EP3565855A1

EP3565855A1 - Reactive polyurethane hot-melt adhesives

Info

Publication number: EP3565855A1
Application number: EP17822161.0A
Authority: EP
Inventors: Julio Albuerne; Rolf Illguth; Raphael Dabbous; Elmar Poeselt
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2016-12-02
Filing date: 2017-12-01
Publication date: 2019-11-13
Also published as: JP2020513454A; WO2018100149A1; CN110023392A; BR112019010556A2; KR20190087440A; US20190316014A1; RU2019120397A

Abstract

The invention relates to a composition containing at least one crosslinkable thermoplastic polyurethane (P) and at least one compound (N) which comprises a conjugated aromatic structure containing nitrogen, as a nucleation agent, said compound (N) being a solid and being present in the composition in an amount in the range of 0.01 to 0.5 wt.% relative to the thermoplastic polyurethane. The invention also relates to a method for producing such compositions, as well as to the use of the claimed compositions as a sealant, coating or adhesive.

Description

Reactive polyurethane hotmelts

The present invention relates to a composition containing at least one crosslinkable thermoplastic polyurethane (P) and at least one compound (N) having a conjugated nitrogen-containing aromatic structure as a nucleating agent, wherein the compound (N) is a solid and in an amount in the range of 0.01 to 0.5% by weight, based on the thermoplastic polyurethane, contained in the composition. Furthermore, the present invention relates to a method for producing such compositions and to the use of the compositions according to the invention as a sealant, coating or adhesive.

Various thermoplastic polyurethanes are known from the prior art. The properties of the thermoplastic polyurethanes can be varied within a wide range by the use of different starting materials or by the use of additives. For example, it is known from EP 0 199 021 A2 that the crystallization behavior of polyurethanes can be influenced by the use of nucleating agents.

Crosslinkable thermoplastic polyurethanes for adhesive applications are also referred to as reactive polyurethane hotmelts. Reactive polyurethane hotmelts are a rapidly growing product group within the application of polyurethanes in the adhesives field. For their construction, preference is given to using linear polyester and / or polyether polyols in combination with an excess of polyisocyanates, preferably diisocyanates.

Essential for the good property profile of the reactive polyurethane hotmelts is their ability, on cooling, to build up cohesive strengths (initial strengths) very quickly, which permits handling of the joined parts immediately after joining. For many applications, a particularly rapid buildup of strength is necessary in order, for example, to enable rapid processing at short cycle times, or to be able to absorb restoring forces of the substrates without any detachment phenomena occurring.

The actual curing of the reactive PUR hotmelts, i. Crosslinking reaction of the components with each other, is usually carried out within hours to days by reaction of the free isocyanate groups with water from the environment or the substrates bonded together to form polyurea. The PUR hotmelts are then only partially melted or soluble in solvents. Because of this, the cured adhesives have good heat resistance and resistance to chemicals such as plasticizers, solvents, oils or fuels.

Reactive hotmelts based on semicrystalline polyesters, as described, for example, in DE 38 27 224 A1, are characterized by a very short open time and an associated rapid build-up of initial strength. This is achieved, for example, by the use of esters based on Dodecanedioic acid, which is known to have a very fast recrystallization kinetics and a high melting point.

It is known, for example, from WO2005 / 066256 that transition temperatures and recrystallization enthalpies of high molecular weight, partially crystalline, thermoplastic polymers, such as, for example, Polyolefins or polyesters can be increased by the addition of nucleating agents. This allows e.g. improve the mold release and thus the cycle times during injection molding. The effect of nucleating agents on the initial strength of high molecular weight solvent-borne thermoplastic polyurethane elastomers is described, for example, in WO

2008/155018 A1.

For many applications it is necessary to achieve good initial adhesion quickly before crosslinking.

The object of the invention was therefore to provide formulations which allow a faster construction of the initial strength. Starting from the prior art, a further object of the present invention was to provide compositions comprising crosslinkable thermoplastic polyurethanes and processes for the preparation of such compositions, which are simple and inexpensive available and their adhesion behavior can be well adjusted. According to the invention, this object is achieved by a composition comprising at least one crosslinkable thermoplastic polyurethane (P) and at least one compound (N) which has a conjugated, nitrogen-containing aromatic structure as a nucleating agent, wherein the compound (N) is a solid and in in an amount in the range of 0.01 to 0.5% by weight, based on the thermoplastic polyurethane, contained in the composition.

In the context of the present invention, suitable crosslinkable thermoplastic polyurethane (P) are in principle all thermoplastic polyurethanes which can first cure and / or crystallize in a defined temperature range and preferably have functional groups which permit crosslinking of the cured or crystallized polyurethane. In particular, those thermoplastic polyurethanes are suitable which can be crosslinked, for example, via allophanates, biuret groups, silanes, isocyanurate groups or double bonds. In the context of the present invention, the proportion of free groups and the proportion of crosslinking can be varied within wide ranges. For the purposes of the present invention, a crosslinkable thermoplastic polyurethane (P) is preferably a thermoplastic polyurethane which, after curing and / or crystallization, has a concentration of free NCO groups in the range from 0.1 to 10 % By weight, preferably in the range from 0.5 to 8% by weight, more preferably in the range from 1 to 5% by weight.

In the present invention, a compound (N) having a conjugated nitrogen-containing aromatic structure is used as a nucleating agent, wherein the compound (N) is a solid at room temperature. In the context of the present invention, the compound (N) is also referred to as nucleating agent. The nucleating agent is selected, for example, from the group consisting of quinacridones, monoazo compounds, perylenes, diketopyrrolopyrroles, isoindolines and phthalocyanines or derivatives of these compounds.

Furthermore, the present invention therefore relates to a process for the preparation of a composition as described above, comprising at least the steps

(i) providing at least one crosslinkable thermoplastic polyurethane (P) or a reaction mixture for preparing a crosslinkable thermoplastic polyurethane (R-P);

(ii) adding at least one compound (N) having a conjugated, nitrogen-containing aromatic structure as a nucleating agent to the at least one thermoplastic polyurethane (P) or the reaction mixture for preparing a crosslinkable thermoplastic polyurethane (RP), wherein the compound ( N) is a solid;

(iii) mixing the nucleating agent and the thermoplastic polyurethane (P) or the reaction mixture (RP), wherein the amount of the sum of the nucleating agents used in the range of 0.01 wt .-% to 0.5 wt .-%, based on the thermoplastic polyurethane (P) or the reaction mixture (RP), is located.

According to the invention, compounds used as compounds (N) have aromatic systems. Suitable compounds in the context of the present invention are, for example, those compounds which are used as organic pigments or also derivatives of these. Some of these products are part of the state of the art for coloring coatings or plastics. A detailed list can be found in the reference "Lehrbuch der Lacke und Beschichtungen" by Hans Kittel, Volume 5 (5th Pigments, Fillers and Colorimetry / Bandhrsg. Jürgen Spille), Chapter 5.4, 2003, ISBN 3-7776-1015-1 The use of a compound (N) containing a conjugated, nitrogen-containing aromatic

Has structure such as quinacridones, monoazo compounds, perylenes, Diketopyrrolopyrrol- len, isoindolines and phthalocyanines or derivatives of these compounds as a color pigment is basically known from the prior art. It has surprisingly been found that solid compounds having a conjugated nitrogen-containing aromatic structure are present in very small amounts in the range from 0.01% by weight to 0.5% by weight as strong nucleating agents for crosslinkable thermoplastic polyurethanes can be used. It is also possible with the process according to the invention to use inexpensive polyesterols as raw materials, for example polyesters obtainable by reacting adipic acid and butanediol or hexanediol, giving products having good properties. Thus, for example, polyesterols based on dodecanoic acid can be avoided.

In particular, compounds selected from the group consisting of quinacridones, monoazo compounds, perylenes, diketopyrrolopyrroles, isoindolines and phthalocyanines or derivatives of these compounds, in particular of quinacridone derivatives, act in very small amounts in the range from 0.01% by weight. to 0.5% by weight as strong nucleating agents for crosslinkable thermoplastic polyurethanes. More preferably, the nucleating agent is selected from the group consisting of quinacridones and perylenes or derivatives of these compounds. According to a further embodiment, the present invention also relates to a composition as described above, wherein the nucleating agent is selected from the group consisting of quinacridones, monoazo compounds, perylenes, diketopyrrolopyrroles, isoindolines and phthalocyanines or derivatives of these compounds. According to a further embodiment, the present invention also relates to a composition as described above, wherein the nucleating agent is selected from the group consisting of quinacridones and perylenes or derivatives of these compounds.

According to the invention, the at least one compound (N) can also be used in combination with other nucleating agents, for example in combination with one or more nucleating agents selected from the group consisting of talc, carbon black and shear-thinning additives.

Surprisingly, it has been found that it is precisely the small amount of nucleating agent used, in particular the quinacridone derivatives and perylenes, which has a strong nucleating effect. In addition, due to the small amount used, the residual properties of the crosslinkable thermoplastic polyurethane are not or only slightly impaired. This effect occurs even with small amounts, for example amounts in the range of 0.02 wt .-% to 0.3 wt .-%, preferably amounts in the range of 0.03 wt .-% to 0.1 wt .-%. , more preferably amounts in the range of 0.04 wt .-% to 0.08 wt .-%.

At the same time, in the context of the present invention, preferably the molecular weight of the thermoplastic polyurethane used is not adversely affected.

According to a further embodiment, the present invention also relates to a composition as described above, wherein the amount of the sum of the nucleating agents used onsmittel in the range of 0.03 wt .-% to 0.1 wt .-%, based on the thermoplastic polyurethane (P).

Examples of suitable compounds according to the invention are the following families

corresponding so-called Color Index (C.I.):

Monoazo: Not laked yellow 1, 3, 5, 6, 60, 65, 73, 74, 75, 97, 98,

1 1 1, 1 16, orange 1; Laked yellow 1 13, 168, 169, 183, 190, 191;

Perylene red 123, 149, 178, 179, 190, 224 and violet 29;

Phthalocyanines blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 68, and green 7, 36;

Chinacridone orange 48, 49, red 122, 192, 202, 206, 207, 209, violet 19,

30, 42;

Diketopyrrolopyrroles red 254, 255;

Isoindoline / one yellow 1 10, 139, 173, 185, orange 61, 66, 69, red 260 and brown 38.

In principle, the compounds used as nucleating agents can also be subjected to a treatment, for example to improve the miscibility with the thermoplastic polyurethane.

According to a further embodiment, the present invention also relates to a composition as described above, wherein a nucleating agent is used, which has been subjected to a treatment comprising grinding, treatment with a solvent, alkalis, acids, lead, crystallization or extraction, and flocculation or reduce clumping, control production to particle size, or regulate manufacturing to control viscosity.

Typically, the nucleating agents are used in the context of the present invention as a solid. Preferably, the at least one nucleating agent has a high specific surface area (unless otherwise specified by gas adsorption BET method according to ISO 9277), for example a specific surface area in the range from 10 m ² / g to 150 m ² / g, preferably specific surface area greater than 35 m ² / g, more preferably greater than 55 m ² / g.

According to a further embodiment, the present invention also relates to a composition as described above, wherein the nucleating agent is used as a solid having a specific surface area in the range from 10 m ² / g to 150 m ² / g. According to one embodiment, at least one quinacridone derivative is used as nucleating agent. Suitable compounds are known per se to those skilled in the art and are also used in relatively large amounts as color pigments. Suitable quinacridone Derivatives are, for example, substituted or unsubstituted quinacridone derivatives, substituted or unsubstituted dihydroquinacridone derivatives and substituted or unsubstituted quinacridonequinone derivatives.

The quinacridone derivative is preferably selected from the group consisting of quinacridone derivatives of the formula (I), dihydroquinacridone derivatives of the formula (II) and quinacridonequinone derivatives of the formula (III):

wherein Ri and R2 are independently selected from the group consisting of fluorine, chlorine, bromine, C1 to C6 alkyl or C1-C6 alkoxy, and n and m are independently an integer from 0 to 4, n and m preferably independently 0 or 1.

Mixtures of two or more quinacridone derivatives can also be used according to the invention.

According to the invention, the quinacridone derivatives used can have different substitutions. Preference is given to using quinacridone derivatives having halogen substituents or alkyl substituents, for example with chlorine or methyl substituents. Suitable compounds are, for example, compounds having the following structures:

wherein R1, R2, n and m are as defined above. According to a further embodiment, at least one diketopyrrolopyrrol derivative is used as nucleating agent. Suitable compounds are known per se to those skilled in the art and are also used in relatively large amounts as color pigments. The diketopyrrolopyrrole derivative is preferably selected from the group consisting of diketopyrrolopyrrole derivatives of the formula (IV):

wherein R 1 and R 2 are independently selected from the groups consisting of hydrogen, C 1 -C 6 -alkyl, C 1 -C 4 -alkoxy, phenyl, cyano or halogen and R 3 and R 4 are also independently selected from the groups consisting of hydrogen, C 1 -C 4 -alkyl, C 18 -alkyl, C 1 -C 12 -alkenyl, C 1 -C -alkynyl, C 2 -C -alkoxycarbonyl, carbamoyl, C 2 -C 6 -alkyl, C 1 -C 4 -alkoxycarbonyl, phenyl or phenyl-substituted by chlorine, bromine, C 1 -C 4 -alkyl, alkyl, C 1 -C 4 -alkoxy, trifluoromethyl or nitro.

Mixtures of two or more diketopyrrolopyrrole derivatives can also be used according to the invention. According to the invention, the diketopyrrolopyrrole derivatives used can have different substitutions. Preference is given to using diketopyrrolopyrrole derivatives having halogen substituents or aromatic substituents, for example with chlorine or phenyl substituents. Suitable compounds are, for example, compounds having the following structures: or

According to the invention, phthalocyanines can also be used as nucleating agents. The phthalocyanine derivative is preferably selected from the group consisting of aluminum phthalocyanine, nickel phthalocyanine, cobalt phthalocyanine, iron phthalocyanine, zinc phthalocyanine, copper phthalocyanine, polychloroprene phthalocyanine, hexadecachlorophthalocyanine, hexadecabromophthalocyanine and manganese phthalocyanine and derivatives thereof.

For example, the following phthalocyanines or derivatives thereof can be used in the context of the present invention:

Aluminum phthalocyanine, for example CAS No: 14154-42-8,

Nickel phthalocyanine, for example CAS No: 14055-02-8,

Cobalt phthalocyanine, for example CAS No: 3317-67-7,

Iron phthalocyanine, for example with CAS No: 132-16-1,

Zinc phthalocyanine, for example with CAS No: 14320-04-08,

Copper phthalocyanine, for example with CAS No: 147-14-8,

- Polychloroproterphthalocyanine, for example with CAS No: 1328-53-6,

Hexadecachlorophthalocyanine, for example CAS No: 28888-81 -5,

Hexadecabromophthalocyanine, for example CAS No: 28746-04-5,

Manganese phthalocyanine, for example with CAS No: 14325-24-7.

In the context of the present invention, preference is given to copper phthalocyanine having the following structure or derivatives thereof:

As crosslinkable thermoplastic polyurethane (P), it is possible according to the invention to use all common crosslinkable thermoplastic polyurethanes. It is also possible in the context of the present invention that mixtures of different crosslinkable thermoplastic polyurethane are used. In the context of the present invention, a crosslinkable thermoplastic polyurethane is understood as meaning a polyurethane which is thermoplastic and has free functional groups which are suitable for crosslinking. After crosslinking has taken place, the polyurethane usually has no thermoplastic properties. Depending on the type of crosslinking, however, this can also be reversible in the context of the present invention. For example, the crosslinking can in some cases be thermally split. After cleavage of the crosslinking, the polyurethane may again have thermoplastic properties. In particular, those thermoplastic polyurethanes are suitable which, via allophanates,

Silanes, biuret groups, isocyanurate groups or double bonds can be crosslinked.

Preferably, crosslinking in the context of the present invention takes place at room temperature. The crosslinking can continue to take place at an atmospheric humidity in the range of 50 to 100%. According to the invention, it is also possible that the crosslinking is initiated and / or accelerated by the addition of suitable catalysts or by radiation.

Thermoplastic polyurethanes are usually prepared by reacting at least one polyol composition, at least one chain extender and at least one polyisocyanate composition. Accordingly, a reaction mixture for preparing a crosslinkable thermoplastic polyurethane (RP) typically comprises at least one polyol composition, optionally a chain extender, and at least one polyisocyanate enantoin composition. It is within the scope of the present invention possible that the nucleating agent is added, for example, the polyol composition. It is likewise possible that the nucleating agent is added to the reaction mixture after addition of all components, ie in particular after mixing of the polyol composition and the isocyanate composition. Suitable polyol compositions for the production of thermoplastic polyurethanes are known in principle to the person skilled in the art. Suitable polyols are, for example, selected from the group consisting of polyetherols, polyesterols, polycarbonate alcohols and Hybridpolyolen, preferably selected from the group consisting of polyetherols and polyester terols. Particularly preferred are polyester polyols, for example those based on adipic acid and a diol. Suitable diols are, in particular, 1,4-butanediol, 1,6-hexanediol or mixtures of these compounds.

Such polyols are generally known to the person skilled in the art and are described, for example, in "Kunststoffhandbuch, Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1. Particular preference is given to using polyesterols or polyetherols as polyols. Likewise, polycarbonates can be used. Copolymers can also be used in the context of the present invention. The number-average molecular weight of the polyols used according to the invention is preferably in the range from 0.5 × 10 ³ g / mol to 8 × 10 ³ g / mol, preferably in the range from 0.6 × 10 ³ g / mol to 5 × 10 ³ g / mol, in particular in the range from 0.8 x 10 ³ g / mol to 3 x 10 ³ g / mol. Unless otherwise indicated, the data refer to molecular weights determined by GPC using PMMA standards with molecular weights between 0.2 and 47 kg / mol. Preferred polyetherols according to the invention are polyethyleneglycols, polypropylene glycols and polytetrahydrofurans.

Polyesterols are e.g. prepared from alkanedicarboxylic acids and polyhydric alcohols, polythioether polyols, polyester amides, hydroxyl-containing polyacetals and / or hydroxyl-containing aliphatic polycarbonates, preferably in the presence of an esterification catalyst. Further possible polyols are given, for example, in "Kunststoffhandbuch, Volume 7, Polyurethanes", Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1.

The polyesterols preferably used can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms, and polyhydric alcohols. Suitable dicarboxylic acids are, for example: aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid and 1,12-dodecanedioic acid and aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can be used singly or as mixtures, e.g. in the form of an amber, glutaric and adipic acid mixture. For the preparation of the polyesterols, it may be advantageous to use, instead of the dicarboxylic acids, the corresponding dicarboxylic acid derivatives, such as dicarboxylic acid esters having 1 to 4 carbon atoms in the alcohol radical, dicarboxylic acid anhydrides or dicarboxylic acid chlorides. Examples of polyhydric alcohols are glycols having 2 to 10, preferably 2 to 6 carbon atoms, such as ethylene glycol, diethylene glycol, butanediol-1, 4, pentanediol-1, 5, hexanediol-1, 6, decanediol-1, 10, 2,2-

Dimethylpropanediol-1, 3, propanediol-1, 3 and dipropylene glycol, triols having 3 to 6 carbon atoms, such as glycerol and trimethylolpropane and as higher-grade alcohol pentaerythritol. ever according to the desired properties, the polyhydric alcohols may be used alone or optionally in mixtures with one another.

Preferred polyesterols are according to the invention after the reaction of adipic acid with butanediol-1, 4, adipic acid with hexanediol-1, 6, 1, 12-dodecanedioic acid with butanediol-1, 4, and 1, 12-dodecanedioic acid with hexanediol-1,6 ,

Preferably, the polyols used have an average OH functionality between 1, 8 and 2.3, preferably between 1, 9 and 2.2, in particular 2. Preferably, the polyols used in the invention have only primary hydroxyl groups.

According to the invention, the polyol can be used in pure form or in the form of a composition comprising the polyol and at least one solvent. Suitable solvents are known per se to the person skilled in the art.

A chain extender can also be used to prepare the thermoplastic polyurethanes, but it is also possible to use mixtures of different chain extenders. As chain extenders usually compounds with hydroxyl or amino groups can be used, in particular with 2 hydroxyl or amino groups. According to the invention, however, it is also possible that mixtures of different compounds are used as chain extenders. In this case, according to the invention, the average functionality of the mixture is preferably 2.

Preferred chain extenders according to the invention are compounds having hydroxyl groups, in particular diols. It is possible with preference to use aliphatic, araliphatic, aromatic and / or cycloaliphatic diols having a molecular weight of from 50 g / mol to 220 g / mol. Preference is given to alkanediols having 2 to 10 C atoms in the alkylene radical, in particular di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols. For the present invention are particularly preferably 1, 2-ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol. Also, aromatic compounds such as hydroxyquinone (bis (2-hydroxyethyl)) ether can be used.

According to the invention, it is also possible to use compounds having amino groups, for example diamines. Likewise, mixtures of diols and diamines can be used.

Preferably, the chain extender is a diol having a molecular weight Mw <220 g / mol. According to the invention, it is possible that only a diol having a molecular weight Mw <220 g / mol is used for the preparation of the thermoplastic polyurethane. According to a further embodiment, the chain extender is selected from the group consisting of 1, 2-butanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol and hydroxyquinone (bis (2-hydroxyethyl)) ether. Furthermore, at least one polyisocyanate is used for the preparation of the thermoplastic polyurethane. Mixtures of two or more polyisocyanates can also be used according to the invention.

Preferred polyisocyanates in the context of the present invention are diisocyanates, in particular aliphatic or aromatic diisocyanates, more preferably aromatic diisocyanates.

According to a further embodiment, the present invention accordingly relates to a process as described above, wherein the polyisocyanate is an aromatic diisocyanate.

Furthermore, in the context of the present invention, pre-reacted prepolymers can be used as isocyanate components in which some of the OH components are reacted with an isocyanate in an upstream reaction step. These prepolymers are reacted in a subsequent step, the actual polymer reaction, with the remaining OH components and then form the thermoplastic polyurethane. The use of prepolymers offers the possibility to also use OH components with secondary alcohol groups.

The aliphatic diisocyanates used are customary aliphatic and / or cycloaliphatic diisocyanates, for example tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, 2-ethyltetramethylene 1, 4-diisocyanate, hexamethylene-1,6-diisocyanate (HDI), pentamethylene-1,5-diisocyanate, butylene-1,4-diisocyanate, trimethylhexamethylene-1,6-diisocyanate, 1-isocyanato 3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1, 4- and / or 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), 1, 4-cyclohexane diisocyanate, 1-methyl 2,4-and / or 1-methyl-2,6-cyclohexane diisocyanate, 4,4'-, 2,4'- and / or 2,2'-methylenedicyclohexyl diisocyanate (H12MDI).

Preferred aliphatic polyisocyanates are hexamethylene-1,6-diisocyanate (HDI), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and 4,4'-, 2,4'- and / or 2,2 '- methylene dicyclohexyl diisocyanate (H12MDI); 4,4'-, 2,4'- and / or 2,2'-methylenedicyclohexyl diisocyanate (H12MDI) and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane or mixtures thereof are particularly preferred.

Accordingly, according to a further embodiment, the present invention relates to a process as described above, wherein the polyisocyanate is selected from the group consisting of 4,4'-, 2,4'- and / or 2,2'-methylenedicyclohexyl diisocyanate (H 12MDI), Hexamethylene endiisocyanate (HDI) and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI) or mixtures thereof. Suitable aromatic diisocyanates are in particular 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 1, 5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-toluene diisocyanate (TDI), 3,3'-dimethyl-4,4'-diisocyanato-diphenyl (TODI), p-phenylene diisocyanate (PDI), diphenylethane-4,4'-diisoyanate (EDI), diphenylmethane diisocyanate, 3,3'- Dimethyl diphenyl diisocyanate, 1, 2-diphenylethane diisocyanate and / or phenylene diisocyanate.

Preferred aromatic polyisocyanates are in particular 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI).

According to the invention, the polyisocyanate can be used in pure form or in the form of a composition comprising the polyisocyanate and at least one solvent. Suitable solvents are known to the person skilled in the art. Suitable examples include non-reactive solvents such as ethyl acetate, methyl ethyl ketone and hydrocarbons.

According to the invention, further starting materials can be added during the reaction, for example catalysts or auxiliaries and additives. Suitable auxiliaries and additives are known per se to the person skilled in the art. Mention may be made, for example, of surface-active substances, flame retardants, nucleating agents, oxidation stabilizers, antioxidants, lubricants, dyes and pigments, stabilizers, eg. As against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, fibers, reinforcing agents and plasticizers. Suitable auxiliaries and additives can be found, for example, in the Kunststoffhandbuch, Volume VII, edited by Vieweg and Hochtlen, Carl Hanser Verlag, Munich 1966 (S103-1 13).

Suitable catalysts are also known in principle from the prior art. According to the invention, it is possible, in particular, for the nucleating agent to be used in combination with further additives, for example waxes.

According to a further embodiment, the present invention accordingly also relates to a process for preparing a composition (I) at least comprising a crosslinkable thermoplastic polyurethane (P) as described above, wherein the nucleating agent is used in combination with a further additive.

Suitable additives are, in addition to the abovementioned, for example, disclosed in DE 19735974 A1, in particular on page 9, line 62 to page 12, line 4. In the context of the present invention used additives are for example selected from an antioxidant, a light stabilizer, a metal deactivator, a stabilizer, a filler, a flame retardant, a plasticizer, a wax, another nucleating agent, a processing agent, a dye, a pigment or a combination of at least two additives.

According to the invention, suitable further nucleating agents are any suitable compounds which trigger or promote the formation of a crystalline phase from the melt or solution and / or the crystal growth on existing crystal surfaces. Suitable further nucleating agents which can be used together with the nucleating agent (N) are for example selected from the group consisting of inorganic salts and oxides such as talc, calcite or attapulgite; colloidal silver or gold; Hydrazones, sodium or aluminum benzoates; Aluminum, sodium and calcium salts of aromatic or aliphatic or cycloaliphatic acids such as calcium terephthalate; Derivatives of phosphoric acids or organophosphates; pigments; sorbitols; Pine resins; or polymeric nucleating agents such as polycyclopentene or polyvinylcyclohexane and mixtures of these.

In a further aspect, the present invention also relates to a process for preparing a composition as described above, comprising at least the steps

Thus, the present invention relates to a process for producing a composition containing at least one crosslinkable thermoplastic polyurethane (P) and at least one compound (N) having a conjugated nitrogen-containing aromatic structure as a nucleating agent, wherein the compound (N) is a solid and in an amount in the range of from 0.01 to 0.5% by weight, based on the thermoplastic polyurethane, contained in the composition, comprising at least the steps

(ii) adding at least one compound (N) having a conjugated nitrogen-containing aromatic structure as a nucleating agent to the at least one thermoplastic Polyurethane (P) or the reaction mixture for producing a crosslinkable thermoplastic polyurethane (RP), wherein the compound (N) is a solid;

(iii) mixing the nucleating agent and the thermoplastic polyurethane (P) or the reaction mixture (RP), wherein the amount of the sum of the nucleating agents used in the range of 0.01 wt .-% to 0.5 wt .-%, based on the thermoplastic polyurethane (P) or the reaction mixture (RP), is located. With regard to the preferred embodiments, reference is made to the previous embodiments.

According to a further embodiment, the present invention also relates to a method as described above, wherein the nucleating agent is selected from the group consisting of quinacridones, monoazo compounds, perylenes, diketopyrrolopyrroles, isoindolines and phthalocyanines or derivatives of these compounds.

Furthermore, the present invention also relates to a method as described above, wherein the nucleating agent is selected from the group consisting of quinacridones and perylenes or derivatives of these compounds.

According to a further embodiment, the present invention thus also relates to a method as described above, wherein the amount of the sum of the nucleating agent used in the range of 0.03 wt .-% to 0.1 wt .-%, based on the thermoplastic polyurethane (P ) lies.

The process according to the invention comprises the steps (i) to (iii). First, according to step (i), a crosslinkable thermoplastic polyurethane (P) or a reaction mixture for producing a crosslinkable thermoplastic polyurethane (R-P) is provided. According to step (ii), a nucleating agent as defined above is then added to the at least one thermoplastic polyurethane (P) or the reaction mixture to produce a crosslinkable thermoplastic polyurethane (RP), the amount of the sum of the nucleating agents used being in the range of 0.01 wt .-% to 0.5 wt .-%, based on the thermoplastic polyurethane (P) or the reaction mixture (RP), is located. According to step (iii), the nucleating agent and the thermoplastic polyurethane (P) or the reaction mixture (R-P) are mixed to obtain a composition (I).

The addition or mixing is preferably carried out in equipment usually used for mixing substances, for example in drum mixers, in mills, in screw or disk extruders, rolling mills or kneaders. The at least one crosslinkable thermoplastic polyurethane (P) or the reaction mixture (RP) and the at least one nucleating agent are usually used in the mixing apparatus at an elevated temperature, in particular in the melting range of the crosslinkable thermoplastic polymer used. polyurethane (P), mixed together. The mixing process is carried out usually at pressures of 1 to 200 bar and average residence times of 0.5 to 60 minutes. If the nucleating agent is added to the reaction mixture (RP), this is usually carried out according to the invention under the conditions in which the components of the reaction mixture (RP) are mixed. In the context of the present invention, the nucleating agent can be added to the polyol or the isocyanate, for example.

The process according to the invention can have further steps, in particular temperature treatments of the composition (I).

According to a further embodiment, the present invention accordingly also relates to a process for preparing a composition (I) at least comprising a crosslinkable thermoplastic polyurethane (P) as described above, the process comprising steps (iv) and (v):

(iv) heating the composition (I) to a temperature in the range of the melting range of the thermoplastic polyurethane (P) with at least partial melting of the thermoplastic polyurethane (P);

(v) cooling the composition. The cooling according to step (v) in the context of the present invention is usually carried out at a cooling rate in the range of cooling rates used in DSC measurements, for example at a cooling rate of 20 ° C / min.

In the context of such an embodiment, the composition (I) obtained according to step (iv) is heated to a temperature in the range of the melting range of the thermoplastic polyurethane (P) with at least partial melting of the thermoplastic polyurethane (P). Finally, according to step (v), the composition (I) is cooled.

According to the invention, the heating can take place in any suitable manner known to the person skilled in the art. The heating is preferably carried out by electrical heating, heating by heated oil or water, mechanical friction, shearing, induction fields, warm air, IR radiation or high-energy radiation (laser).

The method according to the invention may comprise further steps.

Preferably, the amount of the sum of the compound (N) used in the range of 0.02 wt .-% to 0.5 wt .-%, based on the thermoplastic polyurethane (P), preferably in the range of 0.03 wt. % to 0.1 wt .-%, more preferably in the range of 0.04 wt .-% to 0.08 wt .-%, each based on the thermoplastic polyurethane (P) or the reaction mixture (RP).

The polyurethane-containing hot melt adhesives according to the invention can be used in many ways, for example as a sealant, coating, as an adhesive, in particular as Hot melt adhesive, as a mounting adhesive for preliminary fixation of components, as a bookbinding adhesive, as an adhesive for the production of cross-bottom valve bags, for the production of composite films and laminates or as edge banding. Furthermore, the present invention therefore also relates to the use of a composition as described above or a composition obtained or obtainable by a process as previously described as a sealant, coating or adhesive. Likewise, the compositions of the invention can be used for the production of films, fibers, films, injection molded products, deformed films or for 3D printing.

According to a further embodiment, the present invention also relates to the use of a composition as described above or a composition obtained or obtainable by a process as described above as hot melt adhesive, assembly adhesive for fixing components, bookbinding adhesive, adhesive for producing composite films, laminates, sandwich components or as edge band.

The application of the composition can take place by means of spraying, spraying or laminating. The compositions of the invention are suitable for bonding a wide variety of materials, such as metal, textiles, wood, ceramics or plastics. The compositions according to the invention can be used in particular for bonding or fixing shaped articles in the automotive industry, consumer goods, sports articles or shoes, for example shoe soles.

The present invention also relates to the use of a composition as described above or a composition obtained or obtainable by a process as described above, wherein the adhesive is used in particular for bonding films, fibers, films, injection molded products, deformed films or for 3D printing, in particular in the automotive industry, consumer goods, sports goods or shoes, for example shoe soles.

Further embodiments of the present invention can be taken from the claims and the examples. It is understood that the features of the subject / method / uses according to the invention mentioned above and those explained below can be used not only in the particular combination indicated, but also in other combinations, without departing from the scope of the invention. So z. Also, the combination of a preferred feature with a particularly preferred feature, or a non-further characterized feature with a particularly preferred feature, etc. implicitly encompasses, even if this combination is not explicitly mentioned. Listed below are exemplary embodiments of the present invention, which are not limitative of the present invention. In particular, the present invention also encompasses those embodiments which result from the back references given below and thus combinations. In particular, is below in naming a range of embodiments, for example, the term "the method according to one of the embodiments 1 to 4" is understood to mean that any combination of the embodiments in this area is explicitly disclosed to those skilled in the art, ie the term is synonymous with "The method according to one of Embodiments 1, 2, 3 and 4 "to understand.

A composition containing at least one crosslinkable thermoplastic polyurethane (P) and at least one compound (N) having a conjugated nitrogen-containing aromatic structure as a nucleating agent, wherein the compound (N) is a solid and in an amount in the range of 0.01 to 0.5 wt .-% based on the thermoplastic polyurethane, is contained in the composition.

Composition according to embodiment 1, wherein the nucleating agent is selected from the group consisting of quinacridones, monoazo compounds, perylenes, diketopyrrolopyrroles, isoindolines and phthalocyanines or derivatives of these compounds.

Composition according to one of embodiments 1 or 2, wherein the nucleating agent is selected from the group consisting of quinacridones and perylenes or derivatives of these compounds.

A composition according to any one of embodiments 1 to 3, wherein the amount of the sum of the nucleating agents used is in the range of 0.03 wt .-% to 0.1 wt .-%, based on the thermoplastic polyurethane (P).

A composition according to any one of embodiments 1 to 4, wherein a nucleating agent subjected to a treatment comprising grinding, solvent treatment, alkalis, acids, bleaching, crystallization or extraction, as well as preparations for reducing or preventing flocculation or agglomeration, is used to control the particle size, or to adjust manufacturing to the viscosity.

Composition according to any one of embodiments 1 to 5, wherein the nucleating agent is used as a solid having a specific surface area in the range from 10 m ² / g to 150 m ² / g.

A process for preparing a composition according to any one of claims 1 to 6, comprising at least the steps

(ii) addition of at least one compound (N) which has a conjugated, nitrogen-containing aromatic structure as nucleating agent to the at least one thermoplastic polyurethane (P) or the reaction mixture for producing a a crosslinkable thermoplastic polyurethane (RP), wherein the compound (N) is a solid;

(iii) mixing the nucleating agent and the thermoplastic polyurethane (P) or the reaction mixture (RP), wherein the amount of the sum of the nucleating agents used in the range of 0.01 wt .-% to 0.5 wt .-%, based on the thermoplastic polyurethane (P) or the reaction mixture (RP), is located. 8. The method according to embodiment 7, wherein the nucleating agent is selected from the group consisting of quinacridones, monoazo compounds, perylenes, diketopyrrolopyrroles, isoindolines and phthalocyanines or derivatives of these compounds.

9. The method according to any one of embodiments 7 or 8, wherein the nucleating agent is selected from the group consisting of quinacridones and perylenes or derivatives of these compounds.

10. The method according to any one of embodiments 7 to 9, wherein the amount of the sum of the nucleating agents used in the range of 0.03 wt .-% to 0.1 wt .-%, based on the thermoplastic polyurethane (P).

1 1. Use of a composition according to any one of embodiments 1 to 6 or a composition obtained or obtainable by a method according to any of embodiments 7 to 10 as a sealant, coating or adhesive.

12. Use according to embodiment 1 1 wherein the adhesive is used as

Hotmelt adhesive, assembly adhesive for fixing components, bookbinding adhesive, adhesive for the production of composite films, laminates, sandwich components or edgebanding.

13. Use according to embodiment 1 1 wherein the adhesive is used for bonding wood, textiles, metals, ceramics or plastics.

14. Use according to embodiment 1 1 wherein the adhesive is used in particular for bonding films, fibers, films, injection molded products, deformed films or for 3D printing, in particular in the automotive industry, consumer goods, sports goods or shoes, for example shoe soles.

The following examples serve to illustrate the invention but are

Way limiting with respect to the subject of the present invention. EXAMPLES

1. Compounds used / composition of the polyurethanes

Table 1: Composition

Isocyanate: mixture of diphenylmethane diisocyanate isomers (4.4 ': 98.6% by weight;

2,4 ': 1,4% by weight) Polyol A: Polypropylene glycol having an average molecular weight of 1970 g / mol and a functionality of 1.9

Polyol B: Polypropylene glycol having an average molecular weight of 4000 g / mol and a functionality of 2.0

Polyol-C: polyester polyol based on adipic acid and 1,6-hexanediol with a

average molecular weight of 3500 g / mol, acid number of max. 2 mg KOH / g, a functionality of 2.0 and a melting peak maximum of 55 ° C (measured by DSC).

Polyol D: polyacrylate copolymer on methyl methacrylates and butyl methacrylates having an average molecular weight of 34,000 g / mol, and a glass transition of 76 ° C (measured by DSC) Solvenon DPM: dipropylene glycol monomethyl ether, CAS No. 34590-94-8, from Company

BASF

Nucleating agent A: Cinquasia K4535, 2,9-dichloro quinacridone, milled, acid extraction, Cl Pigment Red 202, specific surface area 72.4 m ² / g

Nucleating agent-B: Cinquasia K4410, solid solution of gamma quinacridone and 2,9-dimethyl quinacridone (ratio 1: 3), Cl Pigment Red 122, specific surface area 58.5 m ² / g nucleating agent-C: Irgazin Yellow K2060, isoindoline, Pigment yellow 1 10, specific

Surface 26.7 m ² / g Nucleating agent D: Irgazine Yellow K2080, isoindoline, Pigment yellow 1 10, specific surface area 45.6 m ² / g

Nucleating agent E: Paliogen Red Violet K541 1, Perylene, Pigment Violet 29, specific

Surface 78 m ² / g

Nucleating agent-F: Cromophtal Yellow L1061 HD, benzimidazolone (yellow pigment

151), specific surface 26.7 m ² / g

Nucleating Agent G: Paliogen Blue L6470, indanthrone pigment, specific surface area

52 m ² / g

Nucleating agent H: Pigment Red 122

Reference A: Finntalc M05SL, talc with particle size characteristics D98 = 9 micron, d50 = 2.2 micron and 44% particles below 2 micron

Reference B: Irgaclear DM, bis (P-methylbenzylidene) sorbitol, CAS number:

81541 -12-0

Reference C: Irgastab NA287, zinc glycerolate, CAS Number: 16754-68-0 Reference D: ADK Stab NA71, 2,2'-methylenebis (2,4-di-tert-butylphenyl) phosphate Lithium salt, CAS number 85209 -93-4

Reference-E: Millad NX8000, bis (4-propylbenzylidene) propyl sorbitol, CAS Number 882073-43-0

Production of PUR hotmelt

Polyol-A, polyol-B, polyol-C and polyol-D were placed in a reactor. The mixture was heated to 120 ° C and a vacuum of 70 mbar was applied for a period of 1.5 hours. Then the isocyanate was added and the mixture was stirred for a further 3 hours. Solvenon DPM was then added to the reaction mixture. The molar ratio of Solvenon DPM to the remaining isocyante groups was 1: 1. The reaction was stopped and the resulting material was cooled. Inverse titration confirmed the absence of NCO groups. Compounding the PUR hotmelt with nucleating agent

About 1 g of the obtained PUR hotmelt was mixed with the nucleating agent in a mortar. The concentration of the nucleating agent used is given in Table 2. After the polyurethane was completely melted, the nucleating agent was uniformly dispersed in the melt. When the mixture was optically homogeneous, it was cooled and stored.

DSC measurement

About 10 mg of a polyurethane hotmelt and the mixture of polyurethane and nucleating agent were weighed into an aluminum pan. Under nitrogen atmosphere, the sample was heated from room temperature to 120 ° C. After 3 minutes at 120 ° C, the sample was cooled to -80 ° C. Finally, after 3 minutes the sample was reheated isothermally at -80 ° C to 120 ° C. The heating and cooling rate was 20 K / min. The crystallization peak in the cooling step was recorded.

Table 2. Nucleating agent concentration and crystallization (peak) temperature

Concentration Tc

ID nucleating agent

(% By weight) (° C)

1 - 0 12

Nucleating agent 0.3 32

2

A

Nucleating agent 0.3 32

3

B

Nucleating agent 0.3. 30

4

C

Nucleating agent 0.3. 31

5

D

Nucleating agent 0.3. 30

6

e

7 nucleating agent F 0.3 30

Nucleating agent 0.3 33

8th

G

Nucleating agent 0.3 32

9

H

10 Reference A 3 29

1 1 Reference B 0.3 25

12 Reference C 0.3 25

13 Reference-D 0.3 19

14 Reference E 0.3 1 1 The measurements show that when using the nucleating agent according to the invention a change in the crystallization temperature of at least 5 ° C is achieved. When using reference A, an increase in the concentration used by a factor of 10 is necessary to achieve the corresponding change in the crystallization temperature.

Measurement of the adhesive strength when using the PUR hotmelts

The tensile shear strength was measured using plywood samples. Films about 1 mm thick of the PUR hotmelt or the mixture of PUR hotmelt with the nucleating agent were placed between two plates, the overlap being about 10 mm. The plates were pressed at 100 ° C for 10 min (1 kg). Subsequently, the samples were taken and tested at different times. The results are shown in Table 3. The maximum force was determined using a spring balance.

Table 3. Maximum force / time of adhesion

The measurements show that when using the nucleating agent (ID2) according to the invention the adhesive achieves a higher adhesive strength than without nucleating agent or using a nucleating agent according to the prior art (ID10).

Effectiveness of the nucleating agent in PUR hotmelt

In order to demonstrate the effectiveness of the nucleating agent in the PUR hotmelt formulations, the concentration of nucleating agent H in the formulation was varied. The experiment was carried out according to the general description for DSC measurement. The results are summarized in Table 4. The concentration refers to the amount of nucleating agent based on the PUR hotmelt. Table 4: Crystallization peak as a function of the concentration

of the nucleating agent in the PUR hotmelt.

Production of a reactive PUR hotmelt

Polyol-A, polyol-B, polyol-C and polyol-D and the nucleating agent were placed in a reactor. The mixture was heated to 120 ° C and a vacuum of 70 mbar was applied for a period of 1.5 hours. Then the isocyanate was added and the mixture was stirred for a further 3 hours. The composition of the mixture is shown in Table 5. The reaction was stopped and the resulting material was cooled. During storage no agglomeration was observed. Inverse titration was used to determine the NCO content.

, Measurement of the initial adhesion of reactive PUR hotmelts

The tensile shear strength was measured using plywood samples. About 1 mm thick films of PUR hot melt or the mixture of reactive PUR hotmelt with the nucleating agent were placed between two plates, the overlap about

10 mm. The plates were pressed at 100 ° C for 10 min (1 kg) t. The samples were then removed and tested after 15 minutes with a Zwich / Roell test machine at 25 mm / min and 1 N preload. 3 samples were tested for each system. The non-nucleated sample (RHM-ID-1) showed an average maximum force of 55 N while samples with nucleating agent (RHM-ID2 and RHM-Ref1) showed an average maximum force of about 90N. RHM-ID2 showed a similar behavior to sample RHM-Ref1 with only 1/10 of the concentration of nucleating agent.

Quoted literature:

EP 0 199 021 A2

DE 38 27 224 A1

WO2005 / 066256 WO 2008/155018 A1

"Textbook of coatings and coatings" by Hans Kittel, Volume 5 (5th pigments, fillers and colorimetry / Bandhrsg. Jürgen Spille), Chapter 5.4, 2003, ISBN 3-7776-1015-1 "Plastics Handbook, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, chapter 3.1

Claims

claims

A composition comprising at least one crosslinkable thermoplastic polyurethane (P) and at least one compound (N) which has a conjugated, nitrogen-containing aromatic structure as a nucleating agent, wherein the compound (N) is a solid and in an amount in the range of 0, 01 to 0.5 wt .-% based on the thermoplastic polyurethane (P), is contained in the composition.

A composition according to claim 1 wherein the nucleating agent is selected from the group consisting of quinacridones, monoazo compounds, perylenes, diketopyrrolopyrroles, isoindolines and phthalocyanines or derivatives of these compounds.

A composition according to any one of claims 1 or 2, wherein the nucleating agent is selected from the group consisting of quinacridones and perylenes or derivatives of these compounds.

A composition according to any one of claims 1 to 3, wherein the amount of the sum of the nucleating agents used is in the range of 0.03 wt .-% to 0.1 wt .-%, based on the thermoplastic polyurethane (P).

A composition according to any one of claims 1 to 4, wherein a nucleating agent is used which has been subjected to a treatment comprising grinding, solvent treatment, alkalis, acids, bleaching, crystallization or extraction, as well as to reduce or avoid flocculation or clumping operations to control the particle size, or to adjust manufacturing to the viscosity.

A composition according to any one of claims 1 to 5, wherein the nucleating agent is a solid having a specific surface area in the range of 10 m ² / g to 150 m ² / g.

8. The method according to claim 7, wherein the nucleating agent is selected from the group consisting of quinacridones, monoazo compounds, perylenes, diketopyrrolopyrroles, isoindolines and phthalocyanines or derivatives of these compounds.

9. The method according to any one of claims 7 or 8, wherein the nucleating agent is selected from the group consisting of quinacridones and perylenes or derivatives of these compounds.

10. The method according to any one of claims 7 to 9, wherein the amount of the sum of the nucleating agents used in the range of 0.03 wt .-% to 0.1 wt .-%, based on the thermoplastic polyurethane (P).

1 1. Use of a composition according to any one of claims 1 to 6 or a composition obtained or obtainable by a method according to any one of claims 7 to 10 as a sealant, coating or adhesive.

Use according to claim 1 1 wherein the adhesive is used as a hot melt adhesive, assembly adhesive for fixing components, bookbinding adhesive, adhesive for the production of composite films, laminates, sandwich components or as Kantenumleimer.

Use according to claim 1 1 wherein the adhesive is used for bonding wood, textiles, metals, ceramics or plastics.

Use according to claim 1 1 wherein the adhesive is used for bonding films, fibers, films, injection molded products, deformed films or for 3D printing, in particular in the automotive industry, consumer goods, sports goods or shoes, for example shoe soles.