DE2038656C3 - Process for the production of coatings from vinyl polymers on moldings made from acrylonitrile-butadiene-styrene polymers - Google Patents

Description

weight% «, ^ - olefinically unsaturated vinyl monomer Containing copolymer, wherein the α, β-olefinically unsaturated Units in the range from about 0.5 to about 5, preferably from about 0.7 to about 3, per 1000 molecular weight units limited sine.

The acrylates used according to the invention can be divided into three groups. According to the first embodiment, the acrylate is a diacrylate, dimethacrylate or monoacrylate-monomethacrylate of an alkanediol having 2 to 12 carbon atoms, i.e. the Diester from a molar proportion of an alkanediol with 2 to 12 carbon atoms and two molar ones Proportions of acrylic acid or methacrylic acid, or a molar proportion of each. Such diols include without being limited to ethanediol (ethylene glycol), propanediol, butanediol, hexanediol, Octanediol, decanediol and dodecanediol. These diols can be either straight chain or branched chain Be diols. According to the second embodiment, that is Acrylate with a diacrylate, dimethacrylate or mono- ao acrylate-monomethacrylate of a polyether diol 4 to 12 carbon atoms. Powdery diols

col. According to a third embodiment, the acrylate is a triacrylate, trimethacrylate, monoacrylate-dimethacrylate or diacrylate monomethacrylate of a triol having 6 to 12 carbon atoms, e.g. B. trimethylolpropane triacrylate, Trimethylolpropane trimethacrylate, 1,4 - decanetriol triacrylate, 1,4,10 - decanetriol trimethacrylate, 1,5,12-dodecanetriol triacrylate, 1,5,12-dodecanetriol trimethacrylate and the same. Based on a pigment and mineral filler free base and non-polymerizable solvent, the paint binder solution contains about 5 to about 45, levorzugt about 20 to about 35% by weight of one of the acrylates mentioned above or of their · ■ ical.

Per remainder of the paint binder solution, ie 55 to i /; C ew-% of the total mass, consists of a coating binder resin with unsaturated vinyl and optionally monovinyl monomers. The vinyl resin used in the paint is a vinyl monomer containing copolymer and comprises from about 15 to about 100% by weight of the remainder or supplementary material. The Monovinylmoaomeren include 0 to 85, advantageously from 5 to 85 and forthcoming / U £ t 65 to 85% by weight of residues or complementary \ <t.terials. Advantageously, these resins have an average molecular weight in the range of about 1000. is about 25,000, preferably about 5000 to about 15,000.

The vinyl resin has more than about 0.5 and less than about 5 α, / 3-olefinically unsaturated units each ICOO molecular weight units, preferably about 0.7 to about 3 such units per 1000 molecular weight units. A preferred vinyl resin is made by copolymerizing acrylates, e.g. B. methyl methacrylate, Ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like, and an amount of glycidyl methacrylate corresponding to the desired degree of unsaturation manufactured. This is done in a second reaction stage by converting the copolymer introduced with acrylic acid or methacrylic acid. Other vinyl resins are used in the following examples explained.

If the monovinyl monomer component is used it can be styrene, methyl methacrylate, ethyl acrylate, hydroxyethyl methacrylate, butyl acrylate, Butyl methacrylate, 2-ÄthyIhexylmethacrylat, their mixtures and the like.

The term "paint" as used herein includes both the binder including pigment and / or particulate! Filler, the binder without Pigment and / or filler or only with a very low content thereof, and he can optionally be colored. Thus, it can ultimately be converted into a permanent, wear-resistant film Binder means the total or virtually all of the material used to form the film or it can be the carrier for pigments and / or particulate filler material. He can contain a volatile, non-polymerizable solvent which is evaporated before curing can.

The following examples serve to further illustrate the invention without restricting it.

B e i s ρ j e 1 1

A «, ^ - olefinically unsaturated vinyl resin, resin A, is made in the following way:

»5 Jy ~ | · · · · ⁶⁰ p

Methyl methacrylate 196

Ethyl acrylate 333

Glycidyl methacrylate 71

Azobisisobutyromtnl 6

Hydroquinone 0.12

Methacrylic acid 42

Ethylamine 0.96

proceedings

The xylene solvent is added to an inlet tube equipped with a stir bar, addition funnel, thermometer, nitrogenous tube and a cooler-equipped piston. The amount of xylene is equal to the total weight of the to be added Vinyl monomers. The xylene is heated to reflux and nitrogen is passed through the Solution blown during the heating and during the reaction. The combined monomers with the exception of methacrylic acid and initiator (azobisisobutyronitrile) are added to the reflux held solution was added evenly over a period of 2 hours. The weight of the Initiator is 10 parts by weight per 1000 parts by weight of vinyl monomers. The reaction solution is on Maintained reflux until the conversion of the monomer to the polymer is greater than about 97%.

In the second stage, hydroquinone is added as an inhibitor, followed by methacrylic acid for conversion added with the epoxy groups of the polymer. Triethylamine is used as a catalyst. This

Esterification is carried out (determined by the remaining acid number). The xylene is then im Distilled off in vacuo and the polymer removed.

It is a paint binder solution from 25 parts by weight Resin A and 75 parts by weight of methyl methacrylate prepared. This solution is applied to the Surface of an ABS substrate applied to a mean depth of about 25 μm and in a nitrogen atmosphere with an electron beam with an average energy of 275,000 EV of a current intensity of 25 milliamps until the coating is exposed to a total dose of 12 Mrad.

The abbreviation »rad« means radiation? dosage that allows the absorption of 100 ergs of energy each Grams of the absorber, for example the coating film. The abbreviation »Mrad« used here means one million rad. The electron-emitting device can be an electron linear accelerator that is used to develop a direct current potential in the range of about 100,000 to about 500,000 volts is suitable. In such a device, the Electrons usually emitted by a hot filament and by a uniform increase in voltage accelerated. The electron beam, which have a diameter of about 4 mm at this point can, can then be bundled into a funnel-shaped beam and then through a metal window, for example of a magnesium-thorium alloy, aluminum, an alloy of aluminum and a small amount of copper and the like, about 0.07 mm thick. The irradiation is preferably carried out in a practically oxygen-free atmosphere, e.g. B. nitrogen, helium and the like.

The coating is subjected to a standard adhesion test, hereinafter referred to and im each, and the results are given below autgeduured.

Table I.

Adhesion Test - Paint Kit I
Resin A 25% - methyl methacrylate 75%
Substrate Adhesion,%

ABS copolymer 50

Comparative experiment 4

A fourth attempt is made using the same procedure except that the paint binder solution consists of 50 parts by weight of resin A and 50 parts by weight of 2-ethylhexyl acrylate. The adhesion test is performed on the cured coating as indicated above and the results are listed below:

labellc IV

Adhesion test - paint approach IV
_{Resin A} 5 _% _ 2-ethylhexyl acrylate 50%

Substrate Adhesion,%

ABS copolymer 50

15th

Comparative experiment 2

A second attempt is made using the same procedure except that in the paint binder solution the resin component is increased to 50 parts by weight and the amount of Monovinyl monomer is reduced to 50 parts by weight. The adhesion test is carried out as above indicated on the cured coating and the results are given below:

_ ... _DD
laoeiie 11

Adhesion test - paint approach II
Resin A 50% - methyl methacrylate 50%
Substrate Adhesion,%

ABS copolymer 35

Comparative experiment 3

A third verse is made using the The same procedure is carried out with the exception that the vinyl monomer component is in the paint binder solution is replaced by bio acrylate. the Adhesion test is carried out, as in the previous experiment, on the cured coating and the results are reproduced below:

T iv.11 rrr
Adhesion test - paint approach ΠΙ

Resin A 50% - butyl acetate 50y
Substrate adhesiveness, / _o

ABS copolymer 35

25 25

Comparative experiment 5

. ^Em fifth experiment is performed using the same procedure with the exception ^that _t ^{nen Jn the} Anstnchsbmderlosung a Harzkompo. ^te '. ^{Resin> au} * is increased ⁷⁵ percent by weight ^{and that the amount of Monovin} ylmonomerem, _{Methylmethacrylatj} is reduced _{to 25} parts by weight. The adhesion test is carried out as indicated above on the cured coating and the results are given below:

Table V

Adhesion test - initial approach V
^{HafZ A 75%} "methyl methacrylate 25%
Substrate Adhesion,%

Aöb copolymer 10

After the lack of adhesion of paints made of vinyl resin and monovinyl mono-

More in this way with different resin concentrations and with different monomers has been detected, the first test according to the invention is carried out using the same method except that the paint binder solution

Contains 25 parts by weight of Haiz A, 45 parts by weight of methyl methacrylate and 30 parts by weight of ethanediol (ethylene glycol) dimethacrylate. The adhesion ^{test is successful} ? ^ indicated above, on the cured coating, and the results are given below

the reproduced:

Table VI
Adhesion test - initial approach VI

Resin A 25% - methyl methacrylate 45% -

Ethanediol dimethacrylate 30%

Substrate adhesion, ° /

ABS-Conolvmer 100 °

A seventh test is carried out using the same method as in the preceding comparison ^ ⁰ ^ ¹ * ^{1 except} that the Anstrichsbmderlösung 25 Gewichtstefle resin A, 70 parts by weight of methyl methacrylate and S parts by weight

^6s ethanediol dimethacrylate contains The adhesion test is carried out, as in the previous test, on the cured coating, and the results are listed below:

7 8

Table VII as in the previous experiment on the cured

Adhesion Test - Paint Run VII, Coating, and the results are reported below :

Resin A. 25% - methyl methacrylate 70% - Table XI

Ethanediol dimethacrylate 5% ₅ Adhesion test - paint approach XI

* ί _ς Τ, adhesion,% _{resin A} _ _Meth _

ABS copolymer 90 1,4-butanediol dimethacrylate 15%

An eighth attempt is made using the Substrate Adhesion,% same procedure as in the previous Verio ABS Copolymer 100
also carried out with the exception that the paint binder solution contains 25 parts by weight of Resin A, 70 parts by weight. A twelfth experiment is carried out using the same procedure as in the preceding Ver-1,4-butanediol dimethacrylate using the part by weight methyl methacrylate and 5 parts by weight. The adhesion test was carried out with the exception that the anness test was carried out as in the previous experiment, 15 coating binder solution, 50 parts by weight of resin A, 35 parts by weight of the cured coating, and the results were given as follows: 1.4 parts by weight methyl methacrylate and 15 parts by weight: Contains butanediol dimethacrylate. The adhesion test is carried out as in the previous experiment, Table VIII, _{on a} cured coating, and the results are given below: Adhesion test - paint batch VIII * °:
Resin A 25% - methyl methacrylate 70% - Table XII

1,4-butanediol dimethacrylate 5% adhesion test - paint batch XII

^Substrate Adhesion,% _{Resin A50X} _ _{Methyl methacrylate 35 %} _

ABS copolymer 95 25 1,4-butanediol dimethacrylate 15%

A ninth attempt is made using the substrate adhesion,%

same procedure as in the previous ABS copolymer 100

proceed with the exception that the paint binder solution contains 15 parts by weight of resin A, 80 parts by weight. The adhesion test was carried out with the exception that the test was carried out as in the previous test on a paint binder solution, 50 parts by weight of resin A, 35 parts by weight of Gedem cured coating, and the results were given in the weight of butyl acrylate and 15 parts by weight of 1,4-Bu of the following: ³⁵ tanediol - Contains dimethacrylate. The adhesion test

takes place, as in the previous experiment, on the

Table IX cured coating, and the results are shown below

Adhesion ability test - painting approach IX are reproduced:

Resin AJ 5% - methyl methacrylate 80% - ₄₀ Table XIII

Ethanediol dimethacrylate 5% adhesion test - paint approach XTII

Substrate Adhesion,% _{Resin A 5Q%} ._ _{Butyl Acrylate 35 χ} _

ABS copolymer 100 1,4-butanediol dimethacrylate 15%

A tenth attempt is made using the 45 substrate adhesion,%

same procedure as in the previous ABS copolymer 100

carried out with the exception that the request

Line binder solution 25 parts by weight Resin A, 65 Ge. A fourteenth run is used

parts by weight of methyl methacrylate and 10 parts by weight of the same method as in the foregoing

Contains ethanediol dimethacrylate. The adhesiveness 5 <> Trial carried out with the exception that the

test is carried out, as in the previous experiment, on paint binder solution 50 parts by weight of resin A, 35 parts

the cured coating, and the results are by weight 2-ethylhexyl acrylate and 15 parts by weight

The following reproduced: contains 1,4-butanediol dimethacrylate The adhesion test is carried out as in the previous experiment

Table X 55 on the cured coating, and the results are Adhesion test - paint approach X reproduced below: Resin A25% - methyl methacrylate 65% - 'Table XTV Ethanediol dimethacrylate 10% adhesion test - paint approach XTV Substrate Adhesion,% 60 _{Haiz A 50} % _ 2-Ethyihexylacrylat 35% - ABS copolymer 10 ° 1,4-butanediol dimethacrylate 15% An eleventh test was carried out using the same substrate HaftfUgfa *. % Procedure as in the previous experiment with ABS copolymer 100

the assumption that the paint binders ^ S _#

iSsung 25 parts by weight of Hare A, 6Θ parts by weight of Me- Em fifteenth attempt is carried out using the

ftytaethacrylat rad 15 parts by weight 1,4-butanediol - same procedure as in the previous procedure

dmeöacrylat contains The adhesion test is carried out with the exception that the application

Line binder solution 15 parts by weight of resin A, 35 parts by weight Methyl methacrylate, 35 parts by weight of 2-ethylhexyl acrylate and 15 parts by weight of ethanediol dimethacrylate contains. The adhesion test is carried out, as in the previous test, on the cured one Coating, and the results are given below:

Table XV

Adhesion test - paint formulation XV resin A 15% - methyl methacrylate 35% - 2-ethylhexyl acrylate 35% - 1,4-butanediol dimethacrylate 5%

Substrate Adhesion,%

ABS copolymer 100

A sixteenth attempt is made using the same procedure as in the previous one Experiment carried out with the exception that the paint binder solution 50 parts by weight of resin A, 35 ge ao parts by weight of methyl methacrylate and 15 parts by weight of 1,6-hexanediol dimethacrylate. The adhesion test is carried out, as in the previous experiment, on the cured coating, and the results are reproduced below: as

Table XVI

Adhesion test - paint formulation XVI resin A 50% - methyl methacrylate 35% -

1,6-hexanediol dimethacrylate 15% substrate adhesion,%

ABS copolymer 100

A seventeenth attempt is made using the same procedure as your previous one Experiment carried out with the exception that the paint binder solution 25 parts by weight of resin A, 55 parts by weight of methyl methacrylate and 20 parts by weight Contains ethanediol dimethacrylate. The adhesion test is carried out as in the previous experiment the cured coating, and the results are given below:

Table XVII

Adhesion test - paint formulation XVII resin A 25% - methyl methacrylate 55% -

Ethanediol dimethacrylate 20% substrate adhesion,%

ABS copolymer 100 ⁵ °

An eighteenth test is carried out using the same procedure as in the previous test with the exception that the paint solution contains 50 parts by weight of Resin A, 30 parts by weight of methyl methacrylate and 20 parts by weight of 1,4-butanediol dimethacrylate. The adhesion test is carried out as in the previous experiment on the cured coating and the results are given below: 60

TabeDeXVm Adhesion test - paint approach XVHI

Resin A 50% - methyl methacrylate 30% - 1,4-butanedioI dimethacrylate 20%

Substrate Adhesion,% ABS copolymer 100

A nineteenth attempt is made using the same procedure as in the previous one Experiment carried out with the exception that the paint binder solution 25 parts by weight of resin A, 55 parts by weight of methyl methacrylate and 20 parts by weight Contains 1,6-hexanediol diacrylate. The adhesion test is carried out, as in the previous experiment, on the cured coating, and the results are in reproduced the following:

Table XIX

Adhesion test - paint batch XIX resin A 25% - methyl methacrylate 55% -

1,6-hexanediol dimethacrylate 20% substrate adhesion,%

ABS copolymer 100

30th

35

40

45 ^previous attempt to ^{And the} results are in

Table XX
^{Adhesion test} - paint approach XX Har2A5 S ^%

^% ^, ^Methyl methac ^ at3 andiol dimethacrylate 20%

^, Ability,%

ABS copolymer .... ₁₀₀

^ ^{aCrylate and 20} weight ^ - contains ^you ? ethacrylate. the

Table XXl Adhesion test - paint batch XXI f * ??% * methyl methacrylate 30% tetraethylene glycol dimethacrylate 20%

Substrate ABS copolymer

Adhesion, % 100

going VbS ■ ♦ "f ***** ™ as in the previous the AnSi? *, ^{the Aui} » ahme carried out,

teä Ädfol ^ S ¹¹⁶⁰¹³ ^ ¹³ * ^md 20GeWiChS SgkdSiÄ ⁶ ^^ ¹ ^ «*» ». The Haft- juugKeHstest takes place as in the νητ ********* w * «.

Ge

^^ «Ο» »· The HaS ^ »& The previous

U 9TICL

Table ΧΧΠ

Adhesion Test - Paint Approach XXII

Resin A 75% - methyl methacrylate 5% -
Ethanediol dimethacrylate 20%

Substrate adhesion%

ABS copolymer 100

A twenty-third attempt is made using the same procedure as in the previous one Experiment carried out with the exception that the paint binder solution was 25 parts by weight Resin A contains 45 parts by weight of methyl methacrylate and 30 parts by weight of 1,6-hexanediol dimethacrylate. The adhesion test is carried out, as in the previous experiment, on the cured coating, and the results are given below:

Table XXIII
Adhesion Test - Paint Approach XXIII

Resin A 25% - methyl methacrylate 45% -
1,6-hexanediol dimethacrylate 30%

Substrate
ABS copolymer

Adhesion,% 100

A twenty-fourth attempt is made using the same procedure as in the previous experiment with the exception of that the paint binder solution contains 25 parts by weight of Resin A. Contains 45 parts by weight of methyl methacrylate and 30 parts by weight of diethylene glycol dimethacrylate. The adhesion test is carried out, as in the previous experiment, on the hardened top layer, and the results are reproduced below:

Table XXIV
Adhesion test - paint batch XXTV

Resin A 25% - methyl methacrylate 45% -
Diethylene glycol dimethacrylate 30%

Substrate adhesiveness. %

ABS copolymer 100

A twenty-fifth attempt is made using the same procedure as in the previous experiment with the exception of that the paint binder solution 25 parts by weight of resin A, 45 parts by weight of methyl methacrylate and 30 parts by weight of tetrapropylene glycol dimetJiacrylate contains. the Adhesion test is carried out, as in the previous experiment, on the hardened Oberzag, and the results are given below:

Table XXV
Adhesion test - paint batch XXV

Resin A 25% - MeÄjtoneäiaciylat 45% -
Tetrapropylene glycol dimethyl acrylate 30%

Substrate Adhesion,%

ABS copolymer 100

The adhesion test is carried out, as in the previous experiment, on the cured coating the results are given below:

Table XXVI

Hai tbarkeitster.t - Paint approach XXVI

Resin A 25% - methyl methacrylate 45%
Trimethylolpropane triacrylate 30%

Substrate adhesion, ° /

ABS copolymer 100

A twenty-seventh attempt is made using the same procedure as in the previous one prospective experiment carried out with the exception that the paint binder solution 25 weight parts of resin A, 45 parts by weight of methyl methacrylate and 30 parts by weight of 1,5,12-dodecantrioI-trimethacrylate contains. The adhesion test is carried out as in

previous experiment on the cured coating and the results are given below

Table XXVII
Adhesion Test - Paint Approach XXVII

Resin A 25% - methyl methacrylate 45% -

1,5,12-dodecanetriol trimethacrylate 30%

Substrate adhesiveness, /

ABS copolymer 100

Example 2

A twenty-eighth attempt is made under Ver

The same procedure was used as in the previous experiment with the exception that the paint binder solution is 60 parts by weight of resin Λ

and contains 40 parts by weight of ethanediol diacrylate.

Example 3

The procedure of Example 1 is repeated with the only difference that the electrons de Electron beam have an average energy of 350,000 E \.

Example 4

The method according to Example 1 is repeated with the one single difference that the irradiation atmosphere is helium

Example 5

The procedure of Example 1 is the only one Difference repeats that the resin A is replaced by resin I, which contains the following ingredients ii has been manufactured in the manner described below:

Stage I parts by weight

Ethyl acryate 38.8

Methyl methacrylate 23.2

Aylglyddyl ether 37.0

Benzoyl peroxide 1.0

Xylene solvent

55

A twenty-sixth attempt is made using the same procedure as in the previous one Experiment carried out with the exception that the paint binder solution 25 parts by weight of resin A, 45 parts by weight of methyl methacrylate and Contains 30 parts by weight of trimeflrjlohjropane triacrylate A reaction vessel equipped with a cooler, thermometer, stirrer and dropping funnel is placed in the reaction vessel The amount of xylene equal to the weight of the reaction parts to be added in the first reaction stage: The xylene is heated to about 100 to 120 ° C. The four reactants are thoroughly

borrowed mixed and slowly with a dropping funnel to the heated xylene · added over a period of 4 hours. The response will be at this Maintained temperature for 1 to 2 hours after addition is complete and then allowed to return to room temperature cooling down.

The copolymer produced by this process is further reacted in the following way:

stages

Parts by weight

Copolymer from stage I 69.4

Allyl alcohol 30.4

Potassium hydroxide 0.2

A solution of the allyl alcohol and potassium hydroxide is added to the copolymer at room temperature. The mixture is then heated to a temperature of 100 to 120 "C. This temperature is maintained for about 7 hours, and allowed to cool. The reaction mixture from Binderpolymerem is heated to about 6O ⁰ C, and the xylene and * ° excess reactants are in Distilled off under vacuum.

Example 6

The procedure of Example 1 is repeated with the * 5 umpteenth difference that Resin A is replaced by Resin C. Resin C is made up of the following Components manufactured in the manner described below:

Stage I parts by weight

Ethyl acrylate 39

Methyl methacrylate 24

Allyl alcohol 36

Benzoyl peroxide 1

Xylene solvent

An amount of xylene equal to the weight of the reactants to be added in the first reaction stage is introduced into a reaction vessel equipped with a condenser, thermometer, stirrer and dropping funnel. The xylene is heated to about 100 to 120 ⁰ C. The four reaction materials are mixed thoroughly and slowly added via a dropping funnel to the heated xylene over a period of 4 hours. The reaction is held at this temperature for 1 to 2 hours after the addition is complete and then allowed to cool to room temperature.

The copolymer formed by this process is further reacted in the following manner:

Stage II parts by weight

Copolymer from stage I 69

Allyl glycidyl ether 30.8

Potassium hydroxide 0.2

A solution of the allyl glycidyl ether and potassium hydroxide is added to the copolymer at room temperature. The mixture is then heated to a temperature of 100 to 12O ⁰ C. This temperature is maintained for about 7 hours and allowed to cool. The reaction mixture from Binderpolymerem is heated to about 6O ⁰ C, and the xylene and excess reactants are removed by vacuum distillation.

Example 7

The procedure of Example 1 is repeated with the only difference that the resin A through Resin D is replaced. Resin D is made up of the following ingredients in the manner described below manufactured:

Stage I parts by weight

Methyl methacrylate 400

Ethyl acrylate 400

Hydroxyethyl methacrylate 195

Toluene 1000

Benzoyl peroxide 30

The benzoyl peroxide is dissolved in a solution of methyl methacrylate, ethyl acrylate and hydroxyethyl methacrylate and half of the toluene. This solution is added in portions to the rest of the toluene and refluxed for a period of 7 hours with a Endblasentemperatur of about 138 to 140 ⁰ C. The reflux treatment is maintained for a further 3 hours and the solution is cooled.

Stage II parts by weight

Solution from level I 500

Acryloyl chloride 33.8

Toluene 30

The solution from stage I is heated to 6O ⁰ C, and a solution of acryloyl chloride, and toluene is added dropwise over a period of 4 hours while allowing the temperature to about 90 ° C increase. This solution is subjected to a vacuum of less than 10 mm Hg at 70 ^° C. and the acrylic polymer is recovered.

The adhesion is tested in all examples in the following way: cross cut - parallel Lines are drawn 1.6 mm apart on the coating, cutting through to the substrate incised. Further parallel lines 1.6 mm apart will appear in the same Way at right angles to the first group and cut them to cross. Then cellulose tape is used Applied and removed over the incised surface. The adhesiveness is off the number of paint squares remaining in the pasted area in relation to the number of squares that were removed Paint squares, measured. Adhesive tape of the same adhesive quality is used in all experiments. It is applied to and from the coated surface in the same manner in all experiments removed.

The compositions according to Examples 3 to 7 also have excellent adhesiveness to substrates obtained from ABS copolymers.

1 sheet of drawings

Claims (4)

1 2 monomer, which upon polymerization on other claims: substrates, ζ. B. wood or metal, with ionizing radiation result in excellent adhesive strength, 1. Process for the production of coatings say about the desired level of adhesion Vinyl polymers on moldings made from acrylic 5 on ABS substrates. nitrile-butadiene-styrene polymers by applying the task consists in acrylonitrile-butadiene-styrene- Gen of solutions of the vinyl polymers, the copolymer substrates that have a firmly adhering vinyl characterized in that solutions have a paint film that can be quickly attached.
applied on a basis. Surprisingly, it has been found that the free of pigment and particulate! Filler, io adhesiveness of a vinyl resin paint binder or from (A) about 5 to about 45% by weight diacry of a paint binder made from vinyl resin and monovinyl lateu and / or dimethacrylates of an alkanediol monomer on an ABS substrate in unexpected with 2 to 12 carbon atoms, diacrylates and / ways and is considerably improved if the or dimethacrylates of a polyether diol with a paint binder at least 5% by weight of certain, 4 to 12 carbon atoms and / or triacrylates 15 acrylates defined below, and the film and / or trimethacrylates of a triol with 6 up to the ABS substrate with an electron beam 12 carbon atoms and (B) about 55 to about an average energy in the range of about 100,000 95% by weight of a vinyl resin-containing grain up to about 500,000, preferably about 150,000 to about component that is polymerized from 0 to about 85% by weight mono- 450,000 EV. vinyl monomer and about 15 to about 100% by weight ao. The term "acrylates" as used herein includes of a vinyl monomer containing a, /? - olefin ester of an alcohol and either acrylic acid contains nically unsaturated copolymers, the methacrylic acid, d. H. Acrylates and methacrylates, between about 0.5 and about 5 a, /? - olefiniscb unge- The inventive method for producing saturated units per 1000 molecular weight units of coatings of vinyl polymers on moldings has, exist and the molded body 35 body made of acrylonitrile-butadiene-styrene polymers then an electron beam from a durcli application of solutions of the vinyl polymer middle Energy in the range of about 100,000 to sate is characterized by having solutions of about 500,000 EV is exposed. that, on a basis free of 2. The method according to claim 1, characterized in pigment and particulate! Filler, from (A) draws that a copolymer with about 0.7 to 30 about 5 to about 45% by weight of diacrylates and / or about 3 Λ, / J-olennically unsaturated units per dimethacrylate of an alkanediol with 2 to 12 carbons-1000 Molecular weight units is used. Atoms of matter, diacrylates and / or dimethacrylates 3. The method according to claim 1 or 2, characterized in a polyether diol having 4 to 12 carbon atoms characterized in that the film-forming solution by and / or triacrylates and / or trimethacrylates Electrons with an average energy in the range of 35 of a triol with 6 to 12 carbon atoms and (B) about 150,000 to about 450,000 EV is networked. about 55 to about 95% by weight of a vinyl resin 4. The method according to claim 1 to 3, characterized by holding component that is 0 to about 85% by weight characterized in that a vinyl resin containing monovinyl monomer and about 15 to about 100 Ge component from about 15 to about 75% by weight of a Λ, / 9-oledes containing vinyl monomers Copolymers and 85 to 25% by weight of the 40 finically unsaturated copolymer containing Vinyl monomers is used. between about 0.5 and about 5 ", ^ - olefinically unsaturated Units per 1000 molecular weight units, exist and the shaped body closing an electron beam from a middle one 45 energy in the range of about 100,000 to about 500,000 EV is exposed.
The critical features of the invention consist in The invention relates to a method for producing the use of sufficient amounts of the coatings made from vinyl polymers on form- chosen acrylates, the use of which together with bodies made of acrylonitrile-butadiene-styrene polymers 50 an unsaturated vinyl paint binder resin and the application of solutions of the vinyl polymers. Crosslinking of the same with the electron beam on the products obtained according to the method comprise the surface of the ABS substrate.
a solid substrate made of acrylonitrile-butadiene-styrene- After application to the substrate, there is therefore Copolymer that has a vinyl coating on an outer surface without taking into account has adherent film of a vinyl paint, 55 pigment, particulate! Filler and non-polymeric thereupon by an electron beam with a sable diluent essentially from mean energy ranging from about 100,000 to about 55 to about 95 percent by weight of a vinyl resin t about 500,000 EV is polymerized. containing component and about 5 to about 45, In the following, for abbreviation, the acrylonitrile is preferably about 10 to about 35% by weight of diacry-butadiene-styrene copolymers referred to as ABS copolymer 60 lat of an alkanediol with 2 to 12 carbon. This copolymer is atoms in the field, diacrylates of a polyether diol with 4 to of the structural or structural plastics largely displaced 12 carbon atoms and / or triacrylates turns. Triols with 6 to 12 carbon atoms. The vinyl resin Previous attempts to more effectively contain ABS substrates in component containing 0 to about 85, in With a vinyl resin-containing paint 65, advantageously from about 5 to about 85, and preferably to provide featured relatively low about 65 to about 85 weight percent monovinyl monomers Adhesion between the paint film and the substrate. and about 15 to 100, advantageously about 15 to Even paints made of vinyl resin and vinyl - about 75 and preferably about 15 to about 35 ge