DK146047B - POLYMERIZABLE MATERIALS FOR PREPARING COATS WITH GOOD SPOTTING, SCREAM AND SCRAP FACTOR, AND METHOD OF PRODUCING THEREOF - Google Patents

Description

146047

The present invention relates to a polymerizable material for preparing coatings having good stain, scratch and scratch resistance and consisting of one or more monomers which are diesters of a diol with one or two organic acids. The invention also relates to a process for preparing the polymerizable material.

According to the invention, the polymerizable material consists of (a) at least one compound of the general formula R11 CH, CH, R11

I I 3 I 3 I

ch2 = c-co-and2-c-ch2-o-co-c-ch2o-oc-c = ch2 I

wherein R 11 is a hydrogen atom or a methyl group and / or (b) at least one compound of the general formula CH, CH, 9

R C0 ~ 0CH, -C-CEL-0-C0-C-CH-0-0CR II

I I

CH3 CH3 R11

9 10 I

wherein one of the groups R and R is a group of the formula -C = CH_ 11 Z where R is as defined above and the other of the groups R and R is a substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl group, and optionally (c) one or more compounds of the general formula CH, CH, 9 · 1 J 10

R C0-0CHo-C-CH, -0-C0-C-CH, 0-0CR III

2 t 2, 2 CH 3 CH 3 9 10 where R and R have the meaning given above except for a group -C = CH 2.

lu

R

Particularly advantageously according to the invention, the polymerizable material consists of 2.5-35% by weight of one or more compounds of formula I, 30-95% by weight of one or more compounds of formula II and 2.5-35% by weight of a or more compounds of formula III.

According to the invention, the polymerizable material is prepared in the manner specified in claim 3. Thus, hydroxypivalyl hydroxypivalate having the formula CH-CH, I 3 is reacted | 3

HOCH-CCH, OCOCCH ~ OH

CH 2 CH 3 CH 3 with acrylic acid, methacrylic acid or an acid anhydride or acid chloride thereof, and optionally also with a non-polymerizable aliphatic, alicyclic or aromatic monofunctional acid; Reactions occur at a temperature of 50-150 ° C in the presence of an acid catalyst and optionally an inhibitor, and the acrylic compound is added gradually and in such a way that the molar ratio of the total amount thereof to hydroxypaviolyl hydroxypilate is in the range of 1.5: 1 and 1: 5 and the mole ratio of the total amount of acid to said diol is in the range of 2: 1 to 10: 1.

According to the invention, the gradual addition of the acrylic compound is conveniently done by first adding approx. half of the total amount of the acrylic compound to the diol, then the remaining amount thereof is added over 1/4 to 6 hours. The reaction product of the hydroxypivalyl hydroxypivalate and acrylic compound is an acrylic monomer which can be polymerized by ionizing radiation, with actinic light or by the use of free radical-forming catalysts, and the resulting polymer is a hard, scratch resistant material.

The acrylic monanes, alone or together with compounds II and / or compounds III, are highly radiation sensitive. When exposed to low doses of ionizing radiation or actinic light or to free radical-forming catalysts, they polymerize to extremely strong and stain resistant material. These hardened materials have excellent resistance to severe stain tests and are resistant to scratches and scratches.

British Patent No. 1,135,647 discloses esters of trimethyl-1,6-hexanediol with α, β-unsaturated aliphatic monocarboxylic acids having preferably 3-6C atoms and especially acrylic, methacrylic or crotonic acid and optionally a saturated aliphatic C1 -18 monofcerboxylic acid. The compounds should be used as lubricating oil additives or monomers by homo- or copolymerization. The script does not really say what the polymers thus produced can be used for, but it does not appear to be coatings, at least not coatings which are cured and polymerized in situ on the substrate on which the coating is to be formed, such as the present polymerizable material. .

Trimethyl-1,6-hexanediol diacrylate is not an readily available compound, and here it is therefore preferred to make comparative experiments between 1,6-hexanediol diacrylate (HDDA) as a reasonable substitute therefor and thus representative of prior art, and acryloxypivalyl acryloxypivalent ( APAP) as representative of the subject monomer of formula, i. Report on the experiments is shown below, the test technique being also described in these comparative experiments.

Comparative Experiment Experiment 1

Two coating compositions were prepared from the following ingredients:

Preparation A: 95% by weight 1,6-hexanediol diacrylate (HDDA) 5% by weight isobutylbenzoin ether (IBBI)

Preparation B: 95% by weight acryloxypivalylacryloxypivalate (APAP) 5% by weight isobutylbenzoin ethers (IBBE)

The two compositions were individually applied to aluminum panels at a thickness of approx. 0.025 mm. A number of panels thus coated were brought once or three times at different speeds into the air under four medium pressure ultraviolet light emitting mercury vapor lamps, all operating at approx. 200 watts / 2.54 cm, at a distance of approx. 7.6 cm. Several other of the coated panels were once passed at different speeds in nitrogen (oxygen content: about 15 volumes of oxygen per million parts of gas mixture) under one medium-pressure ultraviolet light emitter, the mercury vapor lamp operating at approx. 200 watts / 2.54 can, at a distance of approx. 7.6 cm.

After the ultraviolet light treatment, the coatings were evaluated by the pencil hardness test by testing the following set of pencils in order of increasing hardness: 4B (softest), 3B, 2B, B, HB, F, H, 2H, 4H, 5H, 6H and 7H (hardest). The panels were also evaluated in terms of surface hardening.

The speed at which the panels were conducted under the mercury lamp (s), the curing atmosphere used and the observations made are listed in Table 1.

Table 1

Transport- Passa- Pencil hardness and surface hardening speed, m / min. prepares preparation A preparation B

• _95% HDDA 5% IBBE 95% APAP 5% IBBE

Air 6.1 L H; note 1 2H; note 1 cure 8.2 l Ff note 1 H; note 1 9.1 1 Ff note 1 Hf note 1 _6,1_3_4Hf note 2_4H ·, note 2_

Nitrogen 15.2 1 HBf note 2 Hf note 2 hardening 3o, 5 1 4Bf note 3 HBf note 2 45.7 1 4Bf note 3 Bf note 2 _61.0 1 4Bf note 3 4Bf note 4

Note 1 - Sticky, unacceptable surface

Note 2 - Cured throughout incl. non-sticky surface Note 3 - Dry surface, but insufficient curing of the coating f The coating can be removed with a fingernail.

Note 4 - The cure is marginal

Experiment 2

Two coating compositions containing the following ingredients were prepared:

Preparation C: Commercial resin preparation (also containing a photoengineer) constitutes 80% of the binder, and 1,6-hexanediol diacrylate (HDDA) constitutes 20% by weight of the binder.

Titanium dioxide (rutile) - weight ratio pigment / binder = 0., 5 146047 5

Preparation D: Commercial resin preparation (also containing a photo initiator) constitutes SO% by weight of the binder, and Acryloxypivalylacryloxypivalate constitutes 20% by weight of the binder

Titanium dioxide (rutile) - pigment / binder weight ratio = 0.5

The resin and photoiganger and their relative amounts were similar in both the two compositions C and D. The two compositions were applied as coatings to panels in such a way that the thickness of the coating after curing would be in the range of 0.038-0.051 mm. All of the coated panels were airborne a number of times under medium-pressure ultraviolet light-emitting mercury vapor lamps, all working with approx. 200 watts / 2.54 cm, and at a distance of approx.

7.6 cm, according to the following diagram: one passage with 24.4 m per square meter. per minute, two passes at 12.2 m per minute. per minute and two passages with 6.1 m per minute. minute.

Then the 60 ° gloss of all panels thus treated was measured. The results are listed in Table 2.

Table 2

Coating composition 60 ° gloss, per cent.

C 95 D 99+

The panels were exposed to weather in an outdoor facility in Ft. Lauderdale, Florida, USA, for 15 months. Below, the 60 ° gloss was measured at intervals and the percentage retention of the original 60 ° gloss was determined. The time intervals and results are shown in Table 3.

Table 3

Coating- Preservation of 60 ° gloss, per cent. of original 60 ° gloss preparation after 3 after 6 after 9 after 12 after 15 _ months months months months months_ C 68 49 26 13 7 D 79 65 44 25 30 6 146047

The results shown in the two comparison experiments show that oxygen tends to inhibit surface curing of APAP. In this connection, it should be noted that the pencil hardness test is a measure of the degree of curing of the interior of the coating. It is not a measure of the degree of curing of the coating surface. The first comparison experiment illustrates this relationship.

In Table 1, where HDDA and APAP were exposed to ultraviolet light from four mercury vapor lamps in air at one pass, the pencil hardness of APAP was consistently greater than that of HDDA. In all cases where one passage was used, the surface did not cure sufficiently due to oxygen inhibition. Note that the pencil hardness went down as the carrier speed increased. It required three passes with the lowest transport speed to provide a 4h pencil hardness and a non-sticky surface when the treatment was done in air. This is about the same as exposure to four lamps at a speed of 2 m / min. The data cited show (1) that APAP is better than HDDA, (2) that both systems can have reasonable internal hardness even though the surface is unacceptably hardened, and (3) that oxygen inhibition can be overcome by massive exposure to ultraviolet radiation. A pencil hardness of H or 2H is acceptable for most applications.

The data shown in Table 1 also shows that APAP is better than HDDA in exposure to ultraviolet radiation from one lamp in nitrogen. As no significant amounts of oxygen were present, oxygen inhibition of the surface cure was not a factor here. The data provided shows that the pencil hardness decreases as the carrier speed increases. It is also seen that larger transport speeds and fewer lamps can be used in nitrogen than in air. Of course, this shows that less ultraviolet radiation is needed in nitrogen than in air.

APAP's superiority over HDDA is also evident in the second trial. The test data presented here shows (1) that the original luster of the preparation containing APAP was greater than the luster of the preparation with HDDA, and (2) that the preparation with APAP retained its luster much better than the composition with HDDA.

U® 047 7

Detailed description of the invention

The reaction between the diol and the acrylic compound occurs as mentioned at 50-150 ° C, preferably 95-100 ° C. The molar ratio of total acid to diol is, as mentioned, between 2: 1 and 10: 1, preferably such that 2-2.5 moles of acidic component is used per day. mol diol.

As an acid catalyst, for example, sulfuric acid, p-toluenesulfonic acid, phosphoric acid and / or hydrogen chloride can be used. The catalyst is usually present in an amount of 0.1-5% by weight of the reaction participants.

In most cases, a free radical-forming inhibitor is also used to prevent the reaction participants from solidifying. Any conventional free radical-forming inhibitor, e.g., hydroquinone, methylquinone or p-methoxyphenol, may be used. In-. the hibitor is usually present in a weight range of 0.1-5% by weight of the reaction participants.

The reaction is initiated by adding to the diol a portion of the acrylic compound, catalyst and inhibitor and heating.

As mentioned, it is desirable that the acidic component is added gradually to the mixture, e.g. 50% of the total amount of the acidic component together with the diol, while the remainder is then added over eg 1/4 to 6 hours, advantageously dropwise.

It has been found that if the acidic component is not added gradually, there is a tendency for polymerization in the reaction mixture, thereby substantially reducing the yield of the desired compound. Furthermore, the apparatus in which the reaction takes place is contaminated with polymer and it is difficult to purify the reaction product. If the acrylic compound is added at once, the monomer yield becomes much lower than by the above method. Optionally, a solvent may be used to form an azeotropic mixture with the water resulting from the reaction. Hereby the reaction is more easily completed. Any aliphatic, cycloaliphatic or aromatic hydrocarbon solvent may be used. Examples of particularly suitable solvents are hexane, pentane, cyclopentane, cyclohexane, benzene, toluene and xylene and mixtures thereof. Cyclohexane is particularly preferred.

8 146067

If a solvent is used, the reaction mixture advantageously contains 1-60% by weight thereof.

The present compounds of formula 1 may, with or without the presence of compounds II and III, be homopolymerized in the presence of free radical-forming catalysts or by irradiation, or may be copolymerized with other monomers such as acrylic monomers, e.g., alkyl acrylates and alkyl methacrylates, or may be added to other polymers and is used in the form of mixtures which cure together. Examples of polymers which can be blended with the acrylic monomers of the present invention are polyalkyl acrylates such as polyethyl acrylate, poly (2-ethylhexyl acrylate) and polybutyl acrylate to form more flexible products, and vinyl polymers and copolymers such as vinyl chloride-vinyl acetate copolymer flexible products. Cellulose polymers such as cellulose acetate butyrate (viscosity 0.5 sec) can be cured together with the acrylic monomers concerned to increase the flexibility of the resulting products. Thus, the compounds can be mixed with other monomers or polymers and the mixture can then be cured either using peroxide or by subjecting the mixture to actinic or ionic radiation.

A particularly flexible product is formed when a non-polymerizable monofunctional aliphatic, alicyclic or aromatic acid is included in the reaction mixture with the diol and acrylic compound, so that the monomer mixture produced is copolymerized by irradiation with actinic light or ionizing radiation or treating with a freezing radiator. . The polymers formed, which become more flexible, have also improved. right adhesion to many materials.

Any non-polymerizable, monofunctional aliphatic, alicyclic or aromatic acid may be used to react with the diol and acrylic compound. This acid is not itself polymerizable. Examples of such acids are acetic acid, butyric acid, benzoic acid, propionic acid, capric acid, 2-ethylhexanoic acid, octanoic acid, lauric acid, stearic acid, neo acids such as neodecanoic acid, oleic acid, cyclohexanecarboxylic acid, p-methylbenzoic acid, p-methoxybenzoic acid, p-methoxybenzoic acid chloroacetic acid, trichloroacetic acid and aminoacetic acid, as well as their anhydrides. The preferred non-polymerizable acids are acetic acid, butyric acid, 2-ethylhexanoic acid and benzoic acid.

The mole ratio between the acrylic compound and the diol can vary widely, but is usually between 1.5: 1 and 1: 5. It is preferred to use 1.5-0.75 moles of acrylic compound per day. mol diol.

The remaining portion of the acidic component is the non-polymerizable (aliphatic, alicyclic or aromatic) acid which is added as already mentioned in such an amount that the mole ratio of total acid amount to hydroxypivalyl hydroxypivalate is between 2: 1 and 10: 1, preferably between 2 , 0 and 2.4 moles total acid per mol diol.

Monomers of formula I can be polymerized by irradiation because they are extremely radiation sensitive. Radiation-sensitive monomers are difficult to prepare, and it is difficult to predict which monomers have this property. As used herein, the term "radiation" means high energy radiation and / or secondary energy radiation resulting from the conversion of electrons or other particle energies to X-rays or gamma rays. Although various radiation sources can be used for the desired purpose, such as X-rays and gamma rays, radiation provided by accelerating high-energy electrons has proved to be very suitable and economical in use while achieving very satisfactory results. However, any radiation irrespective of the radiation type and type of apparatus used can be used, provided that the ionizing radiation is equivalent to at least approx. 100,000 electron volts.

There is no upper limit to the electron energy supplied, but the desired effect can be achieved in practice without exceeding 20,000,000 electron volts. In general, the depth of penetration of the solid material under consideration is greater the higher the electron energy used. For other types of radiation, for example gamma and X-rays, energy systems equivalent to the above-mentioned electron-volt region are desirable.

The term "radiation" encompasses ionizing radiation and is defined as radiation containing energy at least sufficient to produce ions or to break down chemical bonds; it thus also includes radiation such as ionizing particle radiation as well as radiation of the type termed "ionizing electromagnetic radiation".

The term "ionizing particle radiation" is used to denote electron emitted or emitted by highly accelerating nuclear particles such as protons, neutrons, α-particles, deutrons and β-particles or analogs thereof, which are directed so as to project the particle into the mass to be irradiated. Charged particles can be accelerated by means of an electrical voltage difference by means of accelerators with resonant chambers, van der Graaf generators, betatrons, synchro- trons, cyclotrons, etc. Neutron emission can be achieved by bombarding a light metal such as beryllium with high-energy positive particles. Particle emission can also be achieved by using atomic miles, radioactive isotopes or other natural or synthetic radioactive materials.

Ionizing electronic radiation is produced when a metal cloud disk, e.g., of tungsten, is bombarded with electrons of appropriate energy content. This energy is allocated to the electrons by potential accelerators exceeding 0.1 million electron volts (m.s.). In addition to selective radiation, commonly called X-ray radiation, ionizing electromagnetic radiation is obtained by means of a nuclear reactor (mile) or using natural or synthetic radioactive substances, e.g. cobalt 60.

In the trade, there are various types of high-power linear accelerators, for example, "ARCO" ® accelerating wave accelerator type Model Mark I, operating at 3-10 million electron volts, and supplied by the High Voltage Engineering Corporation, Burlington, Massachusetts. , or other accelerator types disclosed in U.S. Patent No. 2,763,609 and GB Patent No. 762,953.

The subject monomers are polymerized at any total radiation dose of between 0.2 megarad and 20 megarad. A row is defined as the amount of radiation required to supply 100 g of erg per g of material being processed and a megarad is 10 rad.

146047 11

The total radiation dose is the total amount of radiation absorbed by the monomer. It has been found that the present monomers are polymerized into hard, scratch and stain resistant films using a total radiation dose of less than 4 megarads. The preferred radiation dose is between 0.5 and 10 megarad.

The subject monomers or mixtures thereof may also be polymerized and cured by a free radical mechanism where free-radical-forming catalysts are added and the monomer is heated for polymerization. Any conventional free radical-forming catalyst can be used, for example organic peroxides or hydroperoxides or esters thereof. Examples are benzoyl peroxide, tert-butyl perbenzoate, tert-butyl hydroperoxide, cumene hydroperoxide and azobis (isobutyronitrile). The catalyst is usually used in an amount of 0.1-5% by weight of the monomer or of the monomer mixture.

The monomer and catalyst are heated to cure. The curing temperature varies from monomer to monomer, but temperatures of 24-150 ° C are usually used.

In many cases, it is desirable to polymerize without the application of external heat, in which case an accelerator is usually added to the system instead. Suitable accelerators are cobalt salts such as cobalt octoate and cobalt naphthenate, and amine accelerators such as Ν, Ν-dimethylaniline, N-ethyl-N-hydroxyethyl-m-ethylaniline and N-propyl-N-hydroxyethyl-m-methylaniline.

The present acrylic monomers can also be cured together with other copolymerizable ethylenically unsaturated monomers or with polymeric material using the free radical-forming catalysts described above.

Polymers and copolymers made by polymerization of the present monomers are generally very useful as coatings. Thus, they can be used as protective coatings for wood to form wall panels, as coatings for plastic materials to form floor tiles and as coatings on metals such as aluminum and steel, and these coatings have the advantage of not being easily stained, scratch-resistant and scratch-resistant. , are weather resistant and have chemical resistance to acids and bases. Upon curing, crosslinking occurs extensively in the polymer. The coatings are also relatively flexible, especially if a non-polymerizable acid is used in the preparation of the polymer and is capable of forming a strong bond to various materials.

The coating can be formed by applying the monomer to the material to be coated in a conventional manner, for example using rollers, curtain coating, coating and spraying. The coated material is then cured either by the addition of peroxide to the coating or by exposure to actinic light or ionizing radiation. Many of the monomers have extremely low viscosity, so that the product is easily applied by coating a material.

Polymerization of the subject polymerizable material with ionizing radiation is preferred as it is extremely fast, avoiding the time-consuming baking step and no heating required, thereby avoiding the danger of high temperature damage to heat sensitive materials. Solvents are also avoided and thus the risk of toxic and / or explosive solvent vapors. Finally, the polymerization coating formed using ionizing radiation is more cross-linked and therefore stronger than the coating cured in a conventional manner.

The method according to the invention will be explained in more detail by means of the following exemplary embodiments.

Example 1

An acrylic monomer is prepared as follows: Into a reactor is placed 7140 g of hydroxypivalyl hydroxypipalate of the formula shown in claim 3, 1190 g of cyclohexane, 1324 g of acrylic acid, 62.2 g of sulfuric acid and 124.4 g of hydroquinone. The reaction participants are heated at reflux at 94 ° C and 3972 g of acrylic acid are added dropwise over 30 minutes at 98 ° C. The reaction takes place for a further 4 hours, during which time 2730 g of cyclohexane is added and 1235 g of water is distilled off. Acryloxypivalyl acryloxypivalate is obtained in a yield of 90% by weight after purification by washing.

Example 2 13 14 6 Ο Λ 7

A radiation-sensitive monomer is prepared as follows:

204 g of hydroxypivalyl hydroxypivalate, 47.4 g of methacrylic acid, 3.9 g of hydroquinone, 1.9 g of sulfuric acid and 50 g of cyclohexane are placed in a reaction vessel. The reaction participants are heated to reflux to 100 ° C and 142.1 g of methacrylic acid are added dropwise over 35 minutes. The reaction takes place for a further 3 1/2 hours, during which time 100 cm of cyclohexane is added and 28.6 g of water is distilled off. Methacryloxypivalyl methacryloxy pivalate is recovered after purification.

Example 3

A radiation-sensitive monomer is prepared as follows:

204 g of hydroxypivalyl hydroxypivalate, 19.8 g of acrylic acid, 23.7 g of methacrylic acid, 3.8 g of hydroquinone, 1.9 g of sulfuric acid and 50 g of cyclohexane are placed in a reaction vessel. The reaction participants are heated to 99 ° C and 59.5 g of acrylic acid and 71.1 g of methacrylic acid are added dropwise over 30 minutes. The reaction is continued for 5 hours, during which time 3 85 cm of cyclohexane is added and 34.5 g of water are collected. The resulting acrylate methacrylate is isolated and purified in the same manner as described in Examples 1 and 2.

Example 4

204 g of hydroxypivalyl hydroxypivalate, 33 g of acetic acid, 3.6 g of hydroquionone, 1.8 g of sulfuric acid and 50 g of cyclohexane are placed in a reaction vessel. The reaction participants are heated at reflux to 96 ° C for 1 hour and 118.9 g of acrylic acid are added dropwise over a 1/2 hour at 97 ° C. The reaction is continued at 97 ° C for an additional 4 1/2 hours, during which time 70 cm of cyclohexane and 30 g of water are distilled off. The resulting monomer is obtained in a 92 wt% yield after purification by washing. It has hydroxytal number 11.93 and Gardner-Holdt viscosity A-.

Example 5 14 146047

204 g of hydroxypivalyl hydroxypivalate, 34.3 g of benzoic acid, 4.2 g of hydroquinone, 2.1 g of sulfuric acid and 50 g of cyclohexane are placed in a reaction vessel. The reaction mixture is heated to 100 ° C for 5 hours and 40 minutes. 79.3 g of acrylic acid are then added dropwise over 20 minutes at 97 ° C to the reaction mixture. The reaction is continued at 96 ° C for an additional 4 1/2 3 hours. During the reaction, 120 cm of cyclohexane is added and 35.0 g of water is distilled off. The resulting monomer is obtained in a yield of 86.3% by weight after purification by washing. The product has neutral acid number, hydroxy number 31.71 and Gardner-Holdt viscosity D-E.

Example 6 204 g of hydroxypivalyl hydroxypivalate, 96.9 g of butyric acid, 3.8 g of hydroquinone, 1.9 g of sulfuric acid and 50 g of cyclohexane are placed in a reaction vessel and heated to 94 ° C. Add 79.3 g of acrylic acid over 1/2 hour. The reaction is continued for an additional 3 hours at 96 ° C. During the reaction, 70 cm 2 of cyclohexane is added and 38.9 g of water is distilled off. The resulting product is obtained in a yield of 88.4% by weight after purification by washing. The product had neutral acid number, hydroxytal number 10.3 and Gardner-Holdt viscosity A-.

Example 7 204 g of hydroxypivalyl hydroxypivalate, 79.3 g of 2-ethylhexanoic acid, 4 g of hydroquinone, 2 g of sulfuric acid and 50 g of cyclohexane are placed in a reaction vessel and heated to 99 ° C for 3 hours and 10 minutes. Then 118.9 g of acrylic acid is added over 30 minutes. The reaction is continued for 4 hours and 40 minutes. In the course of the reaction, 168 cm of cyclohexane and 2 g of sulfuric acid are added and 38 g of water is distilled off. The resulting monomer is obtained in a yield of 88.5% by weight after purification by washing. The product has hydroxytal 32.31 and Gardner-Holdt viscosity A-.

Example 8 204 g of hydroxypivalyl hydroxypivalate, 168.6 g of 2-ethylhexane, 4.4 g of hydroquinone, 2.2 g of sulfuric acid and 50 g of cyclohexane are placed in a reaction vessel and heated to 99 ° C for 20 minutes. Then, 79.3 g of acrylic acid are added dropwise over 1/2 hour. The reaction is continued for 5 hours at 98 ° C. During the reaction, 140 cm 2 of cyclohexane was added and 29.2 g of water was distilled off. The resulting monomer is obtained in a yield of 71.9 wt% after purification by washing. The product has an acid number of 5.56, hydroxytic number of 53.84 and Gardner-Holdt viscosity A-.

The following examples (9-12) are examples of applications.

Example 9

The acryloxypivalyl acryloxypivalate prepared by the method of Example 1 is cured as follows:

A steel plate is coated with a mixture of 100 parts by weight of acryloxypivalyl acryloxy equivalent of Example 1 (after hydroquinone has been removed) and 1 part by weight of cumene hydroperoxide. The mixture is heated in a nitrogen atmosphere at 77 ° C for 30 minutes. The resulting cured product is a hard, scratch-resistant film.

Example 10

The acrylic monomers prepared in Examples 1, 2, 3, 4, 6, 7 and 8 are cured by being subjected to ionizing radiation as follows:

The monomers are applied to aluminum plates and subjected to electron radiation at an accelerating voltage of 400 kilovolts and a tube current of 16 milliamps. The film receives a total radiation dose of 4 megarad. The cured films have excellent scratch resistance, are very tough and resistant to stains caused by ink, thimerosal and mustard.

Example 11

A mixture of 75 parts by weight of acryloxypivalyl acryloxypivalate prepared as in Examples 1 and 25 parts by weight of 2-ethylhexyl acrylate is copolymerized by exposing the mixture to electron beams at an accelerating voltage of 400 kilovolts and a tube current of 16 milliamps. The total radiation dose delivered to the mixture is 4 megarad. The resulting copolymer is hard, resistant to scratches and stained only to a very low degree by ink, thimerosal and mustard.

Example 12

The product of Example 4 is polymerized as follows:

A steel plate is coated with a mixture of 100 parts by weight of the product of Example 1 (after removal of hydroquinone) and 1 part by weight of cumene hydrogen peroxide. The mixture is heated in a nitrogen atmosphere at 77 ° C for 30 minutes. The resulting cured film was tough, scratch resistant, stain resistant and relatively flexible.

Claims (3)

148047 Patent Claims —— - —— 1. Polymerizable material for preparing coatings with good stain, scratch and scratch resistance and consisting of one or more monomers which are diesters of a diol with one or two organic acids, characterized in that it consists of (a) at least one compound with the general formula 11 11 CH, CH- R · 1 · II 3 I 3 I CH 2 = C-C0-OCH 2 - (j: -CH 2 -O-C0 - ^ - CH 2 O -C-C = CH 2 R is a hydrogen atom or a methyl group, and / or (b) at least one compound of the general formula iH, CH, 3 I 3 Ί n -CH0-0-C0-C-CHo0-0CR υ II 4 is 2 CH 3 ch 3 r 11 where one of the groups R 9 and R "+ - 0 is a group of the formula -d ^ CH, 11. wherein R has the meaning given above and the other of groups R 10 and R a substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl group, and optionally (c) one or more compounds of the general formula ΐΗ3 ψ3 R9CO-OCH2 - (^ - CH2-O-CO-CJ-CH2O-OCR: L0 III CH3 CH3 g lo where R and R have the meaning given above except a group -c = ch9. * 11 Δ RXJ- Polymerizable material according to claim 1, characterized in that it consists of 2.5-35% by weight of one or more compounds of formula I, 30-95% by weight of one or more compounds of formula II and 2.5-35% by weight. % of one or more compounds of formula III. Process for preparing the polymerizable material of claim 1, characterized in that hydroxypivalyl-hydroxypivalate of the formula