DE2038652A1 - Polyolefin substrate coated with vinyl - Google Patents

Description

DR. A. KOHLER M. SCHROEDER .... PATENTANWÄLTE (· V ^ ° ^D * * TCUCFON 37 * 7 «β ^{β MONCHEN 13} TCLCO ^ MMC: CAH ^ OPAT

UÖ-34-S / Ne

Ford Werke JLk ti engesellschaft,

Cologne - Deutz |

Vinyl-painted polyolefin substrate

The article of daily use according to the invention comprises a solid polyolefin substrate which has a firmly adhering vinyl paint film on an outer surface which has been polymerized thereon by an electron beam with an average energy in the range of about 100,000 Ms about 500,000 EV. After application to the polyolefin substrate, the vinyl coating composition, regardless of pigment, particulate filler and non-polymerizable diluent, consists essentially of about 55 to about 85% by weight of a vinyl monomer-containing copolymer solution and about 15 to about 45, preferably about 20 to about 35% by weight of diacrylates of an alkanediol with 2 to 12 carbon atoms, diacrylates of a polyether diol with 4 to 12 carbon atoms and / or diacrylates of a triol with 6 to 12 carbon atoms. The resin solution contains from 0 to about 85%, advantageously from about 5 to about 85% by weight of monovinyl monomers and from about 15 to 100, advantageously from 15 to 75 and

100808/225 *

preferably 15 to 55 parts by weight of an α, β-olefinically unsaturated one , Vinyl monomer-containing copolymers, in which the cc, olefic unsaturated units to a range of about 0.5 to about 5, preferably about 0.7 to about 3, to 1000 molecular weight units are limited.

The invention relates to polyolefin substrates that have an adherent Have vinyl paint film. The one used here The term "polyolefin" refers to polyethylene, polypropylene and ethylene-propylene copolymers.

Previous attempts to use polyolefin substrates in an effective manner with a paint containing a vinyl resin without pretreating the polyolefin substrates, drew is characterized by extremely poor adhesion between the paint film and the substrate. Even paints made of vinyl resin and Vinyl monomers which gave excellent adhesiveness, when polymerized with ionizing radiation on other substrates failed to be effective Adhesion to a polyolefin substrate.

Surprisingly, it has now been found that the adhesiveness a vinyl resin or an anatricha binder Vinyl resin and honey vinyl monomer on a polyolefin substrate unexpectedly and quite considerably can be improved if the paint binder is at least about 15 Geif.Jt of certain acrylates defined below and the film on the polyolefin surface with an electron beam having an average energy in the range of about 100,000 to about 500,000, preferably about 150,000 to about 450,000 EV is polymerized.

The term "acrylate" as used herein includes esters of one Alcohol and either acrylic acid or methacrylic acid, d. H. Acrylates and metharylates.

BAD ORIGiNAi

109808/2259

The article of daily use or laminated body according to the invention comprises a polyolefin substrate made of polypropylene, polyethylene and / or copolymers made of polypropylene and ethylene and a paint coating which adheres firmly to an outer surface of the substrate and which is characterized in that it has the polymerisation product formed in situ of a film-forming solution which is crosslinked by exposure to beam polymerization initiating electrons having an average energy in the range of about 100,000 to about 500,000 EV, the film-forming solution consisting essentially of (A) about 15 to about, on a pigment and particulate filler base 45 wt. # diacrylates and dimethacrylates of an alkanediol having 2 to 12 carbon atoms, diacrylates and dimethacrylates of a polyether diol having 2 bit 12 carbon atoms and / or triacrylates and trimethacrylates of a triol having 6 to 12 carbon atoms, and (B) 55 to 85 Gev.% of a a Vinyl resin containing Oomponente of 0 to about 85 Gew.fl »Monovinylmonomerem and about 15 to 100 Gew Contains 1000 molecular weight units.

The critical features of the invention are the use Preparation of sufficient quantities of the selected acrylates, their use together with an unsaturated paint binder resin and the crosslinking of the same with an electron beam on the surface of the polyolefin.

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 a monoacrylate ^ onomethacrylate of an alkanediol with 2 to 12 carbon. lenstoffatomen, ie the beast from a molar proportion of an alkanediol with 2 to 12 carbon atoms and two molar proportions of acrylic acid or methacrylic acid or one

109808/2269

molar fraction of each. Etharidiol is one of these diols (Ethylene glycol), propanediol, butanediol, hexanediol, octanediol, decanediol and dodecanediol. These diols can either be straight chain or branched chain diols. According to the second embodiment, the acrylate is a diacrylate, dimethacrylate or Ilonoacrylat-Monomethacrylat of a Polyätherdiols niit

4 to 12 carbon atoms. Such diols include diethylene diol (Glycol), dipropylene diol, triethylene diol, tetraethylene diol and tetrapropylene diol. According to the third embodiment, the acrylate is a triacrylate, trimethacrylate, Honoacrylate dimethacrylate, diacrylate monomethacrylate one Triols of 6 to 12 carbon atoms, e.g. B. TrimethylοIpropane triacrylate, Trimethylolpropane trimethacrylate, 1,4,10-decanetriol triacrylate, 1,4,10-decanetriol trimethacrylate, 1,5i12-I) odecanetriol triacrylate, 1,5,12-dodecanetriol trimethacrylate and the like. Based on a pigment, mineral filler and non-polymerizable solvent base the paint binder contains from about 15 to about 45, preferably about 20 to about 35 weight percent of any of the foregoing Acrylates or their mixtures.

The remainder of the paint binder solution, ie 3> 5 to 85% by weight of the total mass, consists of a paint binder resin with vinyl unsaturation and optionally monovinyl monomers. The vinyl resin used in this paint is a copolymer containing a vinyl monomer and comprises from about 15 to about 100 percent by weight of the remainder or make-up material. The monovinyl monomers comprise from 0 to 85, advantageously

5 to 85 and preferably 65 to 85% by weight of the remainder «Favorably these resins have an average molecular weight in the range from about 1,000 to about 25,000, preferably from 5,000 to 15,000

The vinyl resin used has more than about 0.5 and less than about 5 α, β-olefinically unsaturated units per 1000 molecular weight Right units, preferably about 0.7 to about J of such units per 1000 molecular weight units. A

109808/2259

preferred vinyl resin is made by copolymerization of acrylates, z. B. methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like. And one of the desired extent to the amount of glycidyl methacrylate corresponding to saturation manufactured. This is introduced in a second reaction stage by mixing the copolymer with acrylic acid or Methacrylic acid is implemented. Other vinyl resins are illustrated in the following examples.

The monovinyl monomer component can, if used, styrene, methyl methacrylate, ethyl acrylate, hydroxyethyl methacrylate, Butyl acrylate, butyl methacrylate, 2-ethylhexyl methacrylate, their mixtures and the like. Be.

As used herein, the term "paint" includes both the Binder including pigment and / or particulate! Filler, the binder without pigment and / or filler or only with a very small amount of it, and it may be colored if necessary. Thus, the binder that is finally converted into a permanent, wear-resistant film, all or practically all of it or it may be the mass used to form the film the carrier for pigment and / or particulate filler material be. It can be a volatile, non-polymerizable solvent which can be evaporated before hardening.

The following examples serve to further explain the Invention without limiting it.

example 1

An α, ß-olefinically unsaturated vinyl resin, Resin A, is described in made in the following manner;

I 09808 / 22Sd

Starting materials parts by weight

Xylene 600

Methyl methacrylate 196

Ethyl acrylate 333

Glycidyl Methacrylate · 71

Azobisisobutyronitrile 6

Hydro quinone 0.12

Methacrylic acid ^ 2

Triethylamine 0.96

procedure

The xylene is used as a solvent in a Addition funnel, thermometer, nitrogen inlet tube and Introduced flask equipped with a cooler. The amount of xylene is equal to the total weight of the vinyl monomers to be added. The xylene is heated to reflux and nitrogen is passed through the solution during the heating and during the reaction blown. The combined monomers with the exception of methacrylic acid and initiator (azobisisobutyronitrile) are added evenly to the refluxing solution over a period of 2 hours. The weight of the initiator is 10 parts by weight per 1000 parts by weight Vinyl monomers. The reaction solution is kept under 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, and then the methacrylic acid is used to react with the Epoxy groups of the polymer added. Triethylamine is used as a catalyst. This esterification reaction is at Reflux temperatures carried out until about 80% esterification is reached, determined by the remaining acid number. The xylene is then distilled off in vacuo and that Polymers obtained.

109808 / 22SI

Comparison attempt 1

A paint binder solution is prepared from 25 parts by weight of Resin A and 75 parts by weight of methyl methacrylate. This solution is applied to the surface of various polyolefin substrates to an average depth of about 25 M (0.001 inch) and irradiated in a nitrogen atmosphere with an electron beam having an average energy of 275,000 EV and a current of 25 milliamps until the coating has a total dosage of about 12 Mrad is exposed.

The term "rad" means a dose of radiation that the Absorption of 100 ergs of energy per gram of absorber, for example of the coating film results. The abbreviation "Mrad" used here means 1 million rad. The electron emitti he one direction can be an electron linear accelerator, which is suitable for developing a direct current potential in the range from about 100,000 to about 500,000 volts. In such a Device are usually made of electrons sent out by a hot thread and by a unified one Accelerated voltage rise. The electron beam is about 4 mm (1/8 inch) in diameter at this point can then be focused on a funnel-shaped beam and then through a metal window, for example made of a magnesium-thorium alloy, aluminum, one Alloy made of aluminum and a smaller proportion of copper and the like, about 0.07 mm (0.003 inch) thick be guided. The irradiation is preferably carried out in one practically oxygen-free atmosphere, e.g. B. nitrogen, helium nndögl.

The coatings are subjected to a standard adhesion test, which is identified and described in detail below and the results are shown below:

10930 8/2259

Table I.

Adhesion test - paint batch I resin A * 25% - methyl methacrylate 75 %

Substrate Adhesion,%

Polypropylene O

Propylene-ethylene copolymer O

High density polyethylene o

Comparison attempt 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 ' that the monovinyl monomer is reduced to 50 parts by weight will. The adhesion test is performed on the cured coatings as indicated above, and the results are reproduced below:

Table II

Adhesion test - paint batch II 'resin A 50% - methyl methacrylate 50 %

Substrate Adhesion, %

Polypropylene 0

Propylene-ethylene copolymer 0

High density polyethylene o

Comparison experiment 3

A third attempt is made using the same procedure performed with the exception that in the coating binder solution the vinyl monomer component is changed to butyl acrylate. The adhesion test is carried out as

109808/2259

"in the previous tests on the hardened coatings. The results are given below;

Table III

Adhesion test - paint batch III resin A 50 % - butyl acrylate 75 %

Substrate Adhesion, %

Polypropylene Ό

Propylene-ethylene copolymer es 0 i

High density polypropylene O

Comparison attempt 4

A fourth attempt is made using the same Procedure with the exception that 2-ethylhexyl acrylate is used as the vinyl component in the paint binder solution will. The adhesion test is carried out on the cured coatings as in the previous tests. the Results are given below:

Table IV

Adhesion test - paint batch IV resin A 50 % - 2-ethylhe3q7lacrylate 50 %

Substrate Adhesion, %

Polypropylene 0

Propylene-ethylene copolymer 0

High density polyethylene 0

Comparative smoking ^

A fifth attempt is made using the same procedure except that in the paint

109808/2251

binder solution the resin component is increased to 75% by weight and that the monovinyl monomer is reduced to 25 parts by weight will. The adhesion test is carried out, as in the previous tests, on the cured coatings, the results are reproduced below:

Table V

Adhesion test - paint batch V resin A 75 % - methyl methacrylate 25 %

Substrate. Adhesion,%

Polypropylene O

Propylene-ethylene copolymer O

High density polyethylene o

Matching attempt 6

A sixth attempt is made using the same procedure except that in the paint binder solution the resin component is reduced to 15 parts by weight and that the monovinyl monomer is increased to 85 parts by weight will. The adhesion test is carried out, as in the previous tests, on the cured coatings. The results are reproduced below:

Table VI

Adhesion test - paint mixture VI resin A 15 % - methyl methacrylate 85 % substrate adhesion, %

Polypropylene O

Propylene-ethylene copolymer O Polyethylene O

109808/2259

After the lack of adhesiveness of paint compositions Vinyl resin and monovinyl monomer above in various Resin concentrations and with different monomers was shown, is the first attempt according to the invention using the same procedure with the exception carried out that the paint binder solution 25 parts by weight Resin A, 45 parts by weight of methyl methacrylate and 30 parts by weight Contains Athandiöl (ethylene glycol) dimethacrylate. The adhesion test takes place, as in the previous tests, on the cured coatings, and the results are shown below * listed «

Table VII Adhesion Test - Paint Batch VII

Resin A 25 % - methyl methacrylate 45 % ethanediol dimethacrylate 30 %

Substrate adhesiveness, #

Polypropylene 100

Propylene-ethylene copolymer 100

High density polyethylene 100

Example 2

To get the required amounts of diacrylates used here and triacrylates to investigate and the suitability of various To investigate diacrylates and triacrylates of the types listed above, further experiments are carried out.

An eighth attempt is made using the same procedure as carried out in the previous experiments with the exception that the paint binder solution was 25 parts by weight Hare A, 70 parts by weight of methyl methacrylate and 5 parts by weight of ithfm contains dibt dimethacrylate. The adhesion test is carried out as in the previous experiments, on the hardened

109808/2269

gen, and the results are given below:

Table VIII Adhesion test - coating approach VIII

Resin A 25% - methyl methacrylate 70 % ethanediol dimethacrylate 5 %

Substrate Adhesion, %

Polypropylene 10

Propylene-ethylene copolymer 5

High density polyethylene 0

A ninth attempt is made using the same procedure as in previous experiments with the exception of carried out that the paint binder solution 25 parts by weight Resin A, 70 parts by weight of methyl methacrylate and 5 parts by weight Contains 1,4-butanediol dimethacrylate. The adhesion test is carried out, as in the previous tests, on the cured coatings, and the results are given below:

Table IX Adhesion test - paint approach IX

Resin A 25% - methyl methacrylate 70 % 1,4-butanediol dimethacrylate 5%

Substrate Adhesion, %

Polypropylene 15

Propylene-ethylene copolymer 15

High density polyethylene 5

A tenth run was carried out using the same procedure as in the previous runs except that the paint binder solution was 15 parts by weight

109808/2250

Resin A, 80 parts by weight of methyl methacrylate and 5 parts by weight of ethanediol dimethacrylate contains. The adhesion test is carried out, as in the previous tests, on the cured coatings, and the results are given below:

Table X

Adhesion test - paint approach X

Resin A 15 % methyl methacrylate 80% ethanediol dimethacrylate 5 %

Substrate Adhesion, %

Polypropylene 15

Propylene-ethylene copolymer 10

High density polyethylene 5

An eleventh attempt is made using the same procedure as in the previous experiments with the exception carried out that the paint binder solution 25 parts by weight Resin A, 65 parts by weight of methyl methacrylate and 10 parts by weight Contains ithanediol dimethacrylate. The adhesion test is carried out as in the previous experiments, on the cured coatings, and the results are given below:

Tabel Adhesion test - paint approach XI

. Resin A 25% - methyl methacrylate 65% ithanediol dimethacrylate 10%

Substrate · * »Adhesion, %

Polypropylene 30

Propylene-ethylene copolymer JO

High density polyethylene 15

109808/2259

A twelfth attempt is made using the same procedure as carried out in the previous experiments with the exception that the paint binder solution was 25 parts by weight Resin A, 60 parts by weight of methyl methacrylate and 15 parts by weight 1, A-butanediol dimethacrylate contains. The adhesion test is carried out as in the previous tests on the cured coatings, and the results are given below J

Table XII Adhesion test - paint approach XII

Resin A 25 % - methyl methacrylate 60 % 1, ^ - butanediol dimethacrylate 15 %

Substrate 'Adhesion, %

Polypropylene 60

Propylene-ethylene copolymer 50

High density polyethylene 40

A thirteenth attempt is made using the same procedure as in previous experiments and with the Exception carried out that the paint binder solution 50 parts by weight of resin A, 35 parts by weight of methyl methacrylate and Contains 15 parts by weight of 1,4-butanediol dimethacrylate. The adhesion test is carried out, as in the previous experiments, on the cured coatings, and the results are as follows the reproduced:

Tabel XIII Adhesion test - paint approach XIII

Resin A 50 % - methyl methacrylate 35 % 1,4-butanediol dimethacrylate 15 %

Substrate Adhesion, %

Polypropylene 50

Propylene-ethylene copolymers 45

High density polyethylene 30

109808/2261

·. = -. ■■■ · ■ ■ - 15 - ■■ ■;.

A fourteenth run is made using the same procedure as the previous runs except that the paint binder solution is 50 wt. parts resin A, 35 parts by weight butyl acrylate and 15 parts by weight ■ Contains 1,4-butanediol dimethacrylate. The adhesion test is carried out, as in the previous tests, on the cured coatings, and the results are listed below:

Table XEV

Adhesion test - paint approach 3GEV λ

Resin A 50 % - butyl acrylate 35 % 1,4-butanediol dimethacrylate 15 %

Substrate Adhesion,%

Polypropylene 60

Propylene-ethylene copolymer 45

High density polyethylene 30

A fifteenth attempt is made using the same Procedure carried out as in the previous experiments with the exception that the paint binder solution was 50 parts by weight Resin A, 35 parts by weight of 2-ethylhexyl acrylate and 15 parts by weight 1, ^ - butanediol dimethacrylate contains. The adhesive- '' 1 The strength test is carried out on the cured coatings, as in the previous tests, and the results are given below reproduced:

109808/2259

- 16 Table 3CV

Adhesion test - line approach XV

Resin A 50 % - 2-ethylhexyl acrylate 35 % 1,4-butanediol dimethacrylate 15%

Substrate Adhesion,%

Polypropylene 65

Propylene-ethylene copolymer 55

High density polyethylene 35

A six-tenth experiment is carried out using the same procedure as in the previous tests with the exception that the Ans trichsbinderlösung 15 parts by weight of Resin A, 35 parts by weight of methyl methacrylate, 35 parts by weight of '2-lthylhexylacrylat and 15 parts by weight Contains ethanediol dimethacrylate. The adhesion test is carried out, as in the previous tests, on the cured coatings, and the results are given below:

Table XVI Adhesion Test - Paint Approach XVI

Resin Λ 1J> % - methyl methacrylate 35 %

2-ethylhexyl acrylate 35 % 1, f-butanediol dimethacrylate 15 %

Substrate Adhesion, %

Polypropylene 95

Propylene-ethylene copolymer 95

High density polyethylene 90

A seventeenth test is carried out using the same procedure as in the previous tests with the exception that the paint binder solution is 50 parts by weight of Resin A, 35 parts by weight of methyl methacrylate and 15 parts by weight.

109808/2259

parts contains 1,6-hexanediol dimetliaerylate. The adhesion test is carried out, as in the previous tests, on the cured ones Coatings, and the results are given below:.

• table XVII

Adhesion test - paint approach ZVII

Resin A 50 % - methyl methacrylate 35 % 1, ö-hexanediol diniethacrylate 15 %

Substrate Adhesion, %

Polypropylene 65

Propylene-ethylene copolymer 65

High density polyethylene 60

An eighteenth attempt is made using the same Procedure carried out as in the previous experiments with the exception that the paint binder solution was 25 parts by weight Resin A, 55 parts by weight of methyl methacrylate and 20 parts by weight Contains ethanediol dimethacrylate. The adhesion test takes place, as in the previous tests, on the cured coatings, and the results are given below! '- ■ .. ■' ■

Table XVIII Adhesion test - paint approach XVIII

Resin A 25% - methyl methacrylate 55% ithanediol dimethacrylate 20 %

Substrate Adhesion, % -

Polypropylene 100

Propylene-ethylene copolymer 100

High density polyethylene 85

109808/2259

A nineteenth test is carried out using the same procedure as in the previous tests with the exception that the paint binder solution contains 50 parts by weight of Resin A, J> 0 parts by weight of methyl methacrylate and 20 parts by weight of 1,1-butanediol - Contains dimethacrylate. As in the previous tests, the adhesion test takes place on the cured coatings, and the results are given below:

gabeile ΣΙΧ

Adhesion test - paint approach XIX

Resin Jl 30% - methyl methacrylate 30% 1,4-butanediol dimethacrylate 20 %

Substrate 'Adhesion, %

Polypropylene 90

Propylene-ethylene copolymer 90

High density polyethylene 80

A twentieth run is carried out using the same procedure as in the previous runs except that the paint binder solution contains 25 parts by weight of Resin A, 55 parts by weight of methyl methacrylate and 20 parts by weight of 1,6-hexanediol diacrylate. The adhesion test is carried out, as in the previous tests, on the cured coatings _; and the results are given below:

Table Σ £

Adhesion test - paint batch XX

Resin JL 25 % - methyl methacrylate 55 % 1,6-hexanediol dimethacrylate 20 ^

Substrate adhesiveness

Polypropylene 100

Propylene-ethylene copolymer 100

High density polyethylene ~ 85 ^

A twenty-first attempt is made using the gleieben Procedure as in the previous experiments with the Exception carried out that the paint binder solution 50 wt. parts of resin A, 30 parts by weight of methyl methacrylate and 20 parts by weight Contains ethanediol diaethacrylate. The adhesion test is carried out, as in the previous tests, on the cured ones Coatings, and the results are shown below

Table YXL

Adhesion Test - Paint Approach XI I

Resin A 50 % - methyl methacrylate ^ O % ethanediol dimethacrylate 2D '%

Substrate 'Adhesion, %

Polypropylene 80

Propylene-ethylene copolymer 75

High density polyethylene 60

A twenty-second attempt is made using the same procedure as in previous experiments with the, Exception carried out that the paint binder solution 50 parts by weight Resin A, 30 parts by weight of methyl methacrylate and 20 parts by weight Contains tetraethylene glycol diethacrylate. The detention

109808/2259

-20-2033652

The ability test is carried out as in the previous experiments, on the cured coatings, and the results are given below:

Table XEEI Adhesion test - paint batch XXII

Resin A 50 % - methyl methacrylate 30% tetraethylene glycol dimethacrylate 20 %

Substrate Adhesion, %

Polypropylene 90

Propylene-ethylene copolymer 90

High density polyethylene 80

becomes a twenty-third attempt / using the same Procedure carried out as in the previous experiments with the exception that the paint binder solution was 75 parts by weight Resin A, 5 parts by weight of methyl methacrylate and 20 parts by weight Contains ethanediol dimethacrylate. The adhesion test is carried out, as in the previous tests, on the cured ones Coatings, and the results are given below:

Table XKIII Adhesion test - paint approach XXIII

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

Substrate Adhesion, %

Polypropylene 80

Propylene-ethylene copolymer 70

High density polyethylene 65

109808/2259

A twenty-fourth attempt is made using the same Procedure carried out as in the previous experiments with the exception that the paint binder solution 25 Parts by weight of resin A, 45 parts by weight of methyl methacrylate and 30 parts by weight Contains 1,6-hexanediol dimethacrylate. The adhesion test is carried out, as in the previous experiments, on the cured coatings, and the results are as follows reproduced:

Table XXEV Adhesion test - attack approach XXIV

Resin A 25 ⁰ A - methyl methacrylate 45 % 1,6-hexanediol dimethacrylate JO %

Substrate adhesiveness, #

Polypropylene 100

Propylene-ethylene copolymer 100

High density polyethylene 100

A twenty-fifth attempt is made using the same procedure as in previous experiments 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 diethylene glycol dimethacrylate. Of the Adhesion testing is done on the cured coatings, as in previous experiments, and the results are reproduced below:

109808/2259

2033652

Table XXV Adhesion test - paint approach XXV

Resin A 25% - methyl methacrylate 45 % diethylene glycol dimethacrylate 50%

Substrate adhesiveness,

Polypropylene 100

Propylene-ethylene copolymer 100

High density polyethylene 100

A twenty-sixth attempt is made using the same procedure as in previous experiments performed except that the paint binder solution 25 parts by weight of Harz'A, 45 parts by weight of methyl methacrylate and Contains 50 parts by weight of tetrapropylene glycol dimethacrylate. Of the Adhesion testing is done on the cured coatings, as in previous experiments, and the results are reproduced below:

Table XXYI Adhesion test - paint approach XXVI

Resin A 25 % - methyl methacrylate 45 % tetrapropylene glycol dimethacrylate 50 %

Substrate Adhesion,%

Polypropylene 100

Propylene-ethylene copolymer 100

High density polyethylene 100

A twenty-seventh attempt is made using the same procedure as in previous experiments performed except that the paint binder solution 25 parts by weight of resin A, 45 parts by weight of methyl methacrylate and Contains 50 parts by weight of trimethylolpropane triacrylate. The detention

103808/2259

Capability test is carried out on the cured coatings, as in the previous tests, and the results are in 'following., reproduced!

Table IXVII Adhesion test - paint approach XXVII

Resin A 25 % - methyl methacrylate A5 % trimethylolpropane triacrylate 30 %

Substrate Adhesion, %

Polypropylene 100 |

Propyl-ethylene copolymer High density polyethylene

A twenty-eighth attempt is made using the same procedure as in the previous experiments with the Exception carried out that the paint binder solution Parts by weight of resin A, 45 parts by weight of methyl methacrylate and JO Parts by weight 1,5,12-dodecanetriol trimethacrylate contains · The Adhesion test is carried out as in the previous tests, on the cured coatings and the results are given below:

Table SXVIII Adhesive test - paint application XXVIII

Resin A 25 % - methyl methacrylate 5 % 1,5,12-dodecanetriol trimethacrylate $ 0%

Substrate adhesiveness,

Polypropylene 100

Propylene-ethylene-Oopolyiieres 100

High density polyethylene 100

A twenty-ninth attempt is made using the same procedure as in the previous experiments

109808/2259 ^ ° ^R1QiNAt

_ 24 _ 2033652

except that the paint binder solution 25 parts by weight of resin *., 30 parts by weight of ethyl methacrylate and Contains 4-5 parts by weight of ethanediol dimethacrylate. The adhesion test takes place, as in the previous tests, on the cured coatings, and the results are in reproduced the following:

Table XXIX Adhesion test - imstrichcansatz XXIX

Resin Ä 25 ⁰ Jo - methyl methacrylate 30 % ethanediol dimethacrylate 4-5 %

Substrate Adhesion,%

Polypropylene 100

Propylene-ethylene copolymer 100

High density polyethylene 100

Example 5

A dreissigster test is carried out using the same procedure as in the previous experiments with the Ausr.ahiae that the itnstrichsbinderlösung contains 60 parts by weight teiie resin jl and Mj parts by weight of i-tLandiol dimethacrylate. The adhesion is obtained according to the tests in Example 2, the Juistrich binder solution containing at least 20% by weight of diacrylate.

Example 4

The procedure according to Example 1 is repeated with the only difference that the electrons of the electron beam have an average energy of 350,000 EV.

109808/2259

2030652

Example 5

The procedure of Example 1 is used with the only difference repeats that the irradiation atmosphere is made of helium.

Example 6

The procedures of Examples 1 and 2 are repeated with the only difference that resin A is replaced by resin B. Resin B is prepared from the following ingredients in the manner described below: '. "

Level I parts by weight

Ethyl acrylate 38.8

Methyl methacrylate 23.2

Allyl glycidyl ether 37.0

Benzoy peroxide ■ 1.0

Xylene solvent

An amount of xylene is poured into a reaction vessel equipped with a condenser, thermometer, stirrer and dropping funnel corresponding to the weight of the in the first reaction stage Introduced to be added reactants. The Xylene ™

is heated to about 100 to 120 ° 0. The four reactants are mixed thoroughly and added to the heated one Xylene for a period of 4 hours through a Dropping funnel added slowly. 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 implemented in the following way:

109808/2259

_ 26 - 2033652

Level II 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 vdrd 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 then let it cool down. The reaction mixture from Binderpolymerei ^ is heated to about 60 ° G, and the xylene and excess fieaktionsmittel are distilled off in vacuo.

Example 7

The procedures of Examples 1 and 2 are repeated with the only difference that the Rbtz A is replaced by resin C. Resin C is produced from the following components in the whiteness described below:

Level I parts by weight

Ethyl acrylate 39

Methyl methacrylate 24

Allyl alcohol 36

Benzoyl peroxide 1

Xylene solvent

In one with a cooler, Thermometez *, earphone and drip funnel equipped heating vessel becomes a quantity of xylene according to the weight of the participants to be added in the first reaction stage. The xylene is heated to about 100 to 120 ° 0. The four reaction materials are mixed thoroughly and slowly passed through one Adding funnel to the heated xylene for a period of time of 4 hours added. The reaction is at this temperature

109808/2259

Maintained temperature for 1 to 2 hours after the addition is complete is, and then allowed to cool to room temperature.

The copolymer formed by this process will continue ii. implemented in the following way:

Level II parts by weight

.Copolymers ^ from stage I 69

Allyl glycidyl ether 50.8

Potassium hydroxide 0.2

A solution * from the AiIylglyeidyläther and potassium hydroxide v; is added to the copolymer at room temperature. That Mixture is then heated to a temperature of 100 to 120 ° G heated. This temperature is maintained for about 7 hours, . and you. lets cool. The reaction mixture of binder polymers is heated to about 60 ° C, and the xylene and excess reaction agent are distilled off in vacuo.

Example 8.

The procedures of Examples 1 and 2 are the only ones Difference repeats that Resin A is replaced with Resin D. will. Resin D is made up of the following ingredients in the manufactured in the manner described below:

Level I parts by weight

Methyl methacrylate 400

Ethyl acrylate 400

Hydroxyethyl methacrylate 195

Toluene 1000

Benzoyl peroxide 30

The benzoyl peroxide is in a solution of the methyl methacrylate, ethyl acrylate and hydroxyethyl methacrylate and the

100808/2259 _ßAD

203U652

Half of the toluene dissolved. This solution is then partial to which reads the toluene under reflux for a period from 7 hours at a terminal bubble temperature of about 18 "to 140 ° G. The reflux treatment is continued 3 hours "and the solution cooled.

Stage II. Weighted parts

Solution from level I 500

iLcrylyl chloride 33 <> 8

Toluene 30

The solution at stage i is heated to 60 ° C and a solution of the acrylyl chloride and toluene is added dropwise over a period of 4 hours while the temperature is allowed to rise to about 90 ° C. The solution will be to: a vacuum before: below 10 rc ™. Subjected to Hr at ^r / 0 ° C, and the Acrylpolyr-ero becomes _l c \ ..: ji.u-. The coatings obtained according to Examples 4-8 also showed excellent adhesion

_T. "_ _. ...... _ ability

Dxe naftfaiiXgiic-xr v. ^ Ra m sa.ntiiojj.en examples ir. Acr ιόΊτ-free-der. Veise {jeprüf ^: Kreuzfjchixiut - parallel lines err; itbetand 1.6 mm (1/16 inch) v / ground on the "coating under Daicb-sclir.oicunc; eic ziii substrate einresciiriitteri. Veitorc parallel lines i ~. spacing of 1.6 mm (1/16 inch ) v / eroon in the same. Weine iia right. angle to the first group UT-d these intersecting incised. Cellophane tape is applied cexji over the oir-ger: ^ ij.iotene surface and removed. The Eaf'uimg v. 'ith the AUC "tir.zaLi iijistriehr; squares that in the pasted;... or remain iioreich, ir relation to the remote Ijistrichrcuadrate gerr.esser .. in all the experiments used with DOR same Haftcualität band There v.. .'ird ir_ söl. "Glichen Vr.-i-cucher. applied in the same way to the overdrawn surface ur.c. away from it.

109808/2259

Claims (7)

Claims 1. commodity containing a polyolefin substrate made of polypropylene, polyethylene and / or copolymers of propylene and ethylene and a coating that adheres firmly to an outer surface of the substrate, characterized in that the coating has the polymerization product formed in situ from a film-forming solution, which by Exposure to a beam of polymerization-triggering electrons with an average energy in the range from about 100,000 t to about 500,000 EV ... is crosslinked, the film-forming solution being free of pigment and particulate! J ¹ UlIstoff, essentially from (A) about 15 to about 45 wt.% Diacrylates and dimethacrylates of an alkanediol with 2 to 12 carbon atoms, diacrylates and dimethacrylates of a polyether diol with 2 to 12 carbon atoms and / or triacrylates and trimethacrylates of a triol with 6 to 12 carbon atoms and (B) 55 to 85 wt.% of a Vinylliarz component containing from 0 to about 85 wt.% Monovinylmonqmeren and about 15 to 100 wt.% of an oc, ß-olefinically unsaturated vinyl monomer corresponds μ holding copolymers is provided between about 0.5 and about 5 alpha, beta-olefinic. unsaturated :. Contains units ge 1000 molecular weight units. 2. The article of use according to claim 1, characterized in that the acrylate makes up between about 20 and about J5 % of the film-forming solution. 3. commodity according to claim. 1 to 2, characterized in, that the vinyl resin-containing component consists of 15 to 75% by weight of the copolymer and 85 to 25% by weight Monoviny! Monomers consists. 109808/2259 . , ο - 2033652 4. commodity according to claim 1 to 3 »characterized in that the copolymer between about 0.7
about 3 α, β-olefinically unsaturated units per 1000
Contains molecular weight units. 5- commodity according to claim 1 to 4-, characterized in that that the film-forming solution by electrons with an average energy in the range of about 150,000 to about 450,000 EV has been crosslinked. 6. commodity according to claim 1 to 5i, characterized in that that the coating has been polymerized in a practically oxygen-free atmosphere. 7. commodity according to claim 1 to 6, characterized in that the vinyl resin-containing component consists of 15 to 35 parts by weight of copolymer and 65 to 85% by weight
Vinyl monomers. 109808/2259