DE19602071A1 - Michael adducts of (meth)acrylic cpds. with amino-alkenyl ether cpds. - Google Patents

Abstract

(Meth)acrylic cpds. (I), contg. at least one (meth)acryl gp. in the form of Michael adducts obtd. by addn. of a prim. or sec. amino gp. of an aminoalkenyl ether to the double bond of the (meth)acryl gp., are new.Also claimed are: (i) compsns. capable of free radical or cationic cure, which contain 1-100 wt.% (I) w.r.t. the curable cpds.; (ii) a method for making coatings or mouldings by curing the compsns. with actinic radiation; and (iii) coatings and mouldings made from these compsns.

Description

The invention relates to a (meth) acrylic compound containing at least one (meth) acrylic group, which by addition of a primary or secondary amino group of an aminoalkenyl ether the double bond of the (meth) acrylic group as a Michael adduct lies.

The invention further relates to radical or cationic curable compositions containing the (meth) acrylic compounds.

It is known to be radically curable, in particular radiation curable compositions based on acrylates primary or secondary Add amino compounds so as to increase the reactivity in hardening tion to increase (EP-A 211 978 and DE-A 23 46 424). The primary or secondary amino compounds add up to the dop fur bond of the acrylic group.

The masses obtained in this way show a high reactivity radiation curing; the coatings obtained each have yet a number of still unsatisfactory properties, e.g. B. poor hardness, scratch resistance and chemicals resistance to.

The object of the invention was therefore compounds with high reactivity vitae in radiation curing and good application technology Properties e.g. B. the Be prepared with these compounds layers.

Accordingly, the (meth) acrylic compounds defined above were obtained find. Radically or cationically curable were also found Masses containing these compounds.

It is known that primary or secondary amino groups (Meth) acrylic groups, especially light on acrylic groups according to add to a Michael addition:

Primary amino groups become secondary amino groups, which may re-attach to acrylic groups to form can add tertiary amino groups.

The (meth) acrylic compound defined at the outset is therefore simple way obtainable by aminoalkenyl ether, d. H. Alkenyl ether with a primary or secondary amino group to compounds with (meth) acrylic groups, especially acrylic groups added the.

Suitable aminoalkenyl ethers are e.g. B. those of the formula

wherein R¹ and R² independently represent a hydrogen atom or a C₁-C₄ alkyl group, R³ is water atom or an organic residue with up to 10 carbon atoms and Z and X independently for an organic bandage member, preferably with less than 20 carbon atoms.

R 1 and R 2 are preferably a hydrogen atom.

R³ is preferably a C₁-C₆ alkyl group, especially before moves for a hydrogen atom.

At Z or X it can be z. B. an aliphatic or aromatic link or link with aliphatic and aroma act in groups. Z or X is a C₁-C₁₀, particularly preferably a C₂-C₆ alkylene group.

In particular, mixtures of aminoalkenyl ethers Ver turn.

The aminoalkenyl ethers can e.g. B. in a known manner by implementation of alkanolamines with acetylene or substituted acetylene can be obtained in the presence of basic catalysts (W. Reppe, Liebigs Annalen der Chemie 1956, Vol 601, pages 81 to 138).  

Suitable compounds with (meth) acrylic groups with the amino alkenyl ethers Michael adducts are, for. B. Connections of formula

wherein X is an n-valent C₁-C₂₀ alkyl radical, which given if can be substituted by 1 to 3 hydroxyl groups, R¹ represents a methyl group or preferably an H atom and n has the meaning of an integer from 1 to 6.

Compounds of formula 1 are e.g. B. C₁-C₂₀-, preferably C₁-C₈-alkyl (meth) acrylates, C₂-C₁₀-alkylene di (meth) acrylates or Trimethylolpropane mono-, di- or tri (meth) acrylate, penta erythritol mono-, di-, tri- or tetra (meth) acrylate.

Furthermore, the compounds can be polyester or Act polyether (meth) acrylates. Preferred are such as it by reacting (meth) acrylic acid with 1 to 6, preferably example, 2 to 4 hydroxyl-containing polyesters or poly ethers are available.

The molecular weights Mn of the polyester or polyether are in this case preferably between 100 and 4000.

Such hydroxyl-containing polyesters can e.g. B. in übli cher manner by esterification of dicarboxylic acids or polycarbonate acids with diols or polyols. The exit substances for such hydroxyl-containing polyesters are the subject man known. Preferred dicarboxylic acids are succinic acid, Glutaric acid, adipic acid, sebacic acid, o-phthalic acid, their iso mers and hydrogenation products and esterifiable derivatives, such as Anhydrides, e.g. B. maleic anhydride or dialkyl ester of the genann ten acids are used. As a polycarboxylic acid or its Anhydrides are tri- or tetraacids such as trimellitic anhydride or called benzene tetracarboxylic acid. Preferred as diols consider ethylene glycol, propylene glycol 1,2 and 1,3, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedi methanol and polyglycols of the ethylene glycol type and Propylene glycol.  

The main polyols are trimethylolpropane, glycerol or Pentaerythritol and ditrimethylolpropane, sorbitol and dipentaery to call thrit.

Also suitable as diols or polyols are oxalkylated (e.g. with ethylene oxide or propylene oxide) diols or polyols, ins especially with a degree of oxalkylation of 0 to 10, based on the respective hydroxyl groups of the diol or polyol.

The polyesters to be used according to the invention also include Polycaprolactone diols and triols, their preparation to the person skilled in the art is also known.

As hydroxyl-containing polyethers such. B. those in question which according to known methods by the implementation of two and / or polyhydric alcohols with different amounts of ethylene oxide and / or propylene oxide can be obtained. The same are also polymerization products of tetrahydrofuran or Butylene oxide can be used.

Oxalkylation products of the abovementioned diols are preferred or polyols, in particular with a degree of oxyalkylation of 0 to 10, based on the respective hydroxyl groups of the diol or Polyols, with at least 2 ether groups in the molecule are.

Suitable compounds with (meth) acrylic groups are also ure than (meth) acrylates, such as those obtained by reacting mono-isocyanates or polyisocyanates containing hydroxyl groups (Meth) acrylates, especially those of the formula I, is obtained are.

As polyisocyanates to name z. B. aliphatic, cycloali phatic and aromatic diisocyanates, e.g. B. 1,4-butane diiso cyanate, 1,6-hexane diisocyanate, 2,2,4- and 2,4,4-trimethylhexa methylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane di isocyanate, isophorone diisocyanate, 4,4, -diisocyanatodiphenylmethane, 4,4'-diisocyanatodicyclohexylmethane, 2,4- and 2,6-tolylene diiso cyanate, tetramethylxylylene diisocyanate.

The uretdione, biuret and isocyanurate are also well suited Group-containing addition products, in particular Diiso cyanate.  

Finally, epoxy (meth) acrylates may be mentioned, e.g. B. such as by the reaction of epoxidized olefins or diglyci dyl ethers, e.g. B. aromatic polyepoxides, such as bisphenol-A digly cidyl ethers are available with (meth) acrylic acid.

In general, the acrylates are in the above compounds preferred over the methacrylate compounds.

Particularly preferred compounds with (meth) acrylic groups are polyester and polyether acrylates described above and multifunctional monomers of formula I, especially tri methylolpropane triacrylate, hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and penterythritol acrylates.

The (meth) acrylic compounds according to the invention are, as already mentioned above, by simply adding the aminoalkenyl ether to the above-mentioned compounds with (meth) acrylic groups Lich. Advantageously, to speed up implementation the temperature on z. B. 50 to 100 ° C can be increased.

The amount of aminoalkenyl ether can be chosen so that, for. B. 0.1 to 100 mol% of the (meth) acrylic groups in the form of the Michael ad products with aminoalkenyl ethers. Through the introduced The compound according to the invention contains vinyl ether groups sufficient number of double bonds, even if 100 mol% of (Meth) acrylic groups are in the form of the Michael adduct.

The mean is preferably 0.1 to 50 mol%, particularly preferably 10 to 50 mol% of the (meth) acrylic groups in the form of the Michael Ad products.

The (meth) acrylic compounds according to the invention are suitable as such z. B. for the production of coatings and moldings. However, they can also be mixed with other ethylenic mixtures unsaturated, polymerizable compounds, e.g. B. monomers such as C₁-C₁₀ alkyl acrylates, vinyl aromatics, e.g. B. styrene, vinyl esters, e.g. B. vinyl acetate, vinyl ethers, e.g. B. C₁-C₈ alkyl vinyl ethers, or Oligomers, e.g. B. with the connections described above (Meth) acrylic groups can be used.

The (meth) acrylic compounds according to the invention as such and Mixtures of these (meth) acrylic compounds with other ethyls nisch unsaturated, polymerizable compounds are in hereinafter collectively called "curable compositions".  

The curable compositions can, for. B. 1 to 100 wt .-%, preferred example, 2 to 50 wt .-% of the (meth) acrylic according to the invention Connections exist, with the weight given to all be ethylenically unsaturated, polymerizable compounds pulls.

These masses can addi for the respective use tive, e.g. B. crosslinkers, thickeners, leveling agents, dyes, pig elements or fillers or solvents are added.

The masses can be radical or cationic, with increased Temperature or high-energy radiation z. B. with UV light be hardened.

The compositions can be used for radiation curing with UV light Photoinitiators are added.

Since vinyl ether compounds are preferably cationic and e.g. B. Free-radically polymerize (meth) acrylic compounds, it is recommended that photoinitiators for the cat add ionic and radical polymerization.

Is it the polymerizable, ethylenically unsound saturated groups predominantly around vinyl ether groups, is opposed also only a photoinitiator for the cationic polymer tion sufficient. If the proportion of vinyl ether groups is low, is possibly only a photoinitiator for the radical Polymerization sufficient.

As photoinitiators for radical polymerization in Be traditional costumes B. benzophenone and derivatives thereof, such as. B. Alkylbenzophenones, halogen-methylated benzophenones, Michlers Ke clay, as well as benzoin and benzoin ethers such as ethylbenzoin ether, Benzyl ketals such as benzil dimethyl ketal, acetophenone derivatives such as e.g. B. Hydroxy-2-methyl-phenylpropan-1-one and hydroxycyclohexyl phenyl ketone, antrachinone and its derivatives such as methyl anthra quinone and especially acylphosphine oxides such as B. Lucirin® TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide).

Coming as photoinitiators for cationic polymerization e.g. B. consider those as mentioned in US 5 106 885. May be mentioned for. B. triarylsulfonium salts, especially triphenyl sulfonium hexafluorophosphate, diaryliodonium salts etc.

With radiation curing with UV light, the curable Bulk photoinitiators preferably in a total of 0.1 up to 15% by weight, particularly preferably from 0.5 to 10% by weight  on the polymerizable ethylenically unsaturated compounds added.

The masses can also be generated by electron beams without the addition of Photoinitiators or thermal, optionally with the addition of Initiators for thermal polymerization, e.g. B. peroxides, ge be hardened.

Radiation curing is preferred, in particular with UV light.

The curable compositions can be used to produce coatings, e.g. B. paints or printing inks or moldings, for. B. for the manufacture development of photoresists, in stereolithography or as a casting mass z. B. can be used for optical lenses.

In the manufacture of the coatings or moldings, the hardenable masses applied to the objects to be coated gene or brought into the intended form and then by high-energy radiation, especially UV light, can be cured.

The (meth) acrylic compounds or curable mas sen show high reactivity in radiation curing.

The coatings or moldings obtained have a number very good application properties, e.g. Legs high hardness, good scratch resistance and very good chemicals resistance.

Examples example 1

300 g of a polyester acrylate (Laromer® LR 8799, BASF) were added 75 ° C with 12.8 g (0.147 mol) of a vinyl ether of the formula

H₂N-CH₂-CH₂-O-CH = CH2 (ethanolamine vinyl ether)

added and stirred for 5 h. The reaction product was then fil trated.

Example 2

The procedure corresponded to Example 1. As vinyl ethers 22.4 g (0.143 mol) of the compound

used (diethanolamine divinyl ether).

Comparative Example 1

As example 1. Instead of the vinyl ether, 9 g (0.147 mol) Ethanolamine used.

Comparative Example 2

As example 2. Instead of the vinyl ether, 15.0 g (0.143 mol) Diethanolamine used.

Table 1

Properties of the resins

Application properties

The resins were butyl acetate to a viscosity of 500 mPa · s diluted with 3%, photoinitiator (Irgacure®500, Ciba Geigy) ver sets and with a UV lamp (120 W / cm) from the company IST on one Irradiated conveyor belt.

Reactivity

The rate at which this is measured is the reactivity Conveyor belt on which the samples to be irradiated lie on the UV lamp can be passed for irradiation (in m / min) and harden the samples to tack-free coatings (high Ge speed = high reactivity).  

Pendulum damping

The pendulum damping was determined according to DIN 53 157 and is a measure for the hardness of the coating (high values = high hardness).

Erichsen depression

The Erichsen cupping was determined according to DIN 150 1520 and is a Measure of flexibility, elasticity of a coating (high Values = high flexibility).

Chemical resistance

The chemical resistance was determined according to DIN 68860 B. There at is a manufactured film with various chemicals acts and the appearance judged optically (grade 0 = very good, 5 = bad) (average of 10 individual tests).

Whiteness

The degree of whiteness according to Beyer is a measure of yellowing. Certainly the yellowing increase after ten times exposure to UV Light compared to single exposure.

The results are listed in Table 2.

Table 2

Example 5

226.0 g (1 mol) of hexanediol diacrylate were mixed with 31.4 g (0.22 mol) Diethanolamine divinyl ether was added and the mixture was stirred at 105 ° C. for 25 h until no more amine was detectable in the gas chromatogram.

Comparative Example 6

248.6 g (1 ml mol) of hexanediol diacrylate were mixed with 23.1 g (0.22 mol) Diethanolamine was added and the mixture was stirred at 105 ° C. for 5 h until it was in the gas chromatogram was no longer detectable amine.

Application properties

The compounds from 5 and 6 were used as reactive diluents (20 wt .-%) for a polyester acrylate (Laromer LR 8800) puts.

A) Example 5 B) Comparative Example 6

Irgacure®500 (4% by weight) was used as the photoinitiator.

The resins were in a layer thickness of 100 microns with a Box squeegee mounted on glass and two using UV (2 × 80 W / cm) times at 15 m / min speed of the conveyor belt cured.

Pendulum damping:
A) 115 s
B) 98 s

Claims (7)

1. (meth) acrylic compound containing at least one (Meth) acrylic group, which by addition of a primary or secondary amino group of an aminoalkenyl ether to the dop Pel bond of the (meth) acrylic group is present as a Michael adduct. 2. (meth) acrylic compound according to claim 1, wherein the (Meth) acrylic compound a total of 1 to 6 (meth) acrylic groups contains, of which one, several or all in the form of Michael adducts are available. 3. (meth) acrylic compounds according to claim 1 or 2, wherein the aminoalkenyl ethers are those of the formula where R¹ and R² independently represent a hydrogen atom or a C₁-C₄ alkyl group, R³ has the meaning of a hydrogen atom or organic radical having up to 10 C atoms and Z and X independently of one another represent an organic link. 4. Radically or cationically curable compositions containing 1 to 100 wt .-%, based on the radical or cationic hardness ble compounds, a (meth) acrylic compound according to one of claims 1 to 3. 5. Use of the masses according to claim 4 for the production of Coatings or moldings. 6. Method of making coatings or mold bodies, characterized in that compositions according to claim 4 be cured by high-energy radiation.   7. Coatings or moldings available using of free-radically or cationically curable compositions according to An saying 4.