EFFECT: possibility of simple obtaining of transparent varnish coatings with high resistance to crack formation under atmospheric impact and perfect resistance to scratching, which do not cause any ecological problems.

15 cl, 2 tbl, 4 ex

FIELD: inorganic chemistry.

SUBSTANCE: invention refers to polymer chemistry particularly to polyurethanes and foamed polyurethanes processing technologies. Described method of all-purpose metal-complex modifier for polyurethane implies solution of metal halogenide in solvent. This method is characterized by solution of metal halogenide having variable valence of stable oxidation level, for example manganese chloride (II) tetrahydrate, in N,N-dimethylethanolamine and ε-caprolactam at mole ratio of metal halogenide: dimethylethanolamine: ε-caprolactam 1:5:5-20. Modifying agent is added to laprole component. Polyurethanes produced with modifying agent are characterized by improved physical-mechanical properties such as ultimate breaking stress, rigidity at deformation 40% and comfort coefficient.

EFFECT: production of polyurethanes with improved physical-mechanical properties; increased comfort coefficient rigidity and ultimate breaking stress.

1 cl, 6 tbl

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to mixtures consisting of blocked polyisocyanates designated as hardening agents in monocomponent lacquers of hot drying and comprising: (a) blocked polyisocyanate based on 1,6-diisocyanate hexane; (b) blocked polyisocyanate based on cycloaliphatic diisocyanates chosen from group comprising 1-isocyanato-3,3,5-trimethyl-5-ixocyanatomethylcyclohexane, bis-(4-isocyanatocyclohexyl)methane, 2,6-bis-isocyanatonorbornane, 2,5-bis-isocyanatonorbornane, 1,4-bis-isocyanatomethylcyclohexane and their mixtures, and (c) 3,5-dimethylpyrazole as a single blocking agent of agent of polyisocyanates named in (a) and (b). Blocked polyisocyanates are taken in the weight ratio (a) : (b) = 1:(1.8-2.2). Using mixtures of blocked polyisocyanates provides preparing clear lacquers with good acid resistance, stability against scratching and thermal yellowing.

EFFECT: improved and valuable properties of agents.

1 cl, 6 ex

The invention relates to the technology of polyurethanes, which can be used as adhesives, paints, construction materials

The invention relates to the chemistry of polymers, namely, anti-static polyurethane, which can be used for the manufacture of anti-static products and coatings, in particular rollers, pulleys and couplings in textile machinery

FIELD: chemistry.

SUBSTANCE: invention relates to thermally solidificated covering substances based on aprotic solvent. Claimed is covering substance, which contains at least one compound (A), containing hydroxyl groups, and at least one compound (B), containing isocyanate groups, and one or several components of covering substance have between 2.5 and 97.5 mole % counted per totality of structural units (I) and (II), at least one structural unit of formula (I), where R'=hydrogen, alkyl or cycloalkyl, and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, X,X'=linear and/or branched alkylene or cycloalkylene residue with from 1 to 20 carbon atoms; R"= alkyl, cycloalkyl, aryl or aralkyl, and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, n=0 to 2, m=0 to 2, m+n=2, x,y=0 to 2; and between 2.5 and 97.5 mole % counted per totality of structural units (I) and (II), at least one structural unit of formula (II), where Z=-NH-, -NR-, -O-; R=hydrogen, alkyl, cycloalkyl, aryl or aralkyl and carbon chain can be interrupted by non-adjacent groups of oxygen, sulphur or NRa, with Ra= alkyl, cycloalkyl, aryl or aralkyl, x=0 to 2, and X, R', R" have value, given above; and polyol (A) contains at least one poly(meth)acrylate polyol. Also claimed are multi-step method of applying coating with application of said covering substance, method application and versions of coating application.

EFFECT: possibility of simple obtaining of transparent varnish coatings with high resistance to crack formation under atmospheric impact and perfect resistance to scratching, which do not cause any ecological problems.

15 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: polyacrylic (co)polymer which is curable under the effect of atmospheric moisture and having elastometic properties is a plurality of acrylic prepolymer segments interlinked by urea or urethane links caused by moisture curing. Each of the plurality of prepolymer segments is a homopolymer or a copolymer of methylmethacrylate, C1-C16-alkylacrylate and C1-C16-alkylmethacrylate as the predominant monomer group. The moisture-curing method involves formation of a plurality of segments of an acrylic prepolymer, obtaining isocyanate-functionalised segments of the acrylic prepolymer, storing the isocyanate-functionalised segments in anhydrous state, followed by deposition thereof onto a substrate and moisture-curing to form a polyacrylic polymer.

EFFECT: obtaining polyacrylic (co)polymers cured under the effect of atmospheric moisture and having elastomeric properties, which retain resistance to UV rays, optical transparency, wear and physical properties of conventional thermoplastic acrylic polymers.

14 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: multicomponent aqueous composition contains an aqueous dispersion and a component containing a material having functional groups. The components are mixed with each other before applying the composition onto the substrate. The aqueous dispersion contains a polycarbonate-polyurethane polymer and an acrylic polyol. The aqueous dispersion also contains an organic solvent. The material having functional groups reacts with functional groups of the acrylic polyol and/or polycarbonate-polyurethane polymer. The acrylic polyol has number-average molecular weight from 500 to 4000. The polycarbonate-polyurethane polymer is obtained via a reaction between hydroxy-functional carbonate-containing material and polyisocyanate. The hydroxy-functional carbonate-containing material contains a product of reaction between carbonic acid or derivative thereof and a diol. The diol is hexane-1,6-diol.

EFFECT: composition has low content of volatile substances, as well as high water resistance and hardness.

20 cl, 3 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: composition contains the following in pts.wt: 100 - copolymer of butadiene and piperylene with molecular weight 1200-3200 and content of hydroxyl groups 0.8-1.1%, 20-polymethylene polyphenyl isocyanate with content of isocyanate groups 29-31%, 70-100 - rubber crumbs, and 25-20 - high-molecular polyethylene with molecular weight 30000-800000.

EFFECT: high dynamic and physical-mechanical properties of the composition based on the filled foamed polyurethane.

1 ex, 2 tbl

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