WO2019057448A1

WO2019057448A1 - At least partly blocked polyisocyanate (bp)

Info

Publication number: WO2019057448A1
Application number: PCT/EP2018/073041
Authority: WO
Inventors: Frederic Lucas; Alexander Panchenko
Original assignee: Basf Se
Priority date: 2017-09-25
Filing date: 2018-08-27
Publication date: 2019-03-28

Abstract

The invention relates to an at least partly blocked polyisocyanate (BP) which is obtained by reacting a polyisocyanate (P) with at least one thermally disassociating blocking agent (BM). The polyisocyanate (P) has a general formula selected from the formulas (la), (Ib), (Ic), or (Id). The invention also relates to the use of the at least partly blocked polyisocyanate (BP) in order to produce paints, dyes, and adhesives.

Description

At least partially blocked polyisocyanate (BP) Description The present invention relates to an at least partially blocked polyisocyanate (BP) obtained by reacting a polyisocyanate (P) with at least one thermally dissociating blocking agent (BM). The polyisocyanate (P) has a general formula selected from the formulas (Ia), (Ib), (Ic) or (Id). Another object of the present invention is the use of at least partially blocked polyisocyanate (BP) for the production of paints, inks and adhesives.

Blocked polyisocyanates play a decisive role in the field of paints and adhesives, and in particular in the paint sector. The main field of use of blocked polyisocyanates are, above all, one-component paints which as a rule contain further compounds containing hydroxyl groups, such as, for example, polyols or polyesters. The blocking agent is reversibly bound to the polyisocyanate and can be removed by heat, prevents the premature reaction between the polyisocyanates and the hydroxy-containing compounds and thus regulates the curing of the coatings in a certain temperature range.

Blocked polyisocyanates are described in the prior art. Thus, for example, EP 1 028 135 A1 discloses a process for the preparation of blocked polyisocyanates based on bis (4-isocyanatocyclohexyl) methane, which are blocked with 1,2,4-triazole. To prepare the blocked polyisocyanates, bis (4-isocyanatocyclohexyl) methane is converted into melt with 1,2,4-triazole to give a powdery cross-linker. Blocked polyisocyanates which are blocked with 1,2,4-triazole are bis (4-isocyanatocyclohexyl) methane and isocyanurates and urethane group-containing adducts of bis (4-isocyanatocyclohexyl) methane with dihydric or trihydric alcohols.

WO 01/85823 discloses mixtures of blocked polyisocyanates in which polyisocyanates based on 1,6-diisocyanatohexane and polyisocyanates based on cycloaliphatic diisocyanates are blocked with 3,5-dimethylpyrazole. As cycloaliphatic polyisocyanates isophorone diisocyanate, bis (4-isocyanatocyclohexyl) methane, 2,6- and / or 2,5-diisocyanatonorbornane or 1,4-bis (isocyanato-methyl) cyclohexane are disclosed. In addition, according to WO 01/85823, the blocked polyisocyanates may additionally have isocyanurate, allophanate, uretdione or urethane groups. Further detailed insights regarding blocked polyisocyanates and their fields of application are presented in the reviews Wieks et al .; Progress in Organic Coatings, 36 (1999), 148 to 172 "and Wieks et al.," Progress in Organic Coatings, 41 (2001), 1 to 83 ". A detailed discussion of the reaction mechanism of blocking as well as the heat-induced removal and the choice of suitable blocking agents is carried out i Wieks et al .; "Progress in Organic Coatings, 43 (2001), 131 to 140".) The adjustment of the temperature necessary to remove the blocking agent from the blocked polyisocyanate is usually superficially based on the choice of the blocking agent, for example, pyrazoles or Triazoles as blocking agents are generally lower in temperature than lactams or oximes, while the influence of the polyisocyanate is only of secondary importance in the prior art.

European application 17171588.1 discloses novel polyisocyanates obtained by reacting cycloaliphatic diisocyanates with at least one alcohol having at least two alcohol groups. The blocking of these novel polyisocyanates with a blocking agent is not disclosed in the European application 17171588.1.

European application 16200079.8 discloses the preparation of trimeric isocyanates based on cycloaliphatic isocyanates. The customary in cycloaliphatic isocyanates formation of by-products can be largely avoided by the particular trans conformation of the two substituted on the cycloalkane ring isocyanate groups and by a halogen-containing catalyst. The blocking of such trimeric isocyanates is likewise not described in European Application 16200079.8.

The object of the present invention is thus to provide a new, at least partially blocked polyisocyanate.

This object is achieved by the at least partially blocked polyisocyanate (BP) obtainable by reacting a polyisocyanate (P) with at least one thermally dissociating blocking agent (BM), characterized in that the polyisocyanate (P) has a general formula selected from the formulas (Ia ), (Ib), (Ic) and (Id) have:

(Ic) (Id) in which k, m, n are independently 0, 1, 2 or 3, the sum of k, m and n being at least 2 and at most 6; and is a linear or branched organic radical having at most 14 carbon atoms, which may optionally contain at least one nitrogen atom and / or at least one oxygen atom,

R ^a , R ^b , R ^{c are} independently selected from radicals of the general

Formulas (IIa), (IIb), (IIc) and / or (Id):

(IIa)

where o is 0 to 10, and

R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ , R ⁴ ' are independently selected from

A group consisting of H, OR ⁵ and unsubstituted or at least monosubstituted C ₁ -C 10 -alkyl, C ₅ -

Ci2-cycloalkyl, C ₂ -C ₀ alkenyl, and C ₆ -C ₄ aryl, wherein R ⁵ CC ₁₀ alkyl.

It has surprisingly been found that the at least partially blocked polyisocyanate (BP) according to the invention has a lower temperature for the removal of the thermally dissociating blocking agent (BM) in comparison to other blocked cycloaliphatic polyisocyanates. For this reason, the at least partially blocked polyisocyanate (BP) is particularly suitable in secondary products as in one-component paints, since the lower temperature for removing the thermally dissociating blocking agent (BM) leads to a faster and more cost-effective curing of the coatings.

The lower temperature to remove the blocking agent (BM) can prevent decomposition of temperature-sensitive components in secondary products such as organic dyes or pigments. Likewise, unwanted thermal effects on temperature-sensitive support materials (substrates) can be applied to the secondary products such as one-component paints are avoided.

The present invention will be explained in detail below.

In the context of the present invention, a polyisocyanate is understood as meaning an organic compound which contains two or more isocyanate groups (-NCO).

In the context of the present invention, a polyurethane is understood as meaning an organic compound which contains two or more urethane groups (-O-CO-NH-). The radicals R ^a , R ^b and R ^{c of} the general formulas (IIa), (IIb), (IIc) and / or (Id) are molecular fragments within the polyisocyanate (P) of the general formulas (Ia), ( Ib), (Ic) and (Id). It is clear to the person skilled in the art that the meandered lines in the general formulas (IIa), (IIb), (IIc) and (Id) show the end of the corresponding molecular fragment and that the corresponding molecular fragment at these sites is substituted by the nitrogen atoms of the isocyanate groups the nitrogen atoms of the urethane groups of the polyisocyanate (P) is linked.

In the context of the present invention, definitions such as "C ¹ -C 10 -alkyl, as defined, for example, for the radicals R ¹ to R ⁴ 'in the formulas (IIa) to (Id), mean that this substituent can be an alkyl radical having 1 to 10 carbon atoms , This may, unless otherwise stated, be linear or branched, but also at the same time, proportionally, have both forms. Examples of corresponding alkyl radicals are methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

In the context of the present invention, definitions such as "C ₅ -C ₁₂ -cycloalky, as defined, for example, for the radicals R ¹ to R ⁴ 'in the formulas (IIa) to (Id), mean that this substituent is a cycloalkyl radical having 5 to 12 carbon atoms can be. Examples of corresponding cycloalkyl radicals are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl or adamantyl. In the context of the present invention, definitions such as "C ₆ -C ₁₄ -aryl, as defined for example by the radicals R ¹ to R ⁴ 'in the formulas (IIa) to (Id), mean that this substituent is an aromatic having 6 to 14 Carbon atoms can be. The aromatic may be a monocyclic, bicyclic or polycyclic aromatic. In the case of polycyclic aromatics, individual rings may be completely or partially saturated. Examples of corresponding aryl radicals are phenyl, naphthyl, anthracyl or phenanthryl.

In the context of the present invention, definitions such as "C ₂ -C 10 -alkenyl", as defined for the radicals R ¹ to R ⁴ 'in the formulas (IIa) to (Id), mean that this substituent is an alkenyl radical having 2 to 10 carbon atoms can. This carbon moiety is preferably monounsaturated, but optionally it may also be two or more times unsaturated. preferably, C ₂ -C ₀ alkenyl in the present invention, vinyl, 1-allyl, 2-allyl, 3-allyl, ice - or trans-2-butenyl or ω-butenyl. The term "unsubstituted" in the context of the present invention means that C ₁ -C ₁₀ -alkyl, C ₅ -C ₁₂ -cycloalkyl, C ₂ -C ₁₀ -alkenyl or C ₆ -C ₁₄ -aryl contains no further substituents except hydrogen (H) The term "at least monosubstituted" means in the context of the present invention that Ci-Ci ₀ -alkyl, C ₅ -C ₁₂ -cycloalkyl, C ₂ -C ₁₀ -alkenyl or C ₆ -C ₁₄ -aryl exactly one substituent or may also have two or more substituents. The substituents may be the same or different and are Ci-Ci ₀ -alkyl, which are as defined above.

The at least partially blocked polyisocyanate (BP) is obtainable according to the invention by reacting a polyisocyanate (P) with at least one thermally dissociating blocking agent (BM), the polyisocyanate (P) having a general formula selected from the formulas (Ia), (Ib), ( Ic) and / or (Id).

Suitable corresponding polyisocyanates (P) and processes for their preparation are known in principle to the person skilled in the art.

In the context of the present invention, the at least partially blocked polyisocyanate (BP) can be prepared both from exactly one polyisocyanate (P) of a general formula selected from the formulas (Ia), (Ib), (Ic) and / or (Id) also from mixtures of different polyisocyanates (P) which have a general formula selected from the formulas (Ia), (Ib), (Ic) and / or (Id). In the case of mixtures of different polyisocyanates (P), each individual polyisocyanate (P) preferably has a structurally similar general formula selected from the formulas (Ia), (Ib), (Ic) and / or (Id). If, for example, a polyisocyanate (P) in such a mixture has the general formula (Ia), preferably all further polyisocyanates (P) in the mixture likewise have the general formula (Ia).

In a first embodiment, the polyisocyanate (P) has the general formula (Ia).

OCN-R ^a -NCO (Ia) selected from radicals of the general formulas (IIa), (IIb), (IIc) or (Id):

in which o is 0 to 10, and R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ , R ⁴ ' are independently selected from

Group consisting of H, OR ^5, and unsubstituted or at least mono-substituted Ci-Ci ₀ alkyl, C ₅ -C ₂ cycloalkyl, C ₂ -C ₁₀ alkenyl and C ₆ -C ₁₄ aryl, wherein R ^{5 is} C ₁ -C ₁₀ alkyl.

Preferably, R ^a in general formula (Ia) is selected from radicals of general formulas (IIa), (IIb), (IIc) or (Id) in which o is 0, 2 or 3 and R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ and R ⁴ 'are independently selected from the group consisting of H and unsubstituted or at least monosubstituted C ₁ -C ₁₀ alkyl.

More preferably, R ^a in the general formula (Ia) is selected from radicals of the general formulas (IIa) or (IIb) in which R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ and R ⁴ 'are independently selected from the group consisting of H, methyl, ethyl and propyl.

Even more preferably R ^a in the general formula (Ia) is selected from radicals of the general formulas (IIa) or (IIb) in which R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ and R ⁴ 'are independently selected from the group consisting of H, methyl and ethyl, wherein at least one of R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ or R ⁴ ' is methyl or ethyl, preferably methyl.

R ^a in the general formula (Ia) is particularly preferably a radical of the general formula (IIb) in which R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ and R ⁴ ' are independent are selected from the group consisting of H, methyl and ethyl, wherein at least one radical and at most 3 radicals R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ or R ⁴ ' is methyl or Ethyl, preferably methyl.

Very particular preference R ^a in the general formula (Ia) is a radical of the general formula (IIb) in which R ¹ , R ¹ ', R ² and R ² ' are independently selected from the group consisting of H and methyl, wherein at least one radical and at most 3 radicals R ¹ , R ¹ ', R ² and R ² ' are methyl, and in which R ³ , R ³ ', R ⁴ and R ⁴ ' are H.

Preferably, the polyisocyanate (P) in this first embodiment is selected from 1,3-diisocyanatocyclohexane, 1,3-diisocyanato-2-methylcyclohexane, 1,3-diisocyanato-4-methylcyclohexane, 1,3-diisocyanato-5-methylcyclohexane , 1, 3-diisocyanato-2-isopropylcyclohexane, 1, 3-diisocyanato-4-isopropylcyclohexane, 3-diisocyanato-5-isopropylcyclohexane, 1, 3-diisocyanato-2,4-dimethylcyclohexane, 1, 3-diisocyanato-2 , 4-dimethylcyclohexane, 1, 3-diisocyanato-2,4-diethyl-6-methylcyclohexane, 1, 3-diisocyanato-2-methyl-4,5-diethylcyclohexane, 1, 3-diisocyanato-2,4,6 triisopropylcyclohexane or 1,3-diisocyanato-2,4,6-tributylcyclohexane.

More preferably, the polyisocyanate (P) in this first embodiment is selected from 1,3-diisocyanatocyclohexane, 1,3-diisocyanato-2-methylcyclohexane, 1,3-diisocyanato-4-methylcyclohexane, 1,3-diisocyanato-5- methylcyclohexane, 1, 3-diisocyanato-2,4-dimethylcyclohexane, 1, 3-diisocyanato-2,4-diethylcyclohexane or 1, 3-diisocyanato-2,4-diethyl-6-methylcyclohexane.

Particularly preferred is the polyisocyanate (P) in this first embodiment selected from 1, 3-diisocyanatocyclohexane, 1, 3-diisocyanato-2-methylcyclohexane, 1, 3-diisocyanato-4-methylcyclohexane or 1, 3-diisocyanato-5-methylcyclohexane.

The polyisocyanate (P) used is preferably a mixture of 1,3-diisocyanato-2-methylcyclohexane and 1,3-diisocyanato-4-methylcyclohexane. The proportions by weight of 1,3-diisocyanato-2-methylcyclohexane and 1,3-diisocyanato-4-methylcyclohexane in this mixture can in principle be arbitrary.

The mixture of the polyisocyanate (P) in this case preferably contains from 50 to 95% by weight of 1,3-diisocyanato-4-methylcyclohexane and from 5 to 50% by weight of 1,3-diisocyanato-2-methylcyclohexane on the total weight of the polyisocyanate (P). The polyisocyanate (P) in this first embodiment preferably has a molecular weight in the range from 130 to 500 g / mol, more preferably from 140 to 350 g / mol.

In a second embodiment, the at least one polyisocyanate (P) has the general formula (Ib):

(I b) in which independently of one another are 0, 1, 2 or 3, the sum of k, m and n giving at least 2 and at most 6; and a linear or branched organic radical having at most 14 carbon atoms, which may optionally contain at least one nitrogen atom and / or at least one oxygen atom, R ^a , R ^b , R ^{c are} independently selected from radicals of the general

Formulas (I Ia), (I Ib), (I Lc) and / or (Id):

(Ia)

where o is 0 to 10, and

Group consisting of H, OR ⁵ and unsubstituted or at least monosubstituted Ci-Ci ₀ -alkyl, C ₅ - Ci2-cycloalkyl, C ₂ -C ₀ -alkenyl and C ₆ -C ₄ -aryl, wherein

R ^{5 is} CC ₁₀ alkyl. k, m and n are independently 0, 1, 2 or 3. The sum of k, m and n gives at least 2 and at most 6, more preferably at most 4.

Preferably, k is at least 2, more preferably at least 3 and at most 4, and m and n are 0. The values for k, m and n can assume odd-numbered values on a statistical average, but they are then based on each individual molecule of isocyanate (P ) of general formula (I) even.

L is according to the invention a linear or branched organic radical having at most 14 carbon atoms, which may optionally contain at least one nitrogen atom and / or at least one oxygen atom, L contains at least one, preferably at least two carbon atoms.

The number of nitrogen and / or oxygen atoms is not limited. As a rule, it is not more than 5 in the radical, preferably not more than 4, and more preferably not more than 3, particularly preferably L contains at most one nitrogen or one oxygen atom. Furthermore, between two nitrogen and / or oxygen atoms usually at least one carbon atom, preferably at least two carbon atoms. In a preferred embodiment, L contains no heteroatoms (ie N or O).

L is preferably a linear or branched, (k + m + n) -value, preferably bi- to hexavalent, more preferably bi- to tetravalent and most preferably trivalent organic radical, which according to its valency with two to six, more preferably two to four and most preferably three urethane groups. For the purposes of the present application, "valence" is understood to mean the number of urethane group-containing radicals which are substituted by an organic radical L.

Preferably, L is a linear or branched aliphatic, cycloaliphatic or aromatic radical having at most 14 carbon atoms, which may optionally contain at least one nitrogen atom and / or at least one oxygen atom. Suitable linear or branched aliphatic, cycloaliphatic or aromatic radicals are derived from corresponding (k + m + n) -valent alcohols, which are described in more detail below.

More preferably, L is a linear or branched aliphatic or cycloaliphatic radical having at most 14 carbon atoms which may optionally contain at least one nitrogen atom and / or at least one oxygen atom.

Even more preferably, L is a linear or branched aliphatic radical having at most 10 carbon atoms which may optionally contain at least one nitrogen atom and / or at least one oxygen atom.

L is more preferably a linear or branched aliphatic radical having at most 6 carbon atoms, which may optionally contain at least one oxygen atom. Preferably, R ^a , R ^b and R ^c in the general formula (Ib) are independently selected from radicals of the general formulas (IIa), (IIb), (IIc), and / or (Id) in which o is 0, 2 or 3 and R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ and R ⁴ ' are independently selected from the group consisting of H and unsubstituted or at least monosubstituted C _" iC ₁₀ - alkyl.

More preferably, R ^a , R ^b and R ^c in the general formula (Ib) are independently selected from radicals of the general formulas (IIa) and / or (IIb) in which R ¹ , R ¹ ', R ² R ² ' , R ³ , R ³ ', R ⁴ and R ⁴ ' are independently selected from the group consisting of H, methyl, ethyl and propyl.

Even more preferably R ^a , R ^b and R ^c in the general formula (Ib) are selected from radicals of the general formulas (IIa) and / or (IIb) in which R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ and R ⁴ ' are independently selected from the group consisting of H, methyl and ethyl, wherein at least one radical R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ or R ⁴ ' is methyl or ethyl, preferably methyl. R ^a , R ^b and R ^c in the general formula (Ib) are particularly preferably radicals of the general formula (IIb) in which R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ and R ⁴ 'are independently selected from the group consisting of H, methyl and ethyl, wherein at least one radical and at most 3 radicals R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ or R ⁴ 'is methyl or ethyl, preferably methyl.

Very particular preference is given to R ^a , R ^b and R ^c in the general formula (Ib) radicals of the general formula (IIb) in which R ¹ , R ¹ ', R ² and R ² ' are independently selected from the group consisting from H and methyl, wherein at least one radical and at most 3 radicals R ¹ , R ¹ ', R ² and R ² ' are methyl, and in which R ³ , R ³ ', R ⁴ and R ⁴ ' are H.

Preferably, the polyisocyanate (P) in this second embodiment has the general formula (Ib) in which k, m, n are independently 0, 1, 2 or 3, wherein the sum of k, m and n is at least 2 and at most 6 results; and

L is a linear or branched aliphatic, cycloaliphatic or aromatic radical having at most 14 carbon atoms which may optionally contain at least one nitrogen atom and / or at least one oxygen atom,

R ^a , R ^b , R ^{c are} independently selected from radicals of the general

Formulas (IIa), (IIb), (IIc) and / or (lld), in which o is 0, 2 or 3, and

Group consisting of H and unsubstituted or at least monosubstituted Ci-Ci ₀ -alkyl.

More preferably, the polyisocyanate (P) in this second embodiment has the general formula (Ib) wherein k, m, n are independently 0, 1, 2 or 3, wherein the sum of k, m and n is at least 2 and at most 6; and a linear or branched aliphatic or cycloaliphatic radical with

at most 14 carbon atoms, optionally at least one

May contain nitrogen atom and / or at least one oxygen atom, R ^a , R ^b , R ^{c are} independently selected from radicals of the general formulas (IIa) and / or (IIb) in which

Group consisting of H, methyl, ethyl and propyl.

Even more preferably, in this second embodiment, the polyisocyanate (P) has the general formula (Ib) in which k is 2 or 3, and m, n are 0, and

L is a linear or branched aliphatic radical of not more than 10

Carbon atoms which may optionally contain at least one nitrogen atom and / or at least one oxygen atom,

R ^{a is} selected from radicals of the general formulas (IIa) and / or (IIb) in which

Group consisting of H, methyl and ethyl, wherein at least one radical R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ or R ⁴ ' is methyl or ethyl, preferably methyl.

More preferably, the polyisocyanate (P) in this second embodiment has the general formula (Ib) in which k is 3 and m, n are 0, and L is a linear or branched aliphatic radical of at most 6

Carbon atoms, which may optionally contain at least one oxygen atom,

R ^{a is} a radical of the general formula (IIb) in which R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ , R ⁴ ' are independently selected

Group consisting of H, methyl and ethyl, where at least one radical and at most 3 radicals R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ or R ⁴ ' is methyl or

Ethyl, preferably methyl.

More preferably, the polyisocyanate (P) in this second embodiment has the general formula (Ib) in which k is 3 and m, n is 0, and L is a linear or branched aliphatic radical of at most 6

Carbon atoms, which may optionally contain at least one oxygen atom,

R ^{a is} a radical of the general formula (IIb) in which

Group consisting of H, methyl and ethyl, wherein at least one radical and at most 3 radicals R ¹ , R ¹ ', R ² , R ² ', R ⁴ and R ⁴ 'are methyl, and in the

R ³ , and R ³ 'H are.

Most preferably, the polyisocyanate (P) in this second embodiment has the general formula (IV):

in which R ¹ ', R ² R ² ', R ⁴ , R ⁴ 'are independently selected from the group consisting of H and methyl, where at least one radical and at most two radicals R ¹ , R ¹ ', R ² , R ² ', R ⁴ or R ⁴ ' are methyl, and R ³ , R ³ 'are H.

The preparation of the polyisocyanate (P) of the general formula (Ib) is described in detail in the European application 17171588.1. The polyisocyanate (P) of the general formula (Ib) is preferably prepared by reacting a reaction mixture containing the following components (a) and (b):

(a) at least one cyclic isocyanate of the general formulas (IIIa), (IIIb), (Never) and / or (IIId):

(IIIb)

where o is 0 to 10, and

R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ , R ⁴ ' are independently selected from the group consisting of H, OR ⁵ and unsubstituted or at least monosubstituted Ci-Ci ₀ -Alkyl, C ₅ -C ₁₂ -cycloalkyl, C ₂ -C ₁₀ -alkenyl and C ₆ -C ₁₄ -aryl, wherein R ^{5 is} C ₁ -C ₁₀ -alkyl, and

(b) at least one alcohol having at least two hydroxy groups.

The term "component (a)" and "at least one cyclic isocyanate of the general formulas (IIIa), (IIIb), (Never) and / or (IIId)" are used synonymously in the context of the present invention. The term "at least one cyclic isocyanate" refers to both exactly one cyclic isocyanate and to mixtures of two or more cyclic isocyanates of the general formulas (IIIa), (IIIb), (Never) and / or (IIId).

Suitable cyclic isocyanates and processes for their preparation are known in principle to the person skilled in the art and can be prepared, for example, by phosgenation of the amines on which they are based.

The radicals R ¹ to R ⁴ 'in the at least one cyclic isocyanate of the general formulas (IIIa), (IIIb), (Never) and / or (IIId) are in principle identical to the radicals R ¹ to R ⁴ ' in the formulas ( IIa) to (Id) of the polyisocyanate (P) of the general formulas (Ib) or (IV). Consequently, for the radicals R ¹ to R ⁴ 'in the general formulas (IIIa) to (IIId), the above statements and preferences for the radicals R ¹ to R ⁴ ' in the formulas (IIa) to (Id) of the polyisocyanate (P ) of the general formula (Ib) or (IV) accordingly. It is therefore clear to the person skilled in the art that as component (a) at least one cyclic isocyanate of the general formulas (IIIa), (IIb), (N ie) and / or (Ild) must be used which does not differ in the radicals R ¹ 'to R ⁴ ' from the corresponding radicals R ¹ 'to R ⁴ ' in the formulas (IIa) to (Id) in the polyisocyanate (P) of the general formulas (Ib) or (IV).

Preferably component (a) is selected from 1,3-diisocyanatocyclohexane,

1, 3-diisocyanato-2-methylcyclohexane, 1, 3-diisocyanato-4-methylcyclohexane, 1, 3-diisocyanato-5-methylcyclohexane, 1, 3-diisocyanato-2-isopropylcyclohexane, 1, 3-diisocyanato 4-isopropylcyclohexane, 1, 3-diisocyanato-5-isopropylcyclohexane, 1, 3-diisocyanato

2,4-dimethylcyclohexane, 1,3-diisocyanato-2,4-diethylcyclohexane, 1,3-diisocyanato-2,4-diethyl-6-methylcyclohexane, 1,3-diisocyanato-2-methyl-4,5-diethylcyclohexane, 1, 3-diisocyanato-2,4,6-triisopropylcyclohexane or 1,3-diisocyanato-2,4,6-tributylcyclohexane.

More preferably, component (a) is selected from 1,3-diisocyanatocyclohexane, 1,3-diisocyanato-2-methylcyclohexane, 1,3-diisocyanato-4-methylcyclohexane, 1,3-diisocyanato-5-methylcyclohexane, 1, 3-diisocyanato-2,4-dimethylcyclohexane, 1,3-diisocyanato-2,4-diethylcyclohexane and 1,3-diisocyanato-2,4-diethyl-6-methylcyclohexane,

Even more preferably, component (a) contains at least 80% by weight, preferably at least 90% by weight and particularly preferably at least 98% by weight of at least one cyclic isocyanate selected from 1,3-diisocyanato-2-methylcyclohexane or 1, 3-diisocyanato-4-methylcyclohexane, based on the total weight of component (a) in the reaction mixture.

Component (a) particularly preferably consists of at least one cyclic isocyanate selected from 1,3-diisocyanato-2-methylcyclohexane or 1,3-diisocyanato-4-methylcyclohexane.

Component (a) is preferably a mixture of 1,3-diisocyanato-2-methylcyclohexane and 1,3-diisocyanato-4-methylcyclohexane. The proportions by weight of 1,3-diisocyanato-2-methylcyclohexane and 1,3-diisocyanato-4-methylcyclohexane in this mixture can in principle be arbitrary.

In this case, component (a) preferably contains from 50 to 95% by weight of 1,3-diisocyanato-4-methylcyclohexane and from 5 to 50% by weight of 1,3-diisocyanato-2-methylcyclohexane, based on the total weight of Component (a). The term "component (b)" and "at least one alcohol having at least two hydroxyl groups" are used synonymously in the context of the present invention. The term "at least one alcohol" refers to exactly one alcohol as well as to mixtures of two or more different alcohols which have at least two hydroxyl groups. "The term" at least two hydroxyl groups "in the context of the present invention means that the component (b) may have exactly two hydroxy groups as well as three or more hydroxy groups. Suitable alcohols having at least two hydroxyl groups are generally known to the person skilled in the art.

The component (b) is preferably selected from ethylene glycol, 1, 1 - dimethylethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 2-ethyl-1, 3-propanediol, 2nd Butyl 2-ethyl-1,3-propanediol, 1,4-butanediol, 2-ethyl-1,4-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1,6 Hexanediol, 2-ethyl-1, 3-hexanediol, 2,4-diethyloctane-1,3-diol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, ditrimethylolpropane, pentaerythritol, dipentaerythritol , Glycerol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, 1,1-bis (hydroxymethyl) cyclohexane, 1,2-bis (hydroxymethyl) cyclohexane, 1,3 Bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexane, 2,2-bis (4-hydroxycyclohexyl) propane, erythritol, threitol, xylitol, adonite (ribitol), arabitol (lyxite), sorbitol, mannitol , Dulcitol (galactitol), maltitol, isomalt, diglycerol, dimethylolpropa n, dipentaerythritol, ribose, arabinose, glucose, mannose, galactose, fructose, catechol, catechol, hydroquinone, pyrogallol, hydroxyhydroquinone, phloroglucinol, hydroxypivalic neopentyl glycol ester, triethanolamine, tripropanolamine, 1,3,5-tris (2-hydroxyethyl) cyanuric acid , Polytetrahydrofuran having a molecular weight between 162 and 4500 g / mol, preferably 250 to 2000 g / mol, poly-1, 3-propanediol or poly-1, 2-propanediol having a molecular weight between 134 and 2000 g / mol or polyethylene glycol with a Molecular weight between 238 and 2000 g / mol.

Component (b) is more preferably selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, trimethylolpropane, trimethylolbutane, Pentaerythritol, glycerol, erythritol, threitol, xylitol, ribitol, arabitol, sorbitol, mannitol, galactitol, diglycerin, dimethylolpropane or dipentaerythritol.

Even more preferably, component (b) is selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, trimethylolethane, trimethylolpropane, trimethylolbutane and glycerol.

Component (b) is particularly preferably selected from ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, trimethylolpropane and glycerol. Component (b) preferably contains at least 80% by weight, preferably at least 90% by weight and particularly preferably at least 98% by weight of at least one alcohol selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3 Propanediol, 1, 4-butanediol, diethylene glycol, trimethylolethane, trimethylolpropane, trimethylolbutane and glycerol, based on the total weight of component (b) in the reaction mixture (RG), wherein ethylene glycol, 1, 2-propanediol, 1, 3-propanediol , 1, 4-butanediol, diethylene glycol, trimethylolpropane and glycerol are particularly preferred.

More preferably, component (b) consists of at least one alcohol selected from the group consisting of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, trimethylolethane, trimethylolpropane, trimethylolbutane and glycerol, wherein ethylene glycol , 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, trimethylolpropane and glycerol are particularly preferred.

Even more preferably, component (b) consists of exactly one alcohol selected from the group consisting of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, trimethylolethane, trimethylolpropane, trimethylolbutane and glycerol, wherein Ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, trimethylolpropane and glycerol are particularly preferred. The molar ratio of component (a) to component (b) is preferably 20: 1 to 5: 1, preferably 15: 1 to 7: 1 and very particularly preferably 12: 1 to 9: 1, based on the total amount of the components ( a) and (b) in the reaction mixture. The reaction of the reaction mixture can in principle be carried out at any temperatures. Preferably, the reaction of the reaction mixture is carried out at a temperature in the range of 20 to 90 ° C, more preferably in the range of 40 to 85 ° C, more preferably in the range of 50 to 80 ° C and most preferably in the range of 60 to 75 ° C. At a reaction temperature below 90 ° C, the formation of undesired by-products in addition to the polyisocyanate (P) of the general formula (Ib) can be reduced or largely avoided.

The reaction of the reaction mixture can be carried out in the presence of at least one catalyst. Suitable catalysts are described for example in European application 17171588.1. However, the reaction of the reaction mixture preferably takes place in the absence of a catalyst. The reaction of the reaction mixture is preferably carried out without solvent, but can also be carried out in the presence of at least one solvent. Suitable solvents are generally known to the person skilled in the art.

As solvents, it is generally possible to use all solvents which have no isocyanate-reactive groups. Examples of such solvents are aromatic, aliphatic and / or cycloaliphatic hydrocarbons and mixtures thereof, chlorinated hydrocarbons, ketones, esters, alkoxylated Alkansäurealkylester, ethers and mixtures of the abovementioned solvents.

Preferably, the reaction of the reaction mixture is stopped by adding at least one component (c) after at least a part of the components (a) and (b) has been reacted.

Suitable components (c) include, for example, organic acids or acid chlorides such as benzenesulfonic acid, benzenesulfonyl chloride, toluene sulfonic acid, toluenesulfonyl chloride, benzoic acid, benzoyl chloride, benzyl chloride, phosphorous acid, phosphoric acid or acid esters of phosphorous acid or phosphoric acid such as dibutyl phosphite, dibutyl phosphate or di ( 2-ethylhexyl) phosphate.

Preferably, the at least one component (c) is selected from toluenesulfonic acid, toluenesulfonyl chloride, benzoyl chloride, benzyl chloride, dibutyl phosphite, dibutyl phosphate or di (2-ethylhexyl) phosphate.

Preferably, unreacted amounts of component (a) and component (b) are separated from the polyisocyanate (P) of general formula (Ib). The separation can be carried out by all methods known in the art, for example by thin film distillation, extraction, crystallization or molecular distillation. The separation is particularly preferably carried out by thin-layer distillation. The separation of the components (a) and (b) from the polyisocyanate (P) is preferably carried out using inert protic or aprotic solvents. Suitable solvents have, inter alia, already been described above and are those which have no isocyanate-reactive groups.

In a third embodiment, the at least one polyisocyanate (P) has the general formula (Ic):

(lc) in the

R ^a , R ^b , R ^{c are} independently selected from radicals of the general

Formulas (IIa), (IIb), (IIc) and / or (Id):

where o is 0 to 10, and

A group consisting of H, OR ⁵ and unsubstituted or at least monosubstituted C ₁ -C 10 -alkyl, C ₅ - C ₁₂ -cycloalkyl, C ₂ -C ₁₀ -alkenyl and C ₆ -C ₁₄ -aryl, wherein

R ^{5 is} CC ₁₀ alkyl.

In a fourth embodiment, the at least one polyisocyanate (P) has the general formula (Id):

(Id) in the

R ^a , R ^b , R ^{c are} independently selected from radicals of the general

Formulas (IIa), (IIb), (IIc) and / or (Id):

where o is 0 to 10, and R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ , R ⁴ ' are independently selected from

Group consisting of H, OR ^5, and unsubstituted or at least mono-substituted Ci-Ci ₀ alkyl, C ₅ - C ₁₂ cycloalkyl, C ₂ -C ₁₀ alkenyl and C ₆ -C ₁₄ -aryl, where

R ^{5 is} CC ₁₀ alkyl.

Preferably, R ^a , R ^b and R ^c in the general formulas (Ic) and (Id) are independently selected from radicals of the general formulas (IIa), (IIb), (IIc), and / or (Id) in which o is 0, 2 or 3 and R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ and R ⁴ ' are independently selected from the group consisting of H and unsubstituted or at least monosubstituted C "iC ₁₀ alkyl.

More preferably, R ^a , R ^b and R ^c in the general formulas (Ic) and (Id) are independently selected from radicals of the general formulas (IIa) and / or (IIb) in which R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ and R ⁴ 'are independently selected from the group consisting of H, methyl, ethyl and propyl.

More preferably, R ^a , R ^b and R ^c in the general formulas (Ic) and (Id) are selected from radicals of the general formulas (IIa) and / or (IIb) in which R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ and R ⁴ 'are independently selected from the group consisting of H, methyl and ethyl, wherein at least one radical R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ or R ⁴ ' is methyl or ethyl, preferably methyl. R ^a , R ^b and R ^c in the general formulas (Ic) and (Id) are particularly preferably radicals of the general formula (IIb) in which R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ and R ⁴ ' are independently selected from the group consisting of H, methyl and ethyl, where at least one radical and at most 3 radicals R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ' , R ⁴ or R ⁴ 'are methyl or ethyl, preferably methyl.

Very particular preference is given to R ^a , R ^b and R ^c in the general formulas (Ic) and (Id) being a radical of the general formula (IIb) in which R ¹ , R ¹ ', R ² and R ² ' are selected independently of one another are from the group consisting of H and methyl, where at least one radical and at most 3 radicals R ¹ , R ¹ ', R ² and R ² ' are methyl, and in which R ³ , R ³ ', R ⁴ and R ⁴ ' H are.

The preparation of the polyisocyanates (P) of the general formulas (Ic) and (Id) is known in principle to the person skilled in the art. The polyisocyanates (P) of the general formulas (Ic) and (Id) are preferably used as a mixture for the preparation of the at least partially blocked polyisocyanate (BP). The preparation of such mixtures is preferably carried out as described in detail in the European application 16200079.8. Preferably, the polyisocyanates (P) of the general formulas (Ic) and (Id) are prepared by trimerization of 3 molecules of component (a) in the presence of at least one trimerization catalyst, wherein component (a) is selected from at least one of the compounds of the general formulas (lilac), (lllb), (lllc) and / or (llld):

where o is 0 to 10, and

Group consisting of H, OR ^5, and unsubstituted or at least mono-substituted Ci-Ci ₀ alkyl, C ₅ - C ₁₂ cycloalkyl, C ₂ -C ₁₀ alkenyl and C ₆ -C ₁₄ aryl, wherein R C ⁵ -C Alkyl. The radicals R ¹ to R ⁴ 'in the at least one cyclic isocyanate of the general formulas (IIIa), (IIIb), (IIIc) and / or (IIId) are in principle identical to the radicals R ¹ to R ⁴ ' in the formulas ( IIa) to (Id) of the polyisocyanates (P) of the general formulas (Ic) and (Id). Consequently, 'the above embodiments and preferences for the radicals R ¹ to R ⁴ (purple) in the general formulas to (IIId)' apply to the radicals R ¹ to R ⁴ in corresponding to the formulas (IIa) to (Id) of the polyisocyanates (P) of the general formula (Ic) and (Id).

It is therefore clear to the person skilled in the art that for obtaining a particular polyisocyanate (P) of the general formulas (Ic) or (Id) as component (a) at least one cyclic isocyanate of the general formulas (IIIa), (IIb), (Never) and / or (IIId) which does not differ in the radicals R ¹ 'to R ⁴ ' from the corresponding radicals R ¹ 'to R ⁴ ' in the formulas (IIa) to (Id) in the polyisocyanates (P) of the general formulas (Ic) and (Id).

Preferably component (a) is selected from 1,3-diisocyanatocyclohexane,

1.3-diisocyanato-2-methylcyclohexane, 1,3-diisocyanato-4-methylcyclohexane, 1,3-diisocyanato-5-methylcyclohexane, 1,3-diisocyanato-2-isopropylcyclohexane, 1,3-diisocyanato-4- isopropylcyclohexane, 1,3-diisocyanato-5-isopropylcyclohexane, 1,3-diisocyanato

In this case, component (a) preferably contains from 50 to 95% by weight of 1,3-diisocyanato-4-methylcyclohexane and from 5 to 50% by weight of 1,3-diisocyanato-2-methylcyclohexane, based on the total weight of Component (a). The at least one trimerization catalyst may be precisely a trimerization catalyst as well as a mixture of two or more different trimerization catalysts.

Preferably, the at least one trimerization catalyst is a fluorine-containing catalyst containing hydrogen fluoride.

The amount of hydrogen fluoride in the at least one trimerization catalyst can vary widely. It is irrelevant whether the at least one trimerization catalyst is a defined monohydrogendifluoride, dihydrogen trifluoride, etc. or any desired mixtures with excess fluoride on the one hand or hydrogen fluoride on the other. Corresponding trimerization catalysts are known in principle to those skilled in the art and are in part commercially available or can be prepared in a simple manner and in any stoichiometry by mixing appropriate fluorides with the desired amount of hydrogen fluoride.

More preferably, the at least one trimerization catalyst selected from Tetraethylammoniumhydrogenpolyfluorid, fluoride Tetraethylphosphoniumhydrogenpoly-, Tetrabutylammoniumhydrogenpolyfluorid, Tetrabutylphosphoniumhydrogenpoly- fluoride, fluoride Tetraoctylammoniumhydrogenpolyfluorid, Tetraoctylphosphoniumhydrogenpoly-, tetrakis (hexadecyl) ammoniumhydrogenpolyfluorid, tetrakis (hexadecyl) - phosphoniumhydrogenpolyfluorid, Methyltrioctylammoniumhydrogenpolyfluorid, Methyltrioctylphosphoniumhydrogenpolyfluorid, Methyltridecylammoniumhydrogen- polyfluoride, Methyltridecylphosphoniumhydrogenpolyfluorid, Tributyl (tetradecyl) -ammonium hydrogen polyfluoride, tributyl (tetradecyl) phosphonium hydrogen polyfluoride, tributyl (hexadecyl) ammonium hydrogen polyfluoride, tributyl (hexadecyl) phosphonium hydrogen polyfluoride, trioctyl (octadecyl) ammonium hydrogen polyfluoride, trioctyl (octadecyl) phosphonium hydrogen polyfluoride, triphenylmethylammonium hydrogen polyfluoride, triphenylmethylphosphonium hydrog enpolyfluoride, triphenyl-n-butyl-ammonium hydrogen polyfluoride, triphenyl-n-butylphosphonium hydrogen polyfluoride, Benzyltrimethylammoniumhydrogenpolyfluorid, Benzyltrimethylphosphoniumhydrogen- polyfluoride, tetrakis (hydroxymethyl) ammonium hydrogen polyfluoride or tetrakis (hydroxymethyl) phosphoniumhydrogenpolyfluorid.

Preferably in the trimerization 0.1 to 5 wt .-%, more preferably 0.5 to 4 wt .-% and particularly preferably 1 to 2 wt .-% of the at least one trimerization catalyst, based on the total weight of the component used (a ) used.

The trimerization can be carried out by any methods known to those skilled in the art. The trimerization can in principle be carried out at any temperatures. Preferably, the trimerization is carried out at a temperature in the range of 10 to 150 ° C, more preferably at 20 to 100 ° C. The pressure during the trimerization can in principle be arbitrary. Preferably, the trimerization is carried out at a pressure in the range of 0.8 to 1, 6 bar, more preferably 0.9 to 1, 2 bar and most preferably at atmospheric pressure (1, 013 bar). Preferably, the trimerization is stopped after 10 to 90 mol%, preferably 15 to 80 mol% and particularly preferably 20 to 70 mol% of component (a), based on the total amount of component (a) were trimerized. The course of the reaction can be followed, for example, by continuous determination of the refractive index or the content of isocyanate groups.

The termination of the trimerization can be carried out by any method known to those skilled in the art. Preferably, the trimerization is stopped by adding at least one component (d) after at least a portion of component (a) has been trimerized. The at least one component (d) deactivates or decomposes the at least one trimerization catalyst and is therefore also termed "catalyst poison." Suitable catalyst poisons as component (d) include, for example, organic acids or acid chlorides, such as benzenesulfonic acid, benzenesulfonyl chloride, toluenesulfonic acid, toluenesulfonyl chloride, Benzoic acid, benzoyl chloride, dodecylbenzenesulfonic acid, dodecylbenzenesulfonyl chloride, phosphorous acid, phosphoric acid or acid esters of phosphorous acid or phosphoric acid such as dibutyl phosphate or di- (2-ethylhexyl) phosphate.

Furthermore, the at least one component (d) also comprises substances which end the trimerization by adsorptive binding of the at least one trimerization catalyst and are then removed by filtration. Suitable substances of this type are, for example, silica gels or bleaching earths.

The at least one component (d) is generally added to the reaction mixture in an amount at least equivalent to the at least one trimerization catalyst. Since the at least one trimerization catalyst is partly already deactivated during the trimerization, however, the addition of an under-equivalent amount of component (d), based on the initially added amount of the at least one trimerization catalyst, is sufficient. If the at least one trimerization catalyst is not soluble in the reaction mixture, the termination of the trimerization may take place by separating the at least one trimerization catalyst from the reaction mixture, for example by filtration, instead of adding component (d).

Furthermore, the trimerization can also be terminated by thermal deactivation of the at least one trimerization catalyst after at least a portion of component (a) has been trimerized.

The mixture of the polyisocyanates (P) of the general formulas (Ic) and (Id) obtained by the trimerization is optionally separated from unreacted amounts of component (a). The separation can be carried out by all methods known to those skilled in the art, for example by thin-layer distillation, extraction, crystallization or molecular distillation and optionally using inert protic or aprotic organic solvents. Suitable solvents include, for example, alcohols, phenols, amines, esters and ketones, and toluene, xylene or higher aromatics and mixtures of such solvents.

The polyisocyanate (P) is preferably selected from polyisocyanates of the general formulas (Ia) and (Ib). The polyisocyanate (P) is particularly preferably a polyisocyanate of the general formula (Ib). The at least partially blocked polyisocyanate (BP) is obtainable according to the invention by reacting a polyisocyanate (P) with at least one thermally dissociating blocking agent (BM).

In the context of the present invention, the term "at least partially blocked polyisocyanate (P)" means that at least part of the isocyanate groups in the polyisocyanate (P) are reacted by reaction with at least one blocking agent (BM) reversibly bound to the isocyanate group (s) The proportion of blocked isocyanate groups in the polyisocyanate (P) can be adjusted by the stoichiometric ratio between the polyisocyanate (P) and the at least one blocking agent (BM) (see below).

The term "at least one blocking agent" refers to exactly one blocking agent as well as to mixtures of two or more different blocking agents. In the context of the present invention, the term "blocking agent" is understood as meaning compounds which have an isocyanate-reactive functional group and which are reversibly bound to the polyisocyanate (P) by reaction with the isocyanate groups of the polyisocyanate (P).

The at least one blocking agent is thermally dissociating according to the invention. In the context of the present invention, the term "thermally dissociating" is understood to mean that the bond between the isocyanate groups of the polyisocyanate (P) and the at least one functional group of the at least one blocking agent (BM) can be cleaved by heat induction.

Suitable blocking agents are well known to those skilled in the art. In principle, any desired thermally dissociating blocking agent can be used to prepare the at least partially blocked polyisocyanate.

In the context of the present inventions, the temperature required to remove the at least one thermally dissociative blocking agent (BM) from the at least partially blocked polyisocyanate (P) is also referred to as the "deblocking temperature".

The structure of the at least one thermally dissociating blocking agent (BM) is basically not critical to the present invention, but generally has an effect on the deblocking temperature of the at least partially blocked polyisocyanate (BP).

Preferably, the at least one thermally dissociating blocking agent (BM) is selected from alcohols, phenols, pyridinols, thiophenols, mercaptopyridines, quinolinols, oximes, amides, lactams, imides, imidazoles, imidazolines, pyrazoles, triazoles, secondary amines, malonic esters, acetoacetic acid esters, acetyl ketones, or mixtures thereof.

Suitable alcohols include, for example, linear and branched aliphatic alcohols such as isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, 2,2-dimethyl-1-propanol, n-hexanol, 2-ethylhexanol, 1-octanol or 2-octanol, cyclohexanol, furfuryl alcohol, monoethers of ethylene glycol, such as 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether or 2- (2-ethylhexyloxy) ethanol, Ν, Ν-dibutylglycolamide, N-hydroxysuccinimide, 2-morpholinoethanol, 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane, 12-hydroxystearic acid or 3-oxazolidinethanol. Suitable phenols, quinolines and pyridinols include the esters of 2-hydroxybenzoic acid and 4-hydroxybenzoic acid, such as methyl 2-hydroxybenzoate, ethyl 2-hydroxybenzoate, 2-ethylhexyl-2-hydroxybenzoate, methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate or 2-ethylhexyl 4-hydroxybenzoate, 2 - [(dimethylamino) methyl] phenol, 2- [(dimethylamino) methyl] -4-nonylphenol, 2-hydroxymethylacrylate, 2-hydroxyethyl acrylate, 2- Hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyquinoline, 8-hydroxyquinoline, 2-hydroxypyridine, 3-hydroxypyridine, 2-hydroxymethylpyridine, 3-hydroxymethylpyridine, 2-chloro-3-hydroxypyridine and para-cresol-formaldehyde resins and phenolic terpene resins.

Thiophenols and mercaptopyridines which can be used as blocking agents (BM) are, for example, thiophenol, 2-methylthiophenol, 4-methylthiophenol, 2-mercaptopyridine, 3-mercaptopyridine, 2-mercaptomethylpyridine, 2-mercaptoethylpyridine, 3-mercaptomethylpyridine or 3-mercaptoethylpyridine.

As oximes, inter alia 2-butanone oxime, 3-methyl-2-butanone oxime, 3,3-dimethyl-2-butanone oxime, 4-methyl-2-pentanone oxime, 5-methyl-2-hexanone oxime, 2-heptanone oxime, 4.6 Dimethyl 2-heptanone oxime, 3-ethyl-2-nonoxime, 2,4-dimethyl-3-pentanone oxime, 2,6-dimethyl-4-heptanone oxime, cyclohexanone oxime, 2,2,6,6-tetra methylcyclohexanone oxime or 2 , 2,4,4-tetramethylcyclobutane-1, 3-dione-1-oxime can be used.

Amides, lactams and imides include, for example, N-methylacetamide, acetanilide, γ-butyrolactam, δ-valerolactam, ε-caprolactam, ζ-enantholactam, ω-laurolactam, 6-methyl-2-piperidone, 3,6-dialkyl-2, 5-piperazinediones or phthalimides.

Suitable imidazoles, imidazolines, pyrazoles and triazoles are, for example, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazoline, 4-methylimidazoline, 2-phenylimidazoline, 4-methyl-2- phenylimidazoline, 3-methylpyrazole, 3,5-dimethylpyrazole, 1, 2,4-triazole or benzotriazole.

Suitable secondary amines are diisopropylamine, dibutylamine, di-tert-butylamine, 2,2,4-trimethylhexamethyleneamine, 2,2,5-trimethylhexamethyleneamine, N-methylhexylamine, N-isopropylcyclohexylamine, dicyclohexylamine, bis (3,3,5 Trimethylcyclohexyl) amine, piperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 4- (dimethylamino) -2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl 4-piperidone, bis (2,2,6,6-tetramethylpiperidinyl) amine, N-methylaniline, diphenylamine or N-phenylnaphthalene.

Malonic acid esters, acetoacetic acid esters and acetyl ketones as blocking agents (BM) include, for example, dimethyl malonate, diethyl malonate, diisopropyl malonate, tert-butyl methyl malonate, di-tert-butyl malonate, isopropylidene malonate (2,2-dimethyl-1,3-bis). dioxan-4,6-dione), methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate, 2-acetoacetoxyethyl methacrylate, 2,4-pentanedione (acetylacetone) or ethyl cyanoacetate. The at least one thermally dissociating blocking agent (BM) is particularly preferably selected from alcohols, phenols, oximes, amides, lactams, imides, imidazoles, pyrazoles, triazoles, secondary amines or mixtures thereof. Most preferably, the at least one thermally dissociating blocking agent (BM) is selected from alcohols, phenols, oximes, lactams, imidazoles, pyrazoles, triazoles or mixtures thereof.

In a preferred embodiment, the at least one thermally dissociating blocking agent (BM) contains at least 50% by weight of at least one blocking agent selected from diethylene glycol monomethyl ether, 2-butanone oxime, 3-methyl-2-butanone oxime, δ-valerolactam, ε-caprolactam, ζ-enantholactam , 3-methylpyrazole, 3,5-dimethylpyrazole, 1, 2,4-triazole, diisopropylamine, dibutylamine, dimethyl malonate, diethyl malonate, diisopropyl malonate or 2,4-pentanedione.

In a more preferred embodiment, the at least one thermally dissociating blocking agent (BM) contains at least 70% by weight of at least one blocking agent selected from diethylene glycol monomethyl ether, 2-butanone oxime, 3-methyl-2-butanone oxime, δ-valerolactam, ε-caprolactam, ζ- Enantholactam, 3-methylpyrazole, 3,5-dimethylpyrazole, 1, 2,4-triazole, diisopropylamine, dibutylamine, dimethyl malonate, diethyl malonate, diisopropyl malonate or 2,4-pentanedione.

In a particularly preferred embodiment, the at least one thermally dissociating blocking agent (BM) comprises at least 90% by weight of at least one blocking agent selected from diethylene glycol monomethyl ether, 2-butanone oxime, 3-methyl-2-butanone oxime, δ-valerolactam, ε-caprolactam, ζ- Enantholactam, 3-methylpyrazole, 3,5-dimethylpyrazole, 1, 2,4-triazole, diisopropylamine, dibutylamine, dimethylmalonate, diethylmalonate, diisopropylmalonate or 2,4-pentanedione. In a very particularly preferred embodiment, the at least one thermally dissociating blocking agent (BM) consists essentially of at least one blocking agent selected from diethylene glycol monomethyl ether, 2-butanone oxime, 3-methyl-2-butanone oxime, δ-valerolactam, ε-caprolactam, ζ-enantho lactam, 3-methyl-pyrazole, 3,5-dimethylpyrazole, 1, 2,4-triazole, diisopropylamine, dibutylamine, dimethylmalonate, diethylmalonate, diisopropylmalonate or 2,4-pentanedione. In the context of the present invention, the term "consists essentially of" means that the at least one thermally dissociating Blocking agent (BM) at least 95% by weight, preferably at least 98% by weight and more preferably at least 99.5% by weight of at least one blocking agent selected from diethylene glycol monomethyl ether, 2-butanone oxime, 3-methyl-2-butanone oxime, δ- Valerolactam, ε-caprolactam, ζ-enantholactam, 3-methylpyrazole, 3,5-dimethylpyrazole, 1, 2,4-triazole, diisopropylamine, dibutylamine, dimethylmalonate, diethylmalonate, diisopropylmalonate or 2,4-pentanedione.

In a most preferred embodiment, the at least one thermally dissociating blocking agent (BM) consists of at least one blocking agent selected from diethylene glycol monomethyl ether, 2-butanone oxime, 3-methyl-2-butanone oxime, δ-valerolactam, ε-caprolactam, ζ-enantholactam, 3 Methylpyrazole, 3,5-dimethylpyrazole, 1, 2,4-triazole, diisopropylamine, dibutylamine, dimethylmalonate, diethylmalonate, diisopropylmalonate or 2,4-pentanedione. In these embodiments, 2-butanone oxime, ε-caprolactam, 3-methylpyrazole, 3,5-dimethylpyrazole, 1, 2,4-triazole and diethyl malonate are particularly preferred.

The reaction of the polyisocyanate (P) with the at least one thermally dissociating blocking agent (BM) can be carried out by all methods known to the person skilled in the art and evaluated as appropriate.

The molar ratio between the at least one thermally dissociating blocking agent (BM) and the polyisocyanate (P) in the reaction is preferably in the range of 1.2: 1 to 10: 1, more preferably in the range of 1.5: 1 to 8: 1, more preferably in the range of 1, 8: 1 to 5: 1, and most preferably in the range of 2: 1 to 4: 1.

Preferably, the reaction is carried out at a temperature in the range of 60 to 160 ° C, more preferably in the range of 70 to 140 ° C and particularly preferably in the range of 80 to 120 ° C. It is clear to the person skilled in the art that the temperature in the reaction is selected as a function of the blocking agent and is below the deblocking temperature of the resulting blocked polyisocyanate (BP).

The reaction can be carried out in the presence of at least one solvent. Suitable solvents are in principle all solvents in which at least part of the polyisocyanate (P) and at least part of the at least one thermally dissociating blocking agent (BM) dissolve.

Suitable solvents are known in principle to the person skilled in the art and have no isocyanate-reactive functional groups. Examples of such solvents are aromatic, aliphatic and / or cycloaliphatic hydrocarbons and mixtures thereof, chlorinated hydrocarbons, ketones, Esters, alkoxylated Alkansäurealkylester, ethers and mixtures of the abovementioned solvents.

Preferably, at least 80% by weight, more preferably at least 90% by weight, and most preferably at least 99% by weight of the polyisocyanate (P) and the at least one thermally dissociating blocking agent (BM) are dissolved in the at least one solvent, based on the total weight of the polyisocyanate (P) and the at least one thermally dissociating blocking agent (BM).

Most preferably, the polyisocyanate (P) and the at least one thermally dissociating blocking agent (BM) are completely dissolved in the at least one solvent. This means that neither the polyisocyanate (P) nor the at least one thermally dissociating blocking agent (BM) can be separated from the at least one solvent by filtration.

In the reaction of the at least one thermally dissociating blocking agent (BM) with the polyisocyanate (P), the at least one thermally dissociating blocking agent (BM), optionally in the presence of at least one solvent, initially and the polyisocyanate (P), optionally in the presence at least one solvent, periodically or uniformly added to the at least one thermally dissociating blocking agent (BM). However, it is also possible to initially charge the polyisocyanate (P), optionally in the presence of at least one solvent, and to add the at least one thermally dissociating blocking agent (BM), optionally in the presence of at least one solvent, periodically or uniformly to the polyisocyanate (P).

The reaction is preferably carried out under a protective gas atmosphere, more preferably under a nitrogen atmosphere.

The reaction conditions and molar ratios in the reaction are preferably selected such that at least 80 mol%, preferably at least 90 mol%, particularly preferably at least 98 mol% and very particularly preferably at least 99.5 mol% of the isocyanate groups in the polyisocyanate ( P), based on the total amount of isocyanate groups in the polyisocyanate (P), are blocked by reaction with the at least one thermally dissociating blocking agent (BM). Most preferably, the reaction conditions and molar ratios in the reaction are chosen so that the isocyanate groups in the polyisocyanate (P), by reaction with the at least one thermally dissociating blocking agent (BM) are completely blocked. This means that the at least partially blocked polyisocyanate (BP) contains 0 mol% of unblocked isocyanate groups.

Preferably, unreacted amounts of the at least one thermally dissociating blocking agent (BM) and the polyisocyanate (P) are separated from the at least partially blocked polyisocyanate (BP) after the reaction. The separation can be carried out by all methods known in the art, for example by thin film distillation, extraction, crystallization or molecular distillation. The separation is particularly preferably carried out by thin-layer distillation.

The separation of the polyisocyanate (P) and the at least one thermally dissociating blocking agent (BM) from the at least partially blocked polyisocyanate (BP) is preferably carried out using inert protic or aprotic solvents. Suitable solvents have, inter alia, already been described above and are those which have no isocyanate-reactive groups.

The total content of free and blocked isocyanate groups in the at least partially blocked polyisocyanate (BP) is preferably in the range of 1 to 40 wt .-%, more preferably in the range of 5 to 35 wt .-% and particularly preferably in the range of 10 to 30 wt .-%, based on the total weight of the at least partially blocked polyisocyanate (BP). The at least partially blocked polyisocyanate (BP) preferably has a deblocking temperature in the range of 100 ° C to 200 ° C, more preferably in the range of 1 10 ° C to 190 ° C and particularly preferably in the range of 120 ° C to 180 ° C. , Another object of the present invention is also a process for the preparation of an at least partially blocked polyisocyanate (BP) by reacting a polyisocyanate (P) with at least one thermally dissociating blocking agent (BM), characterized in that the polyisocyanate (P) selected a general formula from the formulas (Ia), (Ib), (Ic) or (Id):

R ^a , R ^b , R ^{c are} independently selected from radicals of the general

Formulas (IIa), (IIb), (IIc) and / or (Id):

(IIa)

where o is 0 to 10, and

Group consisting of H, OR ^5, and unsubstituted or at least mono-substituted Ci-Ci ₀ alkyl, _C5 - Ci2 cycloalkyl, C ₂ -C ₀ -C ₄ alkenyl and C ₆ -aryl, where

R ^{5 is} CC ₁₀ alkyl.

For the method according to the invention, the preferences and embodiments correspond to the above-mentioned preferences and embodiments for the at least partially blocked polyisocyanate (BP).

The at least partially blocked polyisocyanate (BP) of the present invention is useful for the production of paints, inks, and adhesives because of the lower temperatures required to remove the at least one thermally dissociative blocking agent (BM).

Another object of the present invention is thus also the use of the at least partially blocked polyisocyanate (BP) for the production of paints, inks and adhesives.

The following examples are intended to further illustrate the present invention without, however, being limited thereto.

Examples

As blocking agents (BM), 2-butanone oxime or ε-caprolactam are used in the following examples of execution and comparative examples. In Comparative Examples 1 and 2, isophorone diisocyanate is used as the polyisocyanate. In Comparative Example 3, methylenebis (4-cyclohexylisocyanate) (dicyclohexylmethane-4,4'-diisocyanate) is used as the polyisocyanate. Exemplary embodiments 1 to 3 use MCDI (a mixture of 1,3-diisocyanato-4-methyl) analogously to this. cyclohexane and 1,3-diisocyanato-2-methylcyclohexane). In Comparative Example 4 and Example 3, the reaction products of isophorone diisocyanate or MCDI with trimethylolpropane are used as the polyisocyanate.

5 The determination of the content of NCO groups in polyisocyanates is carried out by the method described below:

0.5 g of a polyisocyanate-containing mixture are weighed exactly and dissolved in 100 ml of N-methylpyrrolidone. To this solution, 10 ml of a 1 N solution of

10 n-dibutylamine in xylene. The resulting mixture is allowed to stand at room temperature for 15 minutes with the polyisocyanate (P) and n-dibutylamine reacting with each other. After complete reaction, the resulting mixture is back-titrated with 1 N hydrochloric acid to the total volume of hydrochloric acid, which is required for the neutralization of unreacted n-dibutylamine in the mixture to

15 determine.

Comparative Example 1

41. 15 g of 2-butanone oxime and 91.10 g of n-butyl acetate 20 are placed in a round bottom flask and heated to 90.degree. C. under a nitrogen atmosphere. Subsequently, 49.95 g of isophorone diisocyanate are added dropwise, the temperature is maintained at 90 ° C until the proportion of free isocyanate groups reaches 0%.

Comparative Example 2

25

53.45 g of ε-caprolactam and 103.40 g of n-butyl acetate are placed in a round bottom flask and heated to 90 ° C. under a nitrogen atmosphere. Subsequently, 49.95 g of isophorone diisocyanate are added dropwise, the temperature is maintained at 90 ° C until the proportion of free isocyanate groups reaches 0%.

30

Comparative Example 3

41.5 g of 2-butanone oxime and 100.5 g of n-butyl acetate are placed in a round bottom flask and heated to 90 ° C. under a nitrogen atmosphere. Subsequently, 35.0 g of methylenebis (4-cyclohexyl isocyanate) are added dropwise, keeping the temperature at 90 ° C. until the proportion of free isocyanate groups reaches 0%.

Comparative Example 4

40 616.72 g of isophorone diisocyanate (I PDI) and 44 g of trimethylolpropane are placed in a 1 L three-necked flask fitted with a thermometer (connected to an adjustable temperature oil bath), stirrer, reflux condenser and nitrogen inlet and stirred heated to 80 ° C. The change in the NCO content during the reaction of the starting materials is determined by titration as described above. The reaction is stopped by adding 300 ppm of a mixture of benzyl chloride and bis (2-ethylhexyl) phosphate (50/50 wt.%) After the NCO content has reached the theoretical value for the complete reaction of the isophorone diisocyanate with trimethylolpropane. The colorless composition thus obtained is purified by thin-layer distillation at 3 mbar and 175 ° C to separate unreacted isophorone diisocyanate. The resulting yellowish powder has a content of isocyanate groups of 13.1%.

In a round bottom flask, 50 g of the yellowish powder and 72.2 g of n-butyl acetate are introduced and heated to 90 ° C under a nitrogen atmosphere. Subsequently, 22.2 g of ε-caprolactam are added dropwise, the temperature is maintained at 90 ° C until the proportion of free isocyanate groups reaches 0%.

Embodiment 1

41. 15 g of 2-butanone oxime and 81.65 g of n-butyl acetate are placed in a round bottom flask and heated to 90 ° C. under a nitrogen atmosphere. Subsequently, 40.50 g of MCDI are added dropwise, the temperature being maintained at 90 ° C. until the proportion of free isocyanate groups reaches 0%.

Exemplary Embodiment 2 53.45 g of ε-caprolactam and 93.95 g of n-butyl acetate are placed in a round bottom flask and heated to 90 ° C. under a nitrogen atmosphere. Subsequently, 40.50 g of MCDI are added dropwise, the temperature being maintained at 90 ° C. until the proportion of free isocyanate groups reaches 0%. Embodiment 3

500 g of MCDI and 44 g of trimethylolpropane are placed in a 1 l three-necked flask equipped with a thermometer (connected to an adjustable temperature oil bath), stirrer, reflux condenser and nitrogen inlet and heated to 80 ° C. with stirring. The change in the NCO content during the reaction of the starting materials is determined by titration as described above. The reaction is stopped by the addition of 300 ppm of a mixture of benzyl chloride and bis (2-ethylhexyl) phosphate (50/50 wt.%) After the NCO content has reached the theoretical value for complete reaction of the MCDI with trimethylolpropane. The colorless composition thus obtained is purified by thin-layer distillation at 3 mbar and 175 ° C to separate unreacted MCDI. The resulting yellowish powder has an isocyanate group content of 15.7%. In a round bottom flask, 50 g of the yellowish powder and 68.5 g of n-butyl acetate are introduced and heated to 90 ° C under a nitrogen atmosphere. Subsequently, 18.5 g of ε-caprolactam are added dropwise, the temperature is maintained at 90 ° C until the proportion of free isocyanate groups reaches 0%.

To determine the temperature required to remove the blocking agent (BM), the blocked polyisocyanates obtained in Comparative Examples 1 to 4 and those in Working Examples 1 to 3 are separated from n-butyl acetate and measured by differential scanning calorimetry (DSC analysis) ,

The DSC analysis is carried out with a DSC meter (DSC 204 F1 Netzsch) under a nitrogen atmosphere in a temperature range of 0 ° C to 300 ° C at a heating rate of 10 ° C / min. For this purpose, for each measurement 5 mg of the corresponding blocked polyisocyanate are sealed in an aluminum crucible. The temperature at which the maximum exotherm occurs corresponds to the temperature required to remove the blocking agent (BM) (referred to as the deblocking temperature in Table 1).

Table 1.

The comparison of Comparative Examples 1 and 3 with Embodiment 1 clearly shows that by using MCDI as the polyisocyanate (P), a blocked polyisocyanate is obtained whose temperature for removing the blocking agent (BM) is 20 ° C lower than for an analogously blocked isophorone diisocyanate , Comparative Examples 2 and 4 and Embodiments 2 and 3 show a very similar behavior.

Claims

claims

1. At least partially blocked polyisocyanate (BP), obtainable by reacting a polyisocyanate (P) with at least one thermally dissociating blocking agent (BM), characterized in that the polyisocyanate (P) has a general formula selected from the formulas (Ia), (Ib ), (Ic) or (Id) has:

(Ic) (Id) in which independently of one another are 0, 1, 2 or 3, the sum of k, m and n giving at least 2 and at most 6; and is a linear or branched organic radical having at most 14 carbon atoms, which may optionally contain at least one nitrogen atom and / or at least one oxygen atom,

R ^a , R ^b , R ^{c are} independently selected from radicals of the general formulas (IIa), (IIb), (I Ic) and / or (Ild):

where o is 0 to 10, and

R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ , R ⁴ ' are independently selected from the group consisting of H, OR ⁵ and unsubstituted or at least monosubstituted Ci-Ci ₀ Alkyl, C ₅ -C ₁₂ cycloalkyl, C ₂ -C ₁₀ alkenyl and C ₆ -C ₁₄ aryl, wherein R ⁵ is d-to-alkyl.

At least partially blocked polyisocyanate (BP) according to claim 1. characterized in that independently of one another are 0, 1, 2 or 3, the sum of k, m and n giving at least 2 and at most 6; and is a linear or branched aliphatic, cycloaliphatic or aromatic radical having at most 14 carbon atoms, which may optionally contain at least one nitrogen atom and / or at least one oxygen atom,

R ^a , R ^b , R ^{c are} independently selected from radicals of the general formulas (IIa), (IIb), (IIc), and / or (Id):

where o is 0, 2 or 3, and

R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ , R ⁴ ' are independently selected from the group consisting of H and unsubstituted or at least monosubstituted C "| -C ₁₀ - alkyl.

At least partially blocked polyisocyanate (BP) according to claim 1 or 2, characterized in that k, m, n are independently 0, 1, 2 or 3, the sum of k, m and n being at least 2 and at most 6; and is a linear or branched aliphatic or cycloaliphatic radical having at most 14 carbon atoms, which may optionally contain at least one nitrogen atom and / or at least one oxygen atom,

R ^a , R ^b , R ^{c are} independently selected from radicals of the general formulas (IIa) and / or (IIb):

in which

R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ , R ⁴ ' are independently selected from the group consisting of H, methyl, ethyl and propyl.

At least partially blocked polyisocyanate (BP) according to one of claims 1 to 3, characterized in that

Is 2 or 3, and m, n are 0, and is a linear or branched aliphatic radical having at most 10 carbon atoms, which may optionally contain at least one nitrogen atom and / or at least one oxygen atom,

R ^{a is} selected from radicals of the general formulas (IIa) and / or

(IIb):

in which

R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ , R ⁴ ' are independently selected from the group consisting of H, methyl and ethyl, where at least one radical R ¹ , R ¹ ', R ² R ² ', R ³ ,

R ³ ', R ⁴ or R ⁴ ' is methyl or ethyl, preferably methyl. 5. At least partially blocked polyisocyanate (BP) according to any one of claims 1 to 4, characterized in that k is 3, and m, n are 0, and is a linear or branched aliphatic radical having at most 6 carbon atoms, optionally at least one oxygen atom a radical of the general formula (IIb) is:

in the

R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ , R ⁴ ' are independently selected from the group consisting of H, methyl and ethyl, wherein at least one radical and at most 3 radicals R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ or R ⁴ ' are methyl or ethyl, preferably methyl.

At least partially blocked polyisocyanate (BP) according to one of claims 1 to 5, characterized in that the at least one thermally dissociating blocking agent (BM) is selected from alcohols, phenols, pyridinols, thiophenols, mercaptopyridines, quinolinols, oximes, amides, lactams, imides , Imidazoles, imidazolines, pyrazoles, triazoles, secondary amines, malonic esters, acetoacetic esters, acetyl ketones, or mixtures thereof.

7. At least partially blocked polyisocyanate (BP) according to any one of claims 1 to 6, characterized in that at least 80 mol%, preferably at least 90 mol%, more preferably at least 98 mol% and most preferably at least 99.5 mol -% of the isocyanate groups in the polyisocyanate (P), based on the total amount of isocyanate groups in the polyisocyanate (P), are blocked by reaction with the at least one thermally dissociating blocking agent (BM), and / or the total content of free and blocked isocyanate groups in at least partially blocked polyisocyanate (BP) in the range of 1 to 40 wt .-%, preferably in the range of 5 to 35 wt .-% and particularly preferably in the range of 10 to 30 wt .-%, based on the total weight of the at least partially blocked Polyisocyanate (BP).

At least partially blocked polyisocyanate (BP) according to one of claims 1 to 7, characterized in that in the reaction, the molar ratio between the at least one thermally dissociating blocking agent (BM) and the polyisocyanate (P) in the range of 1, 2: 1 to 10: 1, preferably from 1, 5: 1 to 8: 1, more preferably from 1, 8: 1 to 5: 1 and most preferably from 2: 1 to 4: 1, and / or the reaction at a temperature in the range of 60 to 160 ° C, preferably from 70 to 140 ° C and more preferably from 80 to 120 ° C, and optionally in the presence of at least one solvent and optionally in the presence of at least one catalyst, and / or unreacted after the reaction Quantities of the at least one thermally dissociating blocking agent (BM) and the polyisocyanate (P) are separated from the at least partially blocked polyisocyanate (BP).

At least partially blocked polyisocyanate (BP) according to one of claims 1 to 8, characterized in that the polyisocyanate (P) has the general formula (Ia) and is selected from 1,3-diisocyanatocyclohexane, 1,3-diisocyanato-2 methylcyclohexane, 1,3-diisocyanato-4-methylcyclohexane, 1,3-diisocyanato-5-methylcyclohexane, 1,3-diisocyanato 2-isopropylcyclohexane, 1, 3-diisocyanato-4-isopropylcyclohexane, 3-diisocyanato-5-isopropylcyclohexane, 1,3-diisocyanato-2,4-dimethylcyclohexane, 1,3-diisocyanato-2,4-diethylcyclohexane, 1, 3-diisocyanato-2,4-diethyl-6-methylcyclohexane, 1,3-diisocyanato-2-methyl-4,5-diethylcyclohexane, 1,3-diisocyanato-2,4,6-triisopropylcyclohexane or 1, 3 diisocyanato-2,4,6-tributylcyclohexan.

At least partially blocked polyisocyanate (BP) according to one of claims 1 to 8, characterized in that the polyisocyanate (P) has the general formula (Ib) and is prepared by reacting a reaction mixture comprising the following components (a) and (b):

where o is 0 to 10, and

R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ , R ⁴ ' are independently selected from the group consisting of H, OR ⁵ and unsubstituted or at least monosubstituted Ci-Ci ₀ -Alkyl, C ₅ -C ₁₂ -cycloalkyl, C ₂ -C ₁₀ -alkenyl and C ₆ -C ₁₄ -aryl, where R s is C ₁ -C ₁₀ -alkyl, and

(b) at least one alcohol having at least two hydroxy groups. At least partially blocked polyisocyanate (BP) according to claim 10, characterized in that i) the component (a) is selected from 1, 3-diisocyanatocyclohexane, 1, 3-diisocyanato-2-methylcyclohexane, 1, 3-diisocyanato-4-methylcyclo - hexane, 1, 3-diisocyanato-5-methylcyclohexane, 1, 3-diisocyanato-2-isopropylcyclohexane, 1, 3-diisocyanato-4-isopropylcyclohexane, 3-diisocyanato nato-5-isopropylcyclohexane, 1, 3-diisocyanato -2,4-dimethylcyclohexane, 1, 3-diisocyanato-2,4-diethylcyclohexane, 1, 3-diisocyanato-2,4-diethyl-6-methylcyclohexane, 1, 3-diisocyanato-2-methyl-4,5-diethylcyclohexane , 1, 3-diisocyanato-2,4,6-triisopropylcyclohexane or 1,3-diisocyanato-2,4,6-tri-butylcyclohexane, and / or the component (b) is selected from ethylene glycol, 1, 1-dimethylethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1, 4- Butanediol, 2-ethyl-1, 4-butanediol, 1, 5-pentanediol, 2-methyl-1, 5-pentanediol, Neopentylgl ykol, 1, 6-hexanediol, 2-ethyl-1, 3-hexanediol, 2,4-diethyloctane-1, 3-diol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, Ditrimethylolpropane, pentaerythritol, dipentaerythritol, glycerol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, 1,1-bis (hydroxymethyl) cyclohexane, 1,2-bis (hydroxy methyl) cyclohexane, 1,3-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexane, 2,2-bis (4-hydroxycyclohexyl) propane, erythritol, threitol, xylitol, adonite (ribitol), Arabitol (lyxite), sorbitol, mannitol, dulcitol (galactitol), maltitol, isomalt, diglycerol, dimethylolpropane, dipentaerythritol, ribose, arabinose, glucose, mannose, galactose, fructose, catechol, catechol, hydroquinone, pyrogallol, hydroxyhydroquinone, phloroglucinol, neopentylglycol hydroxypivalate, Triethanolamine, tripropanolamine, 1, 3,5-tris (2-hydroxyethyl) cyanuric acid, polytetrahydrofuran with a m molecular weight between 162 and 4500 g / mol, preferably 250 to 2000 g / mol, poly-1, 3-propanediol or polypropylene glycol having a molecular weight between 134 and 2000 g / mol or polyethylene glycol having a molecular weight between 238 and 2000 g / mol.

At least partially blocked polyisocyanate (BP) according to any one of claims 1 to 8, characterized in that the polyisocyanate (P) has the general formula (Ic) or (Id) and is prepared by trimerization of 3 molecules of component (a) in the presence at least one trimerization catalyst, wherein component (a) is selected from at least one of the compounds of the general formulas (IIIa), (IIIb), (Never) and / or (IIId):

in which

0 to 10 is, and

R ¹ , R ¹ ', R ² R ² ', R ³ , R ³ ', R ⁴ , R ⁴ ' are independently selected from the group consisting of H, OR ⁵ and unsubstituted or at least monosubstituted Ci-Ci ₀ Alkyl, C ₅ -C ₁₂ cycloalkyl, C ₂ -C ₁₀ alkenyl and C ₆ -C ₁₄ aryl, wherein R ^{5 is} C ₁ -C ₆ alkyl.

At least partially blocked polyisocyanate (BP) according to claim 12, characterized in that i) the component (a) is selected from 1, 3-diisocyanatocyclohexane, 1, 3-diisocyanato-2-methylcyclohexane, 1, 3-diisocyanato-4-methylcyclo - hexane, 1, 3-diisocyanato-5-methylcyclohexane, 1, 3-diisocyanato-2-isopropylcyclohexane, 1, 3-diisocyanato-4-isopropylcyclohexane, 3-diisocyanato nato-5-isopropylcyclohexane, 1, 3-diisocyanato -2,4-dimethylcyclohexane, 1, 3-diisocyanato-2,4-diethylcyclohexane, 1, 3-diisocyanato-2,4-diethyl-6-methylcyclohexane, 1, 3-diisocyanato-2-methyl-4,5-diethylcyclohexane , 1, 3 Diisocyanato-2,4,6-triisopropylcyclohexane or 1,3-diisocyanato-2,4,6-tri-butylcyclohexane, and / or the trimerization catalyst is selected from tetraethylammonium hydrogen polyfluoride, tetraethylphosphonium hydrogen polyfluoride, tetrabutylammonium hydrogen polyfluoride, tetrabutylphosphonium hydrogen fluoride, tetraoctylammonium hydrogen polyfluoride, tetra- octylphosphoniumhydrogenpolyfluorid, tetrakis (hexadecyl) ammoniumhydrogenpolyfluorid, tetrakis (hexadecyl) phosphoniumhydrogenpoly- fluoride, Methyltrioctylammoniumhydrogenpolyfluorid, phoniumhydrogenpolyfluorid Methyltrioctylphos-, Methyltridecylammoniumhydrogenpolyflu- ORID, Methyltridecylphosphoniumhydrogenpolyfluorid, tributyl (tetradecyl) - ammoniumhydrogenpolyfluorid, tributyl (tetradecyl) phosphoniumhydro- genpolyfluorid, tributyl (hexadecyl ) ammonium hydrogen polyfluoride, tributyl (hexadecyl) phosphonium hydrogen polyfluoride, trioctyl (octadecyl) ammonium hydrogen polyfluoride, trioctyl (octadecyl) phosphonium hydrogen polyfluoride, Tr iphenylmethylammoniumhydrogenpolyfluorid, Triphenyl- methylphosphoniumhydrogenpolyfluorid, triphenyl-n-butylammonium hydrogenpolyfluorid, triphenyl-n-butylphosphoniumhydrogenpolyfluorid, Benzyltrimethylammoniumhydrogenpolyfluorid, Benzyltrimethylphospho- niumhydrogenpolyfluorid, tetrakis (hydroxy-methyl) ammonium hydrogen polyfluoride or tetrakis (hydroxymethyl) phosphoniumhydrogenpoly- fluoride.

Use of an at least partially blocked polyisocyanate (BP) according to any one of claims 1 to 13 for the preparation of paints, inks and adhesives.