EP2201055A1

EP2201055A1 - Acrylated polyaminoamides (iii)

Info

Publication number: EP2201055A1
Application number: EP08802785A
Authority: EP
Inventors: Antoine Carroy; Jean-Marc Ballin; Laurence Druene; Morgan Garinet; Douglas Rhubright
Original assignee: Cognis IP Management GmbH
Current assignee: IGM Group BV
Priority date: 2007-10-15
Filing date: 2008-10-04
Publication date: 2010-06-30
Also published as: US20090099279A1; CN101827875A; JP2011500903A; WO2009049780A1

Abstract

The invention relates to radiation-curable acrylated polyaminoamides that are obtained by Michael-Addition of polyaminoamides with terminal amine groups (A) and polyol ester acrylates (B). The molar ratio of the acrylate groups in the polyol ester acrylates (B) in relation to the amino-hydrogen groups in the polyaminoamides (A) is at least 1 : 1. The invention is characterised in that the polyol ester acrylates (B) are acrylated addition products of propylene oxide on trimethylolpropane. Said acrylated polyaminoamides can be used as radiation-curable compounds for producing coatings.

Description

"Acrylated polyaminoamides (III)"

Field of the invention

The invention relates to special acrylated polyaminoamides and their use for radiation-curable coatings.

State of the art

Acrylated amines have been proposed very early as radiation-curable compounds for coating purposes. Thus, US 3,963,771 (Union Carbide, 1976) discloses reaction products of acrylate esters with primary or secondary organic amines.

Coating compositions which are built up from polyester (meth) acrylates and polyamines having primary or secondary amino groups, the two compounds being reacted essentially stoichiometrically with one another, have been described more than 20 years ago in EP 231,442 A2 (PCI Polymerchemie, 1986). proposed.

EP 0,002,801 B1 discloses binders formed from at least two obligatory components, namely (1) a vinyl addition polymer having a plurality of primary or secondary amine groups attached to units in the polymer chain and (2) a material containing at least contains two acryloxy groups (Rohm and Haas, 1978).

US Pat. No. 6,706,821 describes Michael addition products of amine-terminated polyolefins and polyfunctional acrylates. DE 103,04,631 A1 describes negative-type photosensitive resin compositions. These are Michael addition products of specific polyamines with (bifunctional) polyethylene glycol di (meth) acrylates.

EP 0,002,457 Bl (Rohm and Haas, 1978) describes solid polyaminoester polymers having two units, namely (1) acrylic ester monomers having a functionality of at least 2.5 and (2) aliphatic amine monomers having a molecular weight < 1000 and an NH equivalent weight <100, wherein the acrylate: NH equivalent ratio must be in the range of 0.5 to 2.

US 4,975,498 (Union Camp) describes thermally curable aminoamide-acrylate polymers.

EP 381 354 Bl (Union Camp) describes an adhesive process which uses a radiation-curable acrylate-modified aminoamide resin which comprises the Michael addition product of a thermoplastic aminoamide polymer having an amine number of greater than 1 and less than 100 a polyol ester with a variety of acrylate ester groups (polyol ester acrylate). The ratio of the original acrylate groups of the polyol ester to the original amino hydrogen groups of the aminoamide polymer is greater than 0.5 and less than 8. Under Michael addition, the addition of a group NH is understood to a group C = C.

It is apparent from the description of EP 381 354 B1 that the said acrylate-NH ratio is to be understood in the sense of a product-by-process definition (cf., in particular, p. 3, lines 2-8, page 3). Lines 53-56 and page 4, lines 15-31).

According to later EP 505 031 A2 of the same Applicant, the Michael addition is carried out by reacting a mixture of aminoamide polymer with an NH-containing reactive diluent with the polyol ester acrylate. According to WO 93/15151 (Union Camp), the Michael addition is carried out in aqueous dispersion.

The recent application WO 01/53376 A1 (Arizona Chemical Comp.) Is concerned with aminoamide-acrylate polymers of very specific structure which are obtainable by Michael addition of special resin mixtures with multifunctional acrylate esters (such as TMP triacrylate).

No. 6,809,127 B2 (Cognis Corp.) describes liquid radiation-curable compositions comprising the reaction product of an amine-terminated polyaminoamide and a mono- or polyacrylate.

WO 06/067639 A2 (Sun Chemical) describes radiation-curable acrylate-modified aminoamide resins. These are Michael adducts of thermoplastic aminoamide polymers - derived from polymerized unsaturated fatty acids (e.g., dimer fatty acids) - and polyol esters having at least three acrylate groups per molecule. The provisos apply that the aminoamide polymer must have an amine number in the range of 40 to 60 and the ratio of the original acrylate groups in the polyester to the original amino groups of the aminoamide polymer must be at least 4: 1.

WO 07/030643 A1 (Sun Chemical) uses Michael adducts of polyol ester acrylates with polyaminoamides for printing inks, the polyaminoamide being the reaction product of a polyamine with an acid component, with the proviso that this acid component contains two obligatory components, namely (a ) a polymerized unsaturated fatty acid (eg dimer fatty acid) and (b) a fatty acid having 2 to 22 C atoms. Description of the invention

Radiation-curable acrylated polyaminoamides, on the one hand, as shown in the documents discussed above, have a certain tradition, on the other hand, there is a constant need for improvement. Against this background, it was the object of the present invention to provide novel radiation-curable acrylated polyaminoamides. These should generally be suitable for coating purposes and in particular for printing inks, preferably offset inks.

The present invention initially provides radiation-curable acrylated polyaminoamides obtainable by Michael addition of amine terminated polyaminoamides (A) and polyol ester acrylates (B), the molar ratio of the acrylate groups in the polyol ester acrylates (B) to the amino-hydrogen groups in the polyaminoamides ( A) is at least 1: 1, characterized in that the polyol ester acrylates (B) are acrylated adducts of propylene oxide with trimethylolpropane. For the purposes of the present invention, the term "acrylate groups" is understood to mean both acrylate groups and methacrylate groups, which serves to simplify the terminology.

By Michael Addition is meant, in accordance with the prior art cited above, the addition reaction of an amino group to an activated C = C double bond (typically an ester). This can be formally expressed by the following reaction equation:

NH + C = CC (O) -> NC-CHC (O)

Such reactions generally proceed spontaneously with moderate heating. However, one can also use catalysts to accelerate the Michael addition. Although, strictly speaking, this type of reaction would be better described as a Michael-analogous reaction, the more useful term Michael addition used in the cited patent literature should also be retained in the present application, since the person skilled in the art will understand what is meant and this has also been defined above.

For the preparation of the radiation-curable acrylated polyaminoamides according to the invention by Michael addition, the compounds (A) and (B) are used as stated above. These are explained in more detail below:

To the connections (A)

The compounds (A) are polyaminoamides having terminal (terminal) amine groups. These terminal amine groups may be primary or secondary, ie groups NH ₂ or NH. Otherwise, there are no limitations on the nature of the polyaminoamides.

The amine number of the polyaminoamides (A) is determined by HCl titration. In a preferred embodiment, it is above 40 and especially in the range of 45 to 70.

In a preferred embodiment, the amine number of the polyaminoamides (A) is above 40 and in particular in the range from 45 to 70.

The polyaminoamides (A) used are preferably compounds which are obtainable by reacting

• Carboxylic acids with 2 to 54 C atoms per molecule and with two COOH groups per molecule (hence these are dicarboxylic acids) and

• Diamines with 2 to 36 carbon atoms. In one embodiment, the dicarboxylic acids are selected from the group of dimer fatty acids, aliphatic alpha, omega dicarboxylic acids having 2 to 22 carbon atoms and dibasic aromatic carboxylic acids having 8 to 22 carbon atoms. As dicarboxylic acids are preferably used a dimer fatty acids. As is well known to those skilled in the art, dimer fatty acids are carboxylic acids which are obtainable by the oligomerization of unsaturated carboxylic acids, generally fatty acids such as oleic acid, linoleic acid, erucic acid and the like. Typically, the oligomerization takes place at elevated temperature in the presence of a catalyst of about alumina. The resulting substances - technical grade dimer fatty acids - are mixtures, with dimerization products predominating. However, small amounts of monomers (the sum of the monomers in the crude mixture of dimer fatty acids referred to the expert as monomer fatty acids) as well as higher oligomers, in particular so-called trimer fatty acids, are included in the product mixture. Dimer fatty acids are commercially available products and are offered in various compositions and qualities (eg under the brand name Empol® of the Applicant).

In one embodiment, the dicarboxylic acids used are alpha, omega-dicarboxylic acids having 2 to 22 carbon atoms, in particular saturated dicarboxylic acids of this type. Examples of these are: ethanedicarboxylic acid (oxalic acid), propanediocarboxylic acid (malonic acid), butanedicarboxylic acid (succinic acid), Pentanedicarboxylic acid (glutaric acid), hexanedicarboxylic acid (adipic acid), heptanedicarboxylic acid (pimelic acid), octanedicarboxylic acid (suberic acid), nonanedicarboxylic acid (azelaic acid), decanedicarboxylic acid (sebacic acid), undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid (brassylic acid), tetradecanedicarboxylic acid, pentadecanedicarboxylic acid Hexadecanedicarboxylic acid (thapsic acid), heptadecanedicarboxylic acid, octadecanedicarboxylic acid, nonadecanedicarboxylic acid, eicosanedicarboxylic acid.

In one embodiment, the dicarboxylic acids used are dibasic aromatic carboxylic acids having 8 to 22 carbon atoms, for example isophthalic acid. In one embodiment, mixtures of various dicarboxylic acids are used, for example dimer fatty acid mixed with at least one acid from the group of alpha, omega-dicarboxylic acids having 2 to 22 carbon atoms.

As already mentioned, the diamines underlying the polyaminoamides (A) are selected, in particular, from the group of diamines having 2 to 36 carbon atoms. Examples of suitable diamines are ethylenediamine, hexamethylenediamine, diaminopropane, piperazine, aminoethylpiperazine, 4,4'-dipiperidine, toluenediamine, methylenedianiline, xylenediamine, methylpentamethylenediamine, diaminocyclohexane, polyetherdiamine and diamines prepared from dimer acid. In this case, the diamines are selected in particular from the group of ethylenediamine, hexamethylenediamine, diaminopropane, piperazine and aminoethylpiperazine. Piperazine and aminoethylpiperazine are most preferred.

In the preparation of the compounds (A) from dicarboxylic acids and diamines, it may be desirable to carry out the reaction of dicarboxylic acids and diamines in the presence of minor amounts of monocarboxylic acids having 2 to 22 carbon atoms. Preferably, the monocarboxylic acids are used in an amount which is in the range from 1 to 25% of the acid groups, based on the total number of acid groups ex dicarboxylic acids and monocarboxylic acids.

To the compounds (B)

The compounds (B) are acrylated addition products of propylene oxide to trimethylolpropane. These compounds are obtainable by esterifying addition products of propylene oxide onto trimethylolpropane with acrylic acid and / or methacrylic acid, the full esters being preferred. The acrylate functionality of the compounds (B) is 3 in the case of the full esters and is therefore high enough to ensure that the compounds formed during the Michael addition of (A) and (B) still contain free C =C double bonds, which are accessible to radiation curing. This is expressed by the phrase "radiation curable acrylated polyaminoamides" because the word "radiation curable" implies that such C = C double bonds must be present.

It is expressly stated here that the term "acrylate groups" in the context of the present application means both acrylate groups and methacrylate groups, and that the term "acrylic acid" should also encompass the term "methacrylic acid".

Preferably, addition products of from 1 to 30 mol of propylene oxide per mole of trimethylolpropane and in particular from 2 to 10 mol of propylene oxide per mole of trimethylolpropane are used to prepare the compounds (B). In this case, a range of 3 to 6 moles of propylene oxide per mole of trimethylolpropane is particularly preferred.

All of these propoxylates are preferably completely esterified to the corresponding compounds (B), with the acrylic acid esters being preferred.

To the Michael addition

The radiation-curable acrylated polyaminoamides according to the invention are obtainable, as already explained, by Michael addition of the abovementioned polyaminoamides (A) and the polyol ester acrylates (B). It has also already been mentioned that the molar ratio of the acrylate groups in the polyol ester acrylates (B) to the amino hydrogen groups in the polyaminoamides (A) is at least 1: 1.

The Michael addition can be carried out per se in all ways known to those skilled in the art. In one embodiment, a solvent is used. In a further embodiment, working solvent-free. In one embodiment, a catalyst is used to accelerate the Michael addition. However, it is also possible to work without catalysts. Optionally, the Michael addition can be carried out batchwise or continuously, with batch processes being preferred.

In a preferred embodiment, the Michael addition is effected by the compounds (A) and (B) for a few hours, usually 1 to 5 hours, at temperatures in the range of 60 to 90 ⁰ C in the absence of solvents and catalysts be implemented together. The compounds (B) and (A) are preferably used in a molar ratio in the range from 1: 1 to from 3: 1.

In this case, a molar ratio of (B): (A) of 3: 1 is preferred. In this way, an NH function of the compounds (A) is added as a statistical average to each acrylate function of the compounds (B) by Michael addition.

Nevertheless, it may be desirable to increase the molar ratio of (B): (A) above the theoretically sufficient value of 3: 1 for the quantitative procedure. In this way, on the one hand, the "fine structure" of the complex product mixture can be changed, on the other hand there is then (= after the Michael reaction) a mixture of Michael adduct and acrylate (B), which are used in this form as a radiation-curable composition The fine structure of the product mixture is to be understood in particular as the control of the molecular weight of the Michael adduct, in which case the higher the excess of polyol ester acrylate, ie the higher the molar ratio of (B) :( A) above 3: 1 is, the lower tends to decrease the molecular weight of the resulting Michael adduct.

In this sense, in a preferred embodiment, the Michael reaction is carried out with a molar ratio of (B): (A) above 3: 1. In this case, a value of about 4: 1 or higher is particularly preferred. Coating Compositions Another object of the present invention are radiation-curable coating compositions comprising a crosslinkable compound and a photoinitiator, wherein the crosslinkable compound contains at least one acrylated polyaminoamide. In this case, all the above statements apply with regard to the acrylated polyaminoamide. In a preferred embodiment, these compositions are those which additionally contain a pigment and which are thus printing inks; Preferably, such compositions are used for offset printing.

B e i s p e e l e

1. Prttfmethoden

Amine number: The amine numbers of polyaminoamide resins were determined by potentiometric titration with hydrochloric acid on the basis of DIN 53176. The numerical values are given in "mg KOH / g of test substance".

Viscosity: The viscosities of UV offset inks were determined using a Bohlin Rheometer type C-VOR 120 from. Malvern Instruments at a shear rate of 100 sec ^"1 and a temperature of 25 ⁰ C.

Yield point: The flow limits of UV offset inks were determined by means of the rheology software of a Bohlin rheometer type C-VOR 120 from Malvern Instruments.

Water absorption: The water absorption of UV offset inks was determined on a computer-controlled Lithotronic II test instrument from Novomatics GmbH using fixed measuring programs.

Solvent resistance: A cotton wool soaked in acetone is loaded at 1000 g and applied in double strokes over the UV offset color and UV Overprint varnish surface moves. The indication of the solvent resistance takes place in the number of double strokes, until a visible injury of the UV offset color and UV overprint varnish surface to be tested can be seen.

Surface Hardening: The surface hardening is expressed in the number of passes on a M-40-2xl-R-TR-SLC-SO-INERT UV belt dryer made by IST Metz at the constant belt speed necessary to pass the fingernail test to create a scratch-resistant UV offset color surface.

Reactivity: The reactivity of UV overprint varnishes was determined by the maximum belt speed of a UV belt dryer of the type M-40-2xl -R-TR-SLC-SO-INERT from IST Metz, in which the UV overprint varnish film surface is straight still scratch-resistant after the fingernail test is cured.

Persoz pendulum hardness: The Persoz pendulum hardness of UV overprint varnish surfaces was determined in accordance with DIN 53157. The time in seconds was determined, which was necessary to dampen the amplitude of the pendulum from 12 ° to 4 °.

Pencil hardness: The determination of the pencil hardness of UV overprint varnish surfaces was based on ISO 15184 on a hardness scale from 9B (soft) to 9H (very hard). The pencil hardness was determined, from which a straight scratch scrape was visible on the UV overprint varnish surface to be tested. Adhesion: The Tesa adhesive tape No. 4104 was applied to the UV overprint varnish surface to be tested by pressing firmly so that no bubbles were formed. Subsequently, the adhesive tape was peeled off again quickly at a uniform take-off speed and it was assessed whether parts had detached or not from the UV overprint varnish layer to be tested.

2. Production examples

Example 1 (Inventive Michael Adduct Bl)

a) Preparation of amine group-terminated polyaminoamide resin A resin reactor was charged with a mixture of 76.23 parts by weight of Empol 1062 (hydrogenated dimer fatty acid, commercial product of Cognis) and 23.77 parts by weight of N-aminoethylpiperazine. This mixture was refluxed for 1 hour, then heated to 210 ⁰ C and kept at this temperature until an atomic number of 50 was reached. The resin reactor was then cooled to 90 ° C.

b) Preparation of acrylated resin (Michael adduct Bl)

63.38 parts by weight of triacrylate an addition product of 3 mol of propylene oxide to 1 mol of trimethylolpropane were placed in a resin reactor, treated with 0.1 parts by weight of the inhibitor 2,6-di-tert-butyl-4-methylphenol and then heated to 60 ⁰ C. With stirring, 36.52 parts by weight of the amine group-terminated polyaminoamide resin prepared as described under a) above were added at a temperature of 90 ° C. This reaction mixture was held at 70 ^° C. for 2 hours, after which Michael addition was complete. The product obtained is referred to below as B 1. B 1 is an acrylated polyaminoamide, it may also be referred to as polyamide acrylate. Example 2 (Noninventive Michael Adduct VI for Comparison)

A Michael adduct was produced exactly in accordance with Example 1 of WO 2006/067639 A2 (compare there with the paragraph bridging pages 8 and 9).

As can be seen there, the polyaminoamide is based on dimer fatty acid and piperazine, had an amine number of 50, and as polyolester acrylate, glycerol propoxylate

Triacrylate used. The resulting Michael adduct is also referred to below as VI.

Example 3 (non-inventive acrylate V2 for comparison)

A commercial polyester acrylate was used, namely "Photomer 5432" from Cognis (= Applicant) This polyester acrylate is also referred to below as V2.

3. Application examples

a) Production of UV offset inks

UV offset inks were prepared according to the formulation shown in Table 1.

Table 1

Commercially available pigments from Clariant and from Ciba were used as colorants for the yellow, Mageπta, cyan and black UV offset scales. As Oligomeracrylat each of the above-described compounds Bl, Vl and V2 were used individually.

• The epoxy acrylate used was Photomer 3016 F from Cognis.

The monomer acrylate used was photomer 4094 (propoxylated glycerol triacrylate) from Cognis.

As a UV stabilizer, Florstab UV-I from Kromachem was used.

The photoinitiator used was a mixture of Irgacure 369 and Irgacure 184 from Ciba.

b) Production of UV overprint varnishes

UV overprint varnishes were prepared according to the formulation shown in Table 2:

Table 2

The oligomer acrylate used in each case individually was the compounds B1 ₅ V1 and V2 described above.

The monomer acrylate used was photomer 4017 F (1,6-hexanediol diacrylate) from Cognis.

The photoinitiator used was Darocur 1173 from Ciba. c) property profile of the Polvamidacrylats Bl compared to the reference compounds Vl and V2

Printing inspection UV offset inks

All UV offset inks were tested for their offset suitability on a Lithotronic II tester from Novomatics GmbH and on a Bohlin rheometer manufactured by Malvern Instruments.

For this purpose, all UV offset inks on coated cardboard of the type Form 2A from Leneta were printed with the pressure equipment Mikle Proofer of Messrs. Labomat Essor and Little Joe Proofing Press of Little Joe Industries and then cured by irradiation with a mercury medium pressure lamp with a power of 180 W / cm at a belt speed of 20 m / min. The layer thickness of the color films was 6 μm in each case.

The results of the investigations are shown in Table 3.

Table 3

The magenta UV offset ink based on the inventive polyamide acrylate B1 exhibits good offset properties and a color rheology adapted to offset printing. In solvent resistance, the UV offset ink is magenta based on the polyamide acrylate B 1 according to the invention superior to the UV offset color magenta with the reference compound V 1.

Application testing UV varnishing

All UV overprint varnishes were applied to Q-type QD35 steel plates from Q-Panel and to corona-pretreated, Invercote G-coated, PE-coated cardboard (280 g / m 2 coated with 20 g / m 2 LDPE) from Iggesund using a K-metering bar No. 3 from RK Print Coat Instruments Ltd. applied (wet film thickness: 24 microns) and then cured with a medium pressure mercury lamp with a power of 180 watts / cm.

Table 4

The results show that the UV overprint varnish based on the polyamide acrylate Bl according to the invention has better adhesion to polyethylene film and higher reactivity at a comparable persoz hardness than the UV overprint varnish with the reference compound Vl.

The UV overprint varnish produced with the polyamide acrylate B 1 according to the invention is suitable for graphic applications as well as for industrial coatings on plastic, metal and wood surfaces from its property profile.

Claims

claims

1. Radiation-curable acrylated polyaminoamides obtainable by Michael addition of amine-terminated polyaminoamides (A) and polyol ester acrylates (B), the molar ratio of the acrylate groups in the polyol ester acrylates (B) to the amino hydrogen groups in the polyaminoamides ( A) is at least 1: 1, characterized in that the polyol ester acrylates (B) are acrylated addition products of propylene oxide with trimethylolpropane.

2. Acrylated polyaminoamides according to claim 1, wherein the polyaminoamides (A) used are compounds obtainable by reacting dicarboxylic acids and diamines, the dicarboxylic acids being selected from the group of the maleic fatty acids, the alpha, omega-dicarboxylic acids having 2 to 22-C atoms and the aromatic dicarboxylic acids having 8 to 22 carbon atoms and wherein the diamines are selected from the group of diamines having 2 to 36 carbon atoms.

3. Acrylated polyaminoamides according to claim 1 or 2, wherein the polyaminoamides (A) have an amine number above 40.

4. Acrylated polyaminoamides according to any one of claims 1 to 3, wherein the polyaminoamides (A) underlying diamines selected from the group E- thylenediamine, hexamethylenediamine, diaminopropane, piperazine and aminoethylpiperazine.

5. Acrylated polyaminoamides according to claim 4, wherein the polyaminoamide (A) underlying diamine is aminoethylpiperazine.

6. Acrylated polyaminoamides according to any one of claims 1 to 5, wherein the polyaminoamides (A) underlying dicarboxylic acids selected from the

Group of dimer fatty acids.

7. Acrylated polyaminoamides according to any one of claims 1 to 6, wherein as compounds (B) esters are used, which are obtainable by reaction of acrylic and / or methacrylic acid with addition products of from 1 to 30 mol of propylene oxide per mole of trimethylolpropane.

8. Acrylated polyaminoamides according to one of claims 1 to 7, wherein compounds (B) and (A) are used in the Michael addition in a molar ratio in the range of 1: 1 to 3: 1.

9. Acrylated polyaminoamides according to any one of claims 1 to 7, wherein compounds (B) and (A) are used in the Michael addition in a molar ratio of at least 3: 1.

10. Acrylated polyaminoamides according to any one of claims 1 to 7, wherein fertilize compounds (B) and (A) in the Michael addition in a molar ratio of at least 4: 1 used.

11. Acrylated polyaminoamides according to any one of claims 1 to 7, wherein in the preparation of the compounds (A) the reaction of dicarboxylic acids and diamines durchfuhrt in the presence of minor amounts of monocarboxylic acids having 2 to 22 carbon atoms.

12. Acrylated polyaminoamides according to claim 11, wherein the monocarboxylic acids are used in an amount ranging from 1-25% of the acid groups based on the total number of acid groups ex dicarboxylic acids and monocarboxylic acids.

13. A radiation-curable coating composition comprising a crosslinkable compound and a photoinitiator, wherein the crosslinkable compound contains at least one acrylated polyaminoamide according to claims 1 to 12. A composition according to claim 13 which additionally contains a pigment and which is a printing ink. 15. Use of compositions according to claim 14, for offset printing.