DE2063134C3 - Coating composition curable by ionizing radiation on the basis of siloxane-ester-acrylate and unsaturated monomers and process for their application - Google Patents

Description

Electron curable siloxane modified polyester paints are disclosed in US patents 37 512 and 34 37 513. In one embodiment these resins are made by reacting a siloxane with functional hydroxyl or hydrocarbonoxy groups with one diol and subsequent reaction of the siloxane-containing product with two different anhydrides, one of which is olefinically unsaturated in the «, ^ - position Compound, for example maleic anhydride, which has the desired amount of olefinic! ' Introduces Λ, / j unsaturation into the resin. At a Another embodiment is the resin by reacting a hydroxylated polyester with a Hydroxyl or hydrocarbonoxysiloxane produced.

Electron-curable siloxane-acrylate reaction products are proposed in German Patent 19 57 356. These materials are made through implementation a molar proportion of a siloxane having a hydroxyl or hydrocarbonoxy functional gnip pen with preferably two molar proportions of a hydroxyl-containing ester one in ίΧ, / i-position to Carboxyl group obtained from olefinically unsaturated carboxylic acid. Also below is the «, / f-reference to the Carboxyl group of the carboxylic acid based.

One aspect of the invention is siloxane hally Ansirichmassen obtained by irradiation with a Electron beam curable, which show an improved adhesion to the substrate, and which on the different flexibilities can be tailored precisely.

The invention is an ionizing radiation-curable composition based on a silo ester acrylate and unsaturated monomers, which is characterized in that it consists of a film-forming solution of 10 to 90 parts by weight of acrylic and / or vinyl monomers and 90 to K. ) Parts by weight of a siloxane ester acrylic, which is obtained by (1) reaction of a siloxane with at least two functional hydroxyl groups and / or alkoxy groups with a CVCii diol, (2) reaction of the resulting siloxane-containing reaction product of the first reaction with a Ct-Cjb -Dicarboxylic acid or an anhydride thereof, and (3) reaction of the siloxane-containing reaction product of the second reaction stage with a glycidyl acrylate, glyciclyl methacrylate and / or a CrCir monohydroxy ester of a CVCh diol and the acrylic acid or methacrylic acid has been produced.

In special embodiments it also contains a particulate pigment and / or a filler. Conveniently, the fil nbildendc Solution of 20 to 60 parts by weight of the monomers and 80 to 40 parts by weight of the siloxane ester acrylate.

The monomers preferably consist of esters of acrylic acid or methacrylic acid and alcohols 1 to 8 carbon atoms or from a mixture of vinyl hydrocarbons containing 8 to 10 carbon atoms and esters of acrylic acid or methacrylic acid with alcohols having 1 to 8 carbon atoms.

The coating compositions according to the invention provide improved adhesion, weather resistance, Paint film curability and flexibility obtained in electron beam cured coatings. The invention is particularly suitable for covering substrates made of wood, metal, glass and polymers Solids and fabrics or cloths made from synthetic or natural fibers.

The siloxane ester acrylate resins used here are obtained by a three-step reaction, wherein (1) a siloxane with two or more functional Hydroxyl or alkoxy groups per molecule is reacted with a C2-C21-D10I, (2) the siloxane-containing Reaction product of the first reaction stage with a Gi-Cjö dicarboxylic acid or such an anhydride is reacted and (3) the siloxane-containing reaction product of the second reaction stage either with glycidyl acrylate, Glyciflyl methacrylate or a C <-, C | i-Monohydroxyerylat, which is an ester of a CrGt diol and acrylic acid or methacrylic acid, is implemented.

The use of these resins results in significantly improved adhesion effects on the substrates.

In the context of the description, under the

Expression "paint" oiler "paint compound" egg paint including pigment and oiler l'einzteilicni Filler, the hindrance without pigment and / or filler or only with a low level of fatigue, which can be colored if necessary. Thus, the binder that will eventually turn into a permanent Film resistant to the effects of weathering is transferred from the total amount or practically the total amount of materials used to form the film or it can be used as Trügersloff for pigment and / or particulate filler material.

The siloxane ester aerylates used for the manufacture of ties The siloxanes used have reactive hydroxyl or alkoxy groups, preferably with Ci to Ci and particularly preferably alkoxy groups mil Cι or C _> bonded to at least two of the silicon atoms. The term "siloxanes" here denotes compounds. the one bond

-Si-O-Si-

- C-O-Si-

contain, the remaining valences by a hydrocarbon residue, a hydrocarbonoxy group, a hydrogen atom, a hydroxyl group or an oxygen atom which a silicon atom with a such valence connects with another silicon atom, are saturated. The siloxane can do both be cyclic as well as acyclic. Suitable cyclic and acyclic siloxanes for use in the context of Invention are described in detail in the above two patents and in other literature. The preferred siloxanes contain 2 to 5 functional hydroxyl and / or alkoxy groups. the The reactants are advantageously selected so that the siloxane is about 20 to about 60% by weight of the Makes up binder resin, which is obtained in the three-step reaction process.

_{The C 2} -C ^ i -diol used in the first reaction stage consists essentially of carbon, Wasserstol'l and oxygen and preferably of an aliphatic glycol, for example ethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol,
1,3-butylene glycol, 2-butene-1,4-diol!
1,4-butanediol, diethylene glycol,
Neopentyl glycol, 1.5-pen camouflaging hy lenglycol,
1,6-hexamethylene glycol, decamethylene glycol,
Polyethylene glycol and polypropylene glycols.
Aromatic diols can also be used, for example dimethylolbenzenes, dihydroxyethylbenzenes and the like. In the preferred embodiment, a molar proportion of the diol is applied to each molar proportion of the hydroxyl or alkoxy groups of the siloxane in the first reaction step.

The C-i-Cjtr diacid or its anhydride usually consists only of carbon, hydrogen and oxygen and can be either saturated or an unsaturated acid or its anhydride, for example fumaric acid, maleic anhydride. Succinic anhydride, Adipic acid, phthalic anhydride, tetrahydrophthalic anhydride, isophthalic acid, azelaic acid, Sebacic acid, 1,2-cyclohexanedicarboxylic acid

anhydride, I, J-cyclohexanedicarboxylic acid anhydride,

I / l-Cyclohexanedicarboxylic ^{anhyilride, r} > ■ Nurbornen-2,3-dicirbnnsäurciinhydrid, 4-methyl- ^r > -norbornene-2, J-dicarboxylic acid anhydride and the so-called "dimer acids", especially the C | "!) Imer acids, the through Connection in the middle of the molecule of two unsaturated Cm-monocarboxylic acids arise. Other suitable anhydrides include chloromaleic anhydride, dichloromaleic anhydride, chlorendic acid anhydride and the like. The acid is preferably used in the second reaction stage in equimolar amounts with respect to the amount of the diol reacted in the first reaction stage.

The acrylate used in the third reaction column

κ, provides the olefinic α, β-unsaturation for the resin, and can either consist of glycidyl acrylate, glycidyl methacrylate or a CVC.M monohydroxy acrylate, which is an ester of a C.?-Ck diol and acrylic acid or methacrylic acid, for example) 2-hydroxyethyl acrylate or methacrylate, 2-hydroxypropyl acrylate and methacrylate, 2-hydroxybyl acrylate or methacrylate, 2-1-hydroxyoctyl acrylic or methacrylate and similar compounds. This acrylate-type reaction participant is preferably

js se practically in a molar ratio of 1: 1 to the remaining reactive carboxyl groups of the siloxane-containing reaction product from the second Reaction tube used.

The flexibility of the resulting from the siloxane-ester-acrylic-1 lar / es formed in this way, cured paint film can significantly by changing the molar weight of the diol and / or the Dicarboxylic acid or its anhydrides and / or the acrylate can be varied.

.15 The siloxane ester aerylate resin obtained in this way is used with Cj-Cii-Vinylmonomercn to form the Paint binder solution mixed in the usual way, for example by spraying, roller application and the like., Is applied to the base and on it .by ionizing radiation, preferably in the form of an electron beam with an average energy is polymerized in the range of about 100,000 to about 300,000 electron volts.

The vinyl monomers preferably consist of

4S acrylic monomers !!, for example methyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, 2-Äthylhcxylacrylat, the hydroxyacrylates listed above for use in the third reaction stage of the resin production and the like., Or from mixtures of such acrylic monomers and vinyl hydrocarbons, such as. B. styrene and alkylated styrenes such as vinyl toluene, ix-methylstyrene, divinylbenzene and the like. The vinyl hydrocarbons can also be used alone as the vinyl monomer component of the paint binders. In combination with the monoacrylates and / or hydrocarbon monomers, it is also possible to use a small proportion of di-, tri- or tetra-functional acrylates. Also in connection with acrylates or methacrylates !! can use smaller amounts of other vinyl monomers, such as acrylonitrile. Acrylamide, methacrylonitrile, vinyl halides !!, such as e.g. B. vinyl chloride, and vinyl carboxylates such as / .. B. vinyl acetate, can be used.

In the production of the paints according to the invention, the olefinically unsaturated one in i \, / J-Stelhing Resin constituent up to about 90% by weight * of Paint binder solution on a pigment and particulate filler-free basis and down to about IO

CiL ¹ W .- "/ ο. Preferably niiU'lii the llinv etvv.i Ί0 l) is about 80 wt .-% of the I laiv monomer solution, the vinylnionomereu corresponding to about hi) i) is about 20 wt .-% of the solution beiragen. even ^versiänd-1, Ii, also other in Λ, / i-Siellung olefinically unsaturated polymers ANSI elle a clamp portion ties SiIoXaIi-IlStI ¹ I-ACrVIaI-IIiHVx ¹ S according animal invention eiiigesel / t Wertlen.

The abbreviation "Mrad" used here denotes I 000 000 rad. The term "rad" means a radiation dosage which results in an absorption of 100 ergs of energy per gram of absorber, for example a coating film. The electron emitting device may consist of a linear electron accelerator which is suitable for forming a direct current potential in the range specified above. In such a device, the electrons are usually emitted from a heating wire and accelerated by a uniform voltage gradient. The electron beam, which at this point has a diameter of voj) ciwj! 6.3 mm (1/4 inch), is then stretched in one direction so that a funnel-shaped beam results and then through a metal window, for example made of aluminum, with a small amount of copper-plated aluminum, a magnesium chloride -Legieriing. um elwa (), () l) 7 ^r > cm strong gelühri.

The binder is uMVUgswe.se aiii the backing film as koiiiinuiciiichcr from virtually glüchmäßigei I icle applied and cured thereon, preferably Einei would ultimately lead to Beieich elwa 2. ^r> μ to about K) O μ depending on the intended end use and animal-I liilcrlagc ties covered in Proilucles. The forming binder solution should have a sufficiently low viscosity to allow rapid application to the substrate of practically uniform depth, and preferably a sufficiently high viscosity so that a 25μ thick film is held on a vertical surface without dripping. The viscosity of the binder is adjusted by adjusting ties ties molecular weight resin or l \ ^ i resins and / or by varying the relative concentration llarzbcslanclteilcs ties and / or by varying the relative concentrations of the different monomers within the Vinvlmonomer-Besiandteiles. The binder is preferably applied to the substrate practically free of non-polymerizable organic solvents and / or diluents.

,O

at A siloxane window acrylic I larz was made from the made of the following materials: liar / I (! ew parts Siloxane with functional methoxy 412 groups ¹ ) N-copentyl glycol 208 Teiraisopropyl titanate 0.8 Maleic anhydride 196 Glycidyl methacrylate 237 Tetraethylammonium chloride 2.7 Hydroquinone 0.3

s ρ ie I grams. Then the hydroquinone was added. A solution of tetraethylammonium chloride as catalyst and of glycidyl methacrylate was added dropwise during 1 hour while the temperature was maintained at 120 ⁰ C. After a further 2 hours at 120 ° C., the acid content had dropped to 0.1 milliequivalents per gram and the reaction was terminated.

A second siloxane ester resin was made from the following materials using the same Procedure prepared as above:

') Acyclic polysiloxane with a mean molecular weight in the range from 700 to 800 with an average of 3 to 4 limclional methoxy groups per molecule.

The siloxane and the ncopentylglycol were in a stirrer, thermometer, nitrogen inlet tube and apparatus for collecting the volatile reaction products heated reactor equipped. the Tilankialyser was added when the temperature ! 00 C reached. The temperature was gradually increased to 150 "C. over the course of two hours. Within During this period, 57 parts by weight of volatile substances were distilled off. The main part of the distillate consisted from methanol.

The product was cooled to 100 ° C and the maleic anhydride added. The reaction temperature was kept at 120 ⁰ C for 3 hours, where the titratable acidity is 2.21 milliequivalents each

Resin II (Jew. Parts Siloxane with functional methoxy 412 groups, as used in resin I. N-copentyl glycol 170 Tctraisopropyl titanal 0.8 Tetrahydrophthalic anhydride 246 Hydroquinone 0.4 Tetraethylammonium chloride 2.6 Glvddyl methacrylate 230

Resin I and Resin 11 were dissolved in methyl methacrylate so that the resin content would be 60% by weight and 75% by weight, respectively % By weight. Clear films were drawn down and exposed onto phosphated steel panels cured to an electron beam source of 275 kilovolts and 25 milliamps in a nitrogen atmosphere, wherein the following results were obtained:

Resin i

Resin 11

Total dosage

Film thickness μ (mils)

ßlcisüft hardness

Resistance to solvents (rubbed with a sponge soaked in M et hy la t hy lke clay) Reverse Impact Strength (inch pound)

Bend around a core of J.4 mm

10 Mrad 10 Mrad 23 (0.9)
II 2.8 (1.1)
1: [I.
21 I.
more than 100 besveht 20 fails at 4 consists consists

Example 2

The process according to Example 1 up to the hardening stage was repeated, but the base consisted of Wood and the monomers consisted of 75% by weight of the paint binder solution and were a mixture of 2 molar proportions of methyl methacrylate, 2 molar proportions of ethyl acrylate and 1 molar proportion of 2-ethylhexyl acrylate.

Example 3

The procedure of Example 1 up to the hardening stage was repeated, but the paint contained the binder solution 90 parts by weight of the siloxane ester acrylate and 10 parts by weight of methyl methacrylate.

Example 4

The procedure of Example 1 up to the hardening stage was repeated, but the paint contained the binder solution 10 parts by weight of the siloxane ester acrylate binder solution material and 90 parts by weight of monomers from 3 molar proportions of 2-ethylhexyl acrylate, 2 molar Proportions of butyl methacrylate, 1 molar proportion of methyl methacrylate and 1 molar proportion of styrene.

Example 5

The process according to Example 1 up to the hardening stage was repeated, but the base consisted of Glass and the applied monomers contained 50% by weight of the paint binder solution and were one equimolar mixture of methyl methacrylate, styrene and butyl acrylate, while the film-forming solution with particulate titanium dioxide was pigmented.

Example 6

The procedure according to Example I up to the leveling solution was repeated, but the pad consisted of Polypropylene and it was an equimolure amount of poly-L2-propylene glycol with about 21 carbon atoms used per molecule instead of neopentyl glycol in the first stage of the I larzzcrllung and one Equimolarc amount of succinic anhydride was substituted for maleic anhydride in the second stage used in resin production.

Example 7

The procedure according to Example I including the preparation step was repeated, but passed Underlay from a cotton wool tucli and it was an ilqiiimolurc amount of 1,3-butylcnglycol instead of the Neopcntylglycol in the first stage of Hurzherstclking, an equimolure amount of a tV dimer of unsaturated Cw-SlUircn instead of the Muleinsaurcunhydrids in the second stage of the reaction and an Ilquimolurc amount of cilyeidylucrylut instead of the Glycidylmcthnerylutes in the third stage of the I used hat manufacturing.

Example 8

The procedure with example I, including the curing stage, was repeated, but the monomer component of the paint binder solution consisted of a mixture of 3 molar proportions of methyl methacrylate, 1/2 molar portion of vinyl toluene, V ₂ molar portion of carboxyl group / 2 molar portion of hydroxyutyl methacrylate and 1/2 molar proportion of vinyl acetate, while an ilqiiimolure amount of

(Kl adipic acid was used instead of maleic anhydride in the second stage of resin production.

In Examples 2 to 8, too, excellent results were obtained.

Example 9

The procedure of Example 1 up to the hardening step was repeated, but this consisted of the first Reaction stage of the resin production used siloxane from a commercially available cyclic polysiloxane with functional hydroxyl groups with the following properties:

Hydroxyl Content, Dean Stark: 5.5 Percent condensable 0.5 Percent free 1600 Average molecular weight 400 Connection weight 1.531 to 1.539 Refractive index Durran softening point 93 Mercury process, ⁰ C at 60% solids in xylene 1.075 Specific weight at 25 ° C 33 Viscosity at 25 ⁰ C, centipoise A-I Gardner-Holdt

This siloxane was used instead of a functionally equivalent amount of the siloxane according to Example 1 used.

Example 10 became from the A siloxane ester acrylate resin made of the following materials: Gcw.-Partc Hur /. Ill 412 Siloxane (as in example 1) 208 Ncopentyl glycol 0.8 Tetraisopropyl titanate 196 Maleic anhydride 200 Hydroxy ethyl acrylate 0.3 Hydroquinone

The manufacturing process was identical to the one in Example 1 except for the addition of 1 hydrochi-Ih. Hydroxyethyl acrylate and 450 parts by weight of toluene were then added. A barrel was attached to the reaction flask. The reaction mixture was heated to the back until the silure value of the material indicated that 90% esterification had taken place. The toluene solvent was removed in vacuo and the resin obtained was dissolved in 400 parts of methyl methyl acrylate. The I lur /. Mi> nomcr solution was applied to steel sheets and placed under the ","; same conditions, but Elekti'onenstrahlen were applied with Durehsehnillsenergien of about J2 ^r> kilovolts as gchilrtct in Example. 1 Brains with an average strength of 5, 18, 23, 38, 64 and 100 μ were irradiated in this way.

Il

example

The procedure of Example 10 was repeated, but a functionally uquivulcntc amount of the Siloxane according to Example 9, instead of the siloxtin according to Example I, an equimolar amount of a ethylene glycol with an average of about 20 carbon atoms per molecule under the neopentyl glycol in the first Stage of resin production, a liqiiimolnrc amount of

7OÖ036 / 117

ίο

Azelaic acid instead of maleic anhydride in the second reaction stage of resin production and an equimolar amount of 2-hydroxyoctyl acrylate is used instead of the hydroxyethyl acrylate.

Example 12

The procedure of Example 10 was repeated, but the paint binder solution consisted of 20 Parts by weight of methyl methacrylate and 80 parts by weight of the siloxane ester acrylate resin.

Example 13

The process of Example 10 was repeated, but the paint binder solution consisted of 60 parts by weight of methyl methacrylate and 40 parts by weight of the siloxane ester acrylate resin.

Examples 9 to 13 also gave excellent results.

Example 14

The procedure according to Example 10 was repeated, but an equimolar amount of 1,6-hexamethylene glycol was used instead of the neopentyl glycol in the first stage of the resin production and an equimolar amount of 2-hydroxyoctyl methacrylate was used instead of the hydroxyethyl acrylate in the third stage of the resin production.

Example 15

The process according to Example 10 was repeated, except that an equimolar amount of 1-hydroxyethyl methacrylate was used used instead of hydroxyethyl acrylate in the third stage of resin production.

Example 16

S The procedure of Example 10 was repeated, but an equimolar amount of Hydroxypro · pyl methacrylate used instead of hydroxyethyl acrylate in the third stage of resin production.

Example 17

The procedure of Example 10 was repeated except that an equimolar amount of hydroxypropyl acrylate was used used instead of hydroxyethyl acrylate in the third stage of resin production.

Example 18

The procedure of Example 10 was repeated, except that hydroxybutyl acrylate was used instead of hydroxyethyl acrylate used in the third stage of resin production.

Example 19

The procedure of Example 10 was repeated, except that hydroxybutyl methacrylate was used instead of Hydroxyäthylacrylates used in the third stage of the resin production.

ίο Excellent results were also obtained in Examples 14 to 9 .

Claims (6)

Patent claims: 1. Acceptance amounts curable by ionizing radiation on the basis of siloxane-ester-acrylate and unsaturated monomers, which admit that they consist of a transforming IA ₁ UHg of 10 to 90 percent by weight acrylic and / or vinyl monomers and 90 up to 10 parts by weight of a siloxane ester aerylate, which by (!) Reacting of a siloxane with at least two functional hydroxyl groups and / or alkoxy groups with a C _> - C_i | diol, (2) conversion of the resulting siloxane-containing reaction product of the first Reaction step with a CVCVUiearbonsäure or is an anhydride thereof, and (J) conversion of the siloxane-containing reaction product of the second reaction step with a glycidyl acrylate, glyeidyl methacrylate and / or an O.-CirMonohydroxyestcr of a Ci-Ck-diol and acrylic acid or: o methacrylic acid has been produced , consists. 2. Anstriclinuissc according to claim I, characterized characterized in that it additionally contains a pigment and / or a filler. 3. Anstrichmassc according to claim I or 2, characterized characterized that the reforming solution of 20 to 60 parts by weight of the monomers and 80 to 40 There are parts by weight of the siloxane ester acrylate. 4. Paint composition according to claim 1 to 3, characterized in that the monomers of esters of the ^ o Acrylic acid or methacrylic acid and alcohols with 1 to 8 carbon atoms exist. 5. Paint composition according to claim I to 3, characterized in that the monomers consist of one Genetically of vinyl hydrocarbons with 8 to 10 carbon atoms and esters of acrylic acid oils Methacrylic acid with alcohols with 1 to 8 carbon atoms exist. 6. A method for coating a substrate with a paint, characterized in that on the surface of the base in an average layer thickness of 2.5 to 100 μ die Film-forming solution of the paint according to claims 1 to 5 applied and below Application of an electron beam with an average energy in the range of 100,000 networked up to 500,000 volts.