DE2421118A1 - WIRE COATING PROCESS - Google Patents

Description

UEXKÜLL ft STCLUSHG PATENT Λ N WALTE

2 HAMBURG 52

BESELERSTRASSE Λ OR. J.-D. FRHR. by UEXKÜLL DFI. ULRICH GRAP STOLBEFSG

W. R. Grace & Co. (Prio: May 4, 1973 and

DIPL.-ING. JÜRCEN SUCKANTKIi

Grace Plaza March 20, 1974,

US 357 295 and 1114 Avenue of the Americas üS 453 139 - 11323)

New York, N.Y./V.St.A.

Hamburg, April 26, 1974

Wire coating process

The invention relates to a method for forming a solid Plastic coating on wires.

Heretofore known methods for coating wire with a plastic material are that compositions are used which are applied in solvent and then heated in an oven to remove the solvent, and that the compositions are cured and / or adhesively bonded to the wire. These procedures are numerous Disadvantages on. For example, a solvent is needed that will in turn be flammable and toxic and the atmosphere can contaminate; the wire may have to be coated up to 12 times in order to achieve the necessary coating thickness achieve, especially if the coating is used for electrical insulation; it is also very easily possible to do this Coating material to overheat and thereby a crumbling to cause the coating; in addition, for the im

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Heating step essential furnace often requires considerable financial outlay. Thermoplastic materials are normally unsuitable for the formation of electrically insulating coatings on wires because they do not have the have the necessary thermal resistance.

The invention is therefore based on the object, while avoiding these disadvantages, a method for coating Suggest wires. The object is achieved by a method that can be carried out very quickly, in which a through heat hardenable, plastic-forming material is used, wherein neither a solvent nor excessive heat are necessary.

The method of the invention for forming a solid coating on a wire consists in coating the wire with a material that is at the coating temperature is liquid and curable by ultraviolet or high energy radiation to form a solid plastic, and the coated Exposing wire to ultraviolet radiation or high energy radiation to cure the liquid material. The coating temperature, that is the temperature of the liquid material during the coating, is preferably not more than 90 °, especially room temperature.

The coating must be exposed to UV or high energy radiation be hardenable. The term hardenable material is also used to refer to

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those materials understood by such irradiation are polymerizable or crosslinkable or both, or are capable in some other way of curing as a result of the irradiation in heat. For the sake of simplicity, such a coating material is referred to below as radiation-curable. A A material that can be used in this sense is a photopolymerizable one Composition according to US Pat. No. 3,647,498. It is composed of an essentially solid phase which is in the essentially of polymers or copolymers of esters of methacrylic acid with a glass transition temperature of 75 ° C or less and a polymerizable liquid phase consisting essentially of 70 to 90% by weight of polyglycol dimethacrylate and 10 to 20 wt.% Bisphenol-Ä-dimethacrylate, the solid phase and the polymerizable liquid phase are 40 to 80% by weight and 20 to 60% by weight, respectively.

Another radiation-curable material that can be used according to the invention is the photopolymerizable composition according to US Pat. No. 2,760,863. It contains an addition-polymerizable ethylenically unsaturated component which, in the presence of a Addition polymerization initiator activated for exposure to ultraviolet light, and photoinitiated Polymerization forms a high molecular weight polymer, and the initiator for addition polymerization, which is natural is present in small or small quantities.

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Such a photopolymerizable composition can be any of addition-polymerizable monomers or from mixtures thereof and any initiators, alone or as a mixture be composed with other initiators which are photosensitive to ultraviolet light. Because of their light weight Accessibility and their low price are terminally ethylenically unsaturated monomers such as vinylidene or vinyl monomers preferred. These monomers include vinyl carboxylates or their starting materials, which are those in which the Vinyl group is arranged in the acidic part of the molecule, such as acrylic acid and its esters, for example methyl acrylate, Ethyl acrylate, n-butyl acrylate, acrylonitrile, methacrylonitrile, the o ^ l-alkyl acrylates such as methacrylic acid and ethacrylic acid and their esters such as methyl, n-propyl, η-butyl, isopropyl and Cyclohexyl methacrylates and ethacrylates; © C-substituted acrylic acids and their esters such as ethyl o ^ chloroacrylate and ethyl o ^ cyanoacrylate; Viny! Components in which the vinyl group is in the non-acidic part of the molecule is arranged, such as vinyl esters, for example vinyl acetate, vinyl chloroacetate, vinyl trimethyl acetate. Vinyl propionate and vinyl benzoate; Vinyl hydrocarbons such as vinyl aryls such as styrene; Vinylidene halides like vinylidene chloride. These monomers and their mixtures are liquids that boil above room temperature and should be chosen so that coherent, mechanically strong polymeric films result when they are polymeric in substance

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be sated. Because of their relatively high photoinitiated polymerization rate the vinylaryia and / or esters or acrylic and o £ -substituted acrylic acids with hydrocarbons material alcohols with no more than 6 carbon atoms, in particular with alkanols having 1 to 4 carbon atoms, preferably. Styrene and alkyl hydrocarbons are particularly preferred substituted acrylic acids in which the alkyl groups contain 1 to 4 carbon atoms. In the photopolymerizable Composition according to US Pat. No. 2,760,863 can practically any initiator or catalyst for addition polymerization be used, which initiates the polymerization under the influence of actinic light. The preferred of these catalysts or initiators are not thermally activated and are preferably in the polymerizable compound to that extent soluble as necessary to initiate the desired polymerization under the influence of the amount of light energy which in.der the relatively short exposure time of the invention Procedure is absorbed. The photoinitiators suitable according to the invention are thermal at temperatures below 80 to 85.degree not active (although of course the critical temperature is that at which the coating takes place). These initiators for the photopolymerization, amounts from 0.05 to 5% by weight and preferably from 0.1 to 2% by weight are used based on the total weight of the photopolymerizable composition.

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About suitable initiators or catalysts for photopolymerization include vicinal ketaldonyl compounds such as diacetyl and benzil, Q ^ -Ketaldonyl alcohols such as benzoin and Pivaloin, acyloin ethers such as benzoin methyl or ethyl ether, Q ^ hydrocarbon-substituted aromatic acyloins including o £ -methylbenzoin, o ^ -allylbenzoin and o ^ -phenylbenzoin.

The curing radiation is highly energetic, in contrast to the UV radiation, it is usually not necessary to use a catalyst or initiator for photopolymerization of the composition to add.

Most of the commercially available polymerizable monomers and polymers previously listed for use in the present invention normally contain minor amounts (about 50 to 100 ppm by weight) of polymerization inhibitors to prevent premature spontaneous polymerization impede. The presence of these inhibitors, usually antioxidants such as hydroquinone or t-butylcatechol, in the corresponding amounts, do not normally reduce the speed or quality of the polymerization,

Another radiation-curable material which can be used in the present invention is a photo-curable composition which is used in the

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Coating temperature is liquid and contains a polyene, which has at least two reactive unsaturated carbon / carbon bonds per molecule, and a polythiol,
which contains at least two thiol groups per molecule, the total number of reactive unsaturated carbon / carbon bonds per molecule of polyene and thiol groups per molecule of polythiol being greater than four, and, if required, an accelerator for photo-curing, which can be referred to as a photo-initiator.

If the curing is to be effected by UV radiation, it is usually necessary to add a photoinitiator to the composition in order to add the composition quickly enough cure to make the process economically acceptable. If the hardening is carried out by means of high-energy radiation, is usually the addition of a photoinitiator without any benefit.

The preferred amounts of the respective components of these curable ones Composition is about 2 to about 98 weight percent polyene, 98 to about 2 weight percent polythiol, and, if necessary, about 0.0005 to about 50 parts by weight (based on 100 total parts by weight) accelerator for photo-curing. The cheapest The range for the accelerator is between about 0.05 and about 30 parts by weight.

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These radiation curable compositions are usually, and preferably, liquid at room temperature. In order to obtain liquid curable compositions, both polyene and polythiol are preferably liquids. Almost all of the polyenes and polythiols listed in GB-PS 1,215,591, 1,251,232 and 1,294,127 are liquid at room temperature. However, the compositions can be solid, crystalline or semi-solid at room temperature, but liquid at the coating temperature. For example, set a composition at room temperature, but even 1OO ° C be at 90 ⁰ C or liquid.

Under liquid such compositions are understood to have in the presence of a reactive plasticizer such as diallyl phthalate has a viscosity in the range of practically 0 and 20 million centipoise at 70 ⁰ C.

Polyene is understood to mean simple or complex alkenes or alkynes which have at least two reactive unsaturated carbon / carbon bonds exhibit. These bonds are preferably terminal, near terminal and / or in rare chains arranged in the main chain. They can have a double bond character (ethylenic) or a triple bond character (acetylenic) possess. Molecules can also be used which have reactive double and triple bonds at the same time.

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Under reactive unsaturated carbon / carbon bonds are understood to mean those under the action of ultraviolet or high-energy radiation and under suitable Conditions react with thiol groups and form thioether bond fertilizers (-C-S-C-), and are in contrast to unreactive ones Carbon / carbon bonds, by which carbon / carbon multiple bonds are understood, as they are in aromatic nuclei occur (cyclic structures as in benzene, pyridine, anthracene, tropolone and the like), which under do not react with thiols to form thioether bonds under the same conditions. The products of the reaction of polyenes with polythiols are called polythioethers.

One group of the polyenes suitable according to the invention have a molecular weight of about 50 to 20,000, preferably about 500 to about 10,000, and a viscosity of up to 20 million cP at 70 ° C and satisfy the general formula: £ a]] - (X), in which X is a group of the formula R-CR = CR- or R-C ^ c- and m at least 2, and each R is independently hydrogen or halogen or an aryl, substituted aryl, cycloalkyl, substituted cycloalkyl, aralkyl, substituted aralkyl, alkyl groups having 1 to 16 carbon atoms or substituted Are alkyl groups having 1 to 16 carbon atoms, and A is a is a polyvalent organic group that (1) has no reactive carbon / carbon bonds and (2) no unsaturated

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Contains groups in conjugation with the reactive en or in groups in X. Accordingly, A can contain cyclic groups and smaller amounts of heteroatoraes such as N, S, P or O, but contains mainly carbon / carbon, carbon / oxygen or silicon / oxygen linkages without unsaturated reactive carbon / carbon multiple bonds. Polyenes of this type are usually liquid at room temperature. In this context, the British Patent 1,215,591 and 1 251 is pointed. A second group of suitable polyenes includes unsaturated polymers in which the double or triple bonds occur essentially in the main chain of the molecules. Polyenes of this group are described in GB-PS 1,251,232. A third group of polyenes suitable according to the invention include those in which the unsaturated reactive carbon / carbon bonds are conjugated with the adjacent unsaturated groups. Polyenes of this type are described in GB-PS 1,294,127. Examples of these polyenes are poly (oxyethylene) glycol (molecular weight 600) diacrylate, poly (oxytetramethylene) glycol (molecular weight 100) dimethyl acrylate and triacrylates from the reaction product of trimethylolpropane with 20 moles of ethylene oxide.

The preferred polyenes which can be used according to the invention include Triallyl isocyanurate, poly (diallyl orthophthalate), diallyl chlorendate (see Example 3) and the polyenes from the reaction

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of trimethylolpropane diallyl ether with toluene diisocyanate to form an allyl-terminated monoisocyanate and reaction of this allyl-terminated compound with 1,5-di- (2-hydroxyethyl) -ä, 3-dimethylhydantoin in a molar ratio of 2: 1 (see Example 4). This polyene is newly _f as well as its production described above and the compositions containing this polyene and a polythiol.

The term polythiol refers to simple or complex organic compounds with a large number of SH functional parts Groups per molecule that are terminal or arranged in the side chain.

On average, the polythiols must contain two or more SH groups per molecule. Their viscosity is generally up to 20 million. cP at 70 ⁰ C, measured with a Brookfield viscometer. Polythiols in this sense include those materials which, in the presence of reactive plasticizers such as diallyl phthalate, have a viscosity in the above range at 70.degree. The molecular weight of the polythiols is usually from about 66 to about 20,000, preferably from about 100 to about 10,000.

The polythiols which can be used according to the invention satisfy the general formula R _R - (SH), in which η is at least two and Rg is one

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are polyvalent organic groups with no reactive carbon / carbon bond. Thus, R _ß can contain cyclic groups and smaller amounts of heteroatoms such as N, S, P or 0; However, Ro mainly contains carbon-hydrogen, carbon-oxygen or silicon-oxygen bonds that do not have reactive carbon / carbon bonds.

One group of the polythiols which can be used according to the invention corresponds to the general formula: R ₁₀ - (OCO-Rg-SH), in which R _g and R _{10 are} organic groups which have no unsaturated reactive carbon / carbon bonds, and in which η is 2 or larger. These polythiols are esters of thiol-containing acids of the general formula HS-R "-COOOH, in which R _{q is} an organic group without an unsaturated reactive carbon / carbon bond, and a polyhydroxy compound of the general formula R _1Q - (OH), in which R _{1n is} an organic group with no carbon-to-carbon unsaturated bond and η is 2 or greater. Examples of the preferred polythiols include esters of thioglycolic acid (HS-CH COOH), cxi-mercaptopropionic acid (HS-CH (CH ₃ ) -COOH and β-mercaptopropionic acid (HS-CH ₂ CH ₂ COOH) with polyhydroxy compounds such as glycols, triols, tetraols , Pentaols and hexaols. Particularly preferred polythiols include ethylene glycol bis (thioglycolate), ethylene glycol bis (ß-mercapto-

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propionate), trimethylolpropane tris (thioglycolate), trimethylolpropane tris (ß-mercaptopropionate), pentaerythritol tetrakis. (ß-mercaptopropionate). More descriptions and examples of the polythiols which can be used according to the invention can be found in the aforementioned patents. The one in GB-PS 1 294 The various accelerators of photo-curing described (photo-initiators) can be the polyene / polythiol compositions be added, many of them, for example benzophenone / in many of the previously described photopolymerizable Compositions can act as photoinitiators. The photosensitizers are the curing accelerators or photoinitiators, are usually added in the range of 0.0005 to 50% by weight.

The photohardenable compositions can be hardening inhibitors or retarders, for example hydroquinone, p-tertiary butylcatechol 2,6-di-tert-butylparamethylphenol, phenothiazine and Contain N-phenyl-2-naphthylamine.

For further description of the polyene / polythiol compositions attention is drawn to the aforementioned British patents and US Pat. No. 3,645,730.

The photo-curable compositions may contain any of the usual and known additives, such as those according to GB-PS 1 251 232, provided that they do not use the UV photo

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prevent hardening. The proportion of additives is usually up to 150 parts by weight or more per 100 parts by weight of the liquid photo-curable composition, and preferably from 0.005 to 100 parts by weight.

The wire to be coated is preferably first passed through a cleaning or degreasing agent and then before the coating with the photo-curable material dried. These cleaning and degreasing solvents are known to those skilled in the art known; Examples are dichloroethylene / perchlorethylene, methylene chloride, methylene chloroform and acetone.

It may be necessary to heat the radiation-curable material to slightly elevated temperatures, up to about 100 C, so that the composition is in liquid form. This can be done under the condition that the material has an effect the heat does not harden prematurely.

The liquid radiation curable materials usually have Viscosities in the range from about 50 to about 500,000 cP at 25 ° C. If the viscosity is too low, it becomes liquid Material only applied as a thin coating on the wire, so that multiple coatings of the wire and irradiations become necessary in order to obtain the desired coating thickness. On the other hand, if the viscosity is too high, the Coating thicker than desired.

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In either case, the thickness of the coating can be reduced by removing the wire after coating but before irradiation by a device, for example by a mold used in the application of coatings (e.g. floatin ball die) to prevent an excessive amount of radiation curable material from being cured on the wire. Such devices are known to those skilled in the wire coating art.

In a preferred procedure according to the invention The coating is carried out by placing the wire in a bath of the liquid radiation curable material is introduced. The wire is fed continuously through the bath. He can from the bath in the usual way, for example horizontally, that is, parallel to the surface of the bath liquid, or practically vertically out of the bath. The irradiation is then suitably carried out when the wire is continued in the same direction. The vertical lead out is particularly advantageous when a coating device is not used. It was found that in this way a uniform diameter hardened Coating can be formed on the wire. Preferably, however, the wire from the bath is passed through a coating device guided so that the coating has the required thickness before the exposure step, and all the more so

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more if the wire is led out of the bath diagonally or horizontally, because the coating, which is still liquid, is added to it tends to run onto the underside of the wire, resulting in an uneven cured coating. The tool causes concentric distribution of the coating before curing.

The UV radiation can with a dose of 0.0004 to 6 watts /

cm.

Suitable arrangements for the coating process are now intended below will be described with reference to figures which are schematic flow diagrams. According to FIG. 1, an uncoated Wire 1 from a drum roll 12 via a guide roll 2 into a liquid bath of a radiation-curable material 3 and around the guide rollers 4 and 5 vertically out of the bath. The wire 6 with the uncured coating is then passed through the UV lamp device 7 at such a rate that the curing or polymerization or both are done when the wire exits the lamp assembly. Excess radiation curable material must generally be removed by placing the wire 6 through a device (not shown) between the top of the bath and the UV lamp device. The coated wire 8 is then over the guide roller 9 and if necessary by a

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Heating furnace 10 passed. (Heat at, for example, 50 to 250 ° C is sometimes desirable to improve the adhesion of the cured coating to the wire. Of course you have to Care should be taken that the melting or decomposition temperature of the hardened material is not exceeded.) Then the wire with the hardened coating on a roll 11 rolled up and is therefore suitable for further use.

In Fig. 2 is another embodiment of the invention reproduced. Here, the uncoated wire 1 is guided horizontally from the drum 12 into and through the bath 13, which contains the liquid radiation-curable material 3. In the opposite sides of the bath 13 are pairs of slots 14a, 14b, the wire being passed into bath 13 through slot 14a and out of the bath through slot 14b. Numerous of these pairs of slots 14, 14c, 14d, 14e, 14f, etc. are provided so that many wires are coated at the same time in the bath can be. Then the wires can be cured simultaneously in one or more lamp devices. the Liquid 3 continuously flows from the baths through the slots 14a, 14b, 14c, 14d, 14e, 14f, etc. into a tank The level of the liquid 3 in the bath 13 is maintained by the liquid radiation-curable composition 15, the is collected in tank 16, is returned through the return line 17 by means of a pump 18. The wire 6 with the

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uncured coating covering the bath 13 through the slot 14b leaves, is passed through the device 9 and the UV light device 7. The coated wire 8 is then on a Roll 11 rolled up, previously in an oven 10 according to Fig. 1 can be heated. Of course, the radiation-curable composition can also be used in the procedure according to FIG and more than one wire can be coated at the same time in the same bath. If necessary, each the bath can be heated in the usual way. Although it is shown in FIGS. 1 and 2 that the wire unwinds from a drum, it can also be taken directly from a wire drawing device or from A bundling machine come when a wire is to be coated, which consists of different wires twisted together. A tin-coated wire can also be used to increase its resistance to oxidation and its To improve soldering behavior. The method according to the invention can be applied to wire made of pure metal or wire, those with a thermoset or thermoplastic material or other insulating material such as fiberglass is pre-coated, to be coated.

The radiation-curable compositions according to the invention can also by high-energy radiation, preferably high-energy particle radiation (ionizing radiation), gamma rays or X-rays. Inventive

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appropriate radiation using particles also includes the use of positive ions (e.g. protons, «^ -Particles or neutrons), electrons or neutrons. the charged particles can be accelerated to high speeds by stress gradient mechanisms, such as by Van de Graaff generators, cyclotrons, Cockroft-Walton accelerators, Resonant cavity accelerator, betatrone, G.E. Resonance transformers or synchrotrons. Furthermore Particulate radiation can also be generated by radioactive isotopes or a nuclear reactor. gamma rays or X-rays can be obtained by radioisotopes (e.g. cobalt 60) or by particle bombardment of a suitable material (for example, by high energy electron bombardment on a gold metal target).

The radiation dose normally required for the invention Cure of the coating is in the range of 0.00001 to 1000 megarads / second.

The amount of ionizing radiation can be varied within wide limits vary. Usually radiation doses of less than one megarad up to 10 megarads or more are suitable for electrons, preferably 0.02 to 5 megarads of absorbed energy. For gamma rays or x-rays, the radiation doses are about 0.0001 to 5.0 megarads of absorbed energy.

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The irradiation is usually carried out at room temperature; however, it may be carried out at temperatures of about 90 ⁰ C and at temperatures below room temperature up.

In the case of ionizing radiation, the depth of penetration depends on the density of the material to be treated. Will the ionizing Radiation carried out in the form of electrons are usually around 0.2 to 12 million electron volts (mev) used. If gamma rays or X-rays are used, the value is about 0.01 to 5.0 mev. This voltage range allows penetration of aluminum in the range of about 25.4 µm to 31200 µm. If this penetration is not enough to To cure the coating to the desired depth when irradiation is only carried out from one side, several sources of radiation can be used are used, which emit simultaneously or staggered in time from opposite sides of the wire. In addition, shielding can also increase the penetration of radiation into the coating on the opposite side Side of the wire, in relation to the radiation source.

The invention is particularly useful for forming an insulating Coating suitable for a wire to be used as an electrical conductor. The wire can be from the previously

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mentioned metals or a bimetallic combination, such as from a Rupferleitphase with nickel, Aluminum or stainless steel. It can also be "magnet wire", that is, wire that is used as a motor or armature Winding is used. The invention is explained in more detail with reference to the following examples, all part and Percentages are based on weight. Gauges specifications correspond to the American wire gauge gauges.

example 1

An 18 gauge copper wire (1 mm diameter) was passed through a degreasing bath of methylene chloride for cleaning of the wire and then dried. The copper wire was then passed through a bath that was 40.5 parts Triallyl isocyanurate, 59.5 parts of pentaerythritol tetrakis (β-mercaptopropionate) and 2.0 parts of benzophenone. Of the Wire was removed from the bath in the vertical direction, then first through a coating form and then through a Surrounding this height lamp device (Westinghouse 275 watts) at a speed of 1.5 m / sec. directed. The lamps were arranged so that the surface intensity on the

2 photohardenable composition was 4000 microwatts per cm. the The main spectral lines of the sunlamps all lay above 3000 A *. The wire with the cured coating was then through an infrared oven at 150 ° C to improve the

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Adhesion of the hardened coating on the wire. The wire then had a soft hardened coating of a Thickness of 50 µ, which had good flexibility and adhesion when bent.

Example 2

Example 1 was repeated with the difference that, on the one hand, a 28 gauge copper wire was used and the

liquid composition in the bath consisted of the following parts: 80 parts of commercially available poly (diallylorthophthalate), 20 parts of pentaerythritol tetrakis-ß- (mercaptopropionate), 1 part of benzophenone, 0.02 part of phosphoric acid and 0 _# 2 parts of pyrogallol; and, on the other hand, that the wire was finally passed through the altitude lamp device at a speed of 1.8 m per second.

The wire had a soft hardened coating 25 µm thick and showed good flexibility and flexibility when bent Adhesion.

Example 3

Example 1 was repeated with the difference that an aluminum wire having a diameter of 500 µm was coated, the photo-curable composition being composed as follows was: 567 g of commercially available diallyl chlorendate (a polyene of the formula

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- ²³ - 242111b

COO-CH ₂ -CH = CH ₂

C00-CH_-CH = CH-CIi " ²

Cl

42O g of commercial tris (2-hydroxyethyl) isocyanurate tris (ß-mercaptopropionate), 9.9 g benzophenone, 0.2 g phosphoric acid and 0.1 g pyrogallol; an oven was not used.

Example 4 Manufacture of a polyene

253 g of commercially available trimethylolpropane diallyl ether (containing 4.54 milliequivalents of OH groups per g) were
placed drop by drop in a three-necked flask containing 200 g
Toluene diisocyanate (an 80% / 20% mixture of the 2,4 and 2,6 isomers, containing 11.48 milliequivalents of KCO groups
each g) added. The reaction was carried out at 60 ° C. for 8 hours with stirring. 118g of commercially available di (2-hydroxyethyl) dimethylhydantoin (containing
8.92 milliequivalents of OH groups per g) of the formula

CH _Q -

HOCB ₂ OH ₂ -N H-CH ₂ CH ₂ OH

It

added simultaneously with 0.25 g of tin octoate as a catalyst.

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242111a

At the beginning of the reaction it was necessary to heat a little, and thereby the mixture as the reaction proceeded became extremely viscous, it was necessary to increase the temperature to 95 ° C to ensure thorough mixing. the The reaction was kept at this temperature until the reaction was complete, which was indicated by the disappearance of the NCO band was detected in the infrared spectrum. The product of the formula

CH. CH ₀

.0

CH ₀ = CHCK OCH,

2 O

, OCNH

CH ₂ = CHCH ₂ OCH ₂

CH.

CH ₂ OCH ₂ CH = CH ₂

had a glass point of 95 C; unsaturated part: Theoretically 4.03 mmoles per g; found: 4.06 raMoles per g. This polyene is hereinafter referred to as "polyene A".

An aluminum wire with a diameter of 250 ^ µm was made passed through a degreasing bath consisting of methylene chloride and then dried. Then the wire

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2421 '

performed in a bath that was maintained at 85 ⁰ C and contained the following photocurable composition: 60 parts polyene A, 3I ₁ 3 parts of trimethylolpropane tris (beta-mercaptopropionate), 1 part of benzophenone, 0.02 parts of phosphoric acid and 0.02 Share pyrogallol.

The wire was removed vertically from the liquid bath and then through a first device and then through passed a photochemical reactor containing a hollow elliptical cylinder, the inner surface of which was mirrored. The wire with its coating of liquid photohardenable composition was through guided this elliptical mirror along an axis, and a linear high intensity UV light tube, its Main spectral lines above 300 Ä * were along arranged on the other axis of the elliptical cylinder. With this arrangement, the UV light rays are emitted from the linear source reflected from the inner walls and focused on the axis along which the wire moves wherein the photosensitive composition is cured as the wire moves through the reactor at a speed of 1.5 in per second. The wire had a soft hardened coating of one thickness of 12.5 / µm, which gives good adhesion and flexibility when bending showed.

Example 5

Example 3 was repeated with the difference that the

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radiation-curable material was composed as follows:

80 parts of a commercially available triethylene glycol dimethacrylate, 20 parts of a commercially available bisphenol A dimethacrylate,

1 part of the methyl ether of benzoin and 100 ppm hydroquinone.

The wire with the hardened coating had good flexibility when bent.

Example 6

A 30 gauge * copper wire (250 µm diameter) was made passed through a degreasing bath made of methylene chloride and then dried. Then the wire was used in a bath a liquid photopolymerizable composition, which was composed essentially as follows: 45 parts of methyl aerylate, 55 parts of tetraethylene glycol diacrylate, 1 part benzoin ethyl ether and 100 ppm hydroquinone.

Then the wire was in the vertical direction at one speed 1.5 m / sec away from the bath and through an encircling height lamp device (Silvania height lamps, 275 watts), the main spectral lines of which were above 3000 8. The sunsets were arranged so that the surface intensity on the photohardenable composition per cm ^ 000 microwatts. The wire owned a soft hardened surface with a thickness of 25 / µm, and showed good adhesion and flexibility when bent.

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Example 7

This example uses double coating and curing described.

A 12 gauge (205 mm diameter) copper wire

was provided with a photocured coating according to Example 1, but no oven was used. The wire with one 25 * 4 / order thick coating was then transferred to another bath introduced with the photocurable composition according to example 3 and then treated according to example 3. Of the Wire had a soft, hardened double coating 50 µm thick, which provided good adhesion and flexibility when bent exhibited.

Example 8

Manufacture of a polyene

800 ml of toluene and 800 ml (about 14 mol) of allyl alcohol were added to a 3 liter three-necked flask equipped with a stirrer, Dean-Stark trap and heating mantle. 1 g of p-toluenesulfonic acid was treated with 536 g (4 moles) of malic acid and Ig octadecyl-3- (3 _J 5-di-t-butyl-i | - hydroxyphenyl) was added -propiönat (stabilizer) with stirring and the mixture heated to boiling . The trap was slowly distilled for 14 hours, after which no more water was separated out. A total of 172 ml of an aqueous phase was collected in the trap. The cooled mixture was washed with 800 ml of water, then 800 ml of 5 # strength sodium hydrocarbonate solution and then with 2 × 800 ml v / water. The organic phase

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was dried with anhydrous magnesium sulfate, treated with 10 g of activated carbon and filtered. In one Rotavapor, the volatile solvents were removed under reduced pressure. There were 759 g of diallyl malate, one slightly straw-colored liquid, preserved.

376 g (1.76 mol) of Diallylmalats prepared as described were mixed at 50 ⁰ C and 0.42 g stannous octoate catalyst in a I-liter three-neck flask with stirrer and thermometer. 145 g (0.834 mol) of toluene diisocyanate were gradually added with effective stirring to regulate the temperature at 65.degree. After the exothermic reaction had ended, the mixture was heated ^{to 65 ° C. for a further 2 hours.} The polyene (521 g) of the formula:

! 00CH ₂ CH = CH ₂

IH ₀ COOCS = CH ₀

was a slightly colored, viscous liquid and is referred to as polyene B in the following.

A copper wire with a diameter of 250 µm was passed through passed a degreasing bath made of methylene chloride and then dried. The wire was then tied with a fiberglass

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Enclosed insulation and placed in a bath of a liquid radiation-curable composition, which was composed essentially as follows:
521 g of polyene B,
479 E trimethylolpropane tris-mercaptopropionate),

20 g benzophenone,
0.5 g phosphoric acid, 0.1 g hydroquinone and
0.05 g pyrogallol.

The coated wire was passed through the bath, then through a floating ball dye in a horizontal direction and then at a speed of 3 m / sec through an enclosing one UV high light device according to Example 6 passed. The wire had a soft hardened coating of a Thickness of 75 / µm and exhibited good flexibility and flexibility when bent Adhesion. The radiation cured wire had better abrasion and scuff resistance than the same Wire that was only coated with fiberglass insulation.

Example 9

An 18 gauge. Copper wire (diameter 1 mm) was passed through a degreasing bath made of methylene chloride Cleaning the wire passed and then dried. The dried copper wire was passed through a bath at 60 ° C passed, which essentially contained the following liquid, radiation-curable composition:

409847/0890

500 g of commercial diallyl chloro-rendate, 253 g of pentaerythritol tetrakis-tß-mercaptopropionate), 7.6 g of benzophenone,
Oj153 g of phosphoric acid and
0.076 g pyrogallol.

The wire was passed through the bath and when exiting the bath through a coating form (floating ball dye), creating a 38Ο to thick coating remained on the wire. Of the Wire coated in this way was passed through the solar elevation device according to Example 1 at a speed of 4.5 m / sec. The wire had a soft, hardened one Coating a thickness of 380 µm, which is good when bending Flexibility and adhesion showed.

Example 10

A 30 gauge * ". Copper wire is coated with tin to improve its resistance to oxidation and to improve its soldering properties. Various strands of wire were fed into a bundling device and the twisted wire was collected on a winch. The twisted wire was then fed into an extruder in the it was coated with polyvinyl chloride hot and cooled it with water and dried the coated in this Wise wire was then passed into a bath of a liquid radiation-curable composition according to example 8 and cured according to example 8 with the difference;. that

409847/0890

the speed of the wire was 1.5 m / sec. The wire had a soft, cured coating 50.8 µm thick on top of the polyvinyl chloride coating. The overlay with the photopolymers causes better thermal and abrasion resistance of those coated with polyvinyl chloride Wire,

Example 11

An aluminum wire with a diameter of 250 µm was made passed through a degreasing bath made of methylene chloride and then dried. Then the wire was attached to a bath 100 ° C passed, the composition according to example *} contained.

The wire was passed through the bath and led out of the bath in a horizontal direction. The coated wire was then first through a coating form (floating ball dye) and then through at a speed of 6 m / sec an enclosing high lamp arrangement according to Example 1 out. The wire had a soft, hardened coating a 'thickness of 125 / µm, which gives good flexibility when bending and had adhesion.

Example 12

Example 11 was repeated with the difference that the hardening was carried out by passing the wire through a coating mold (floating ball dye) was passed, so that a 125 / µm thick coating was created, and then with a Speed of 6 m / sec through a jet from one

409847/0890

2 Mev-Van de Graaff electron accelerators headed vmrde. The dose of radiation was 1.0 megarads. The wire had a soft hardened coating with a thickness of 125 / µm, which had good flexibility and adhesion when bent.

Example 13

A 500 µm copper wire was made through a degreasing bath Passed methylene chloride and then dried. The wire is then passed into a bath that is radiation-curable Composition according to Example 2 contained.

The wire was passed out of the bath and through a coating mold (floating ball dye), creating a 50 µm thick coating on the wire, and then at a speed of 60 m / min through the beam of a 2 Mev-Van de Graaff- Electron accelerator directed. The dose of radiation was 1.0 megarads. The wire had a soft hardened coating 50 µm thick which had good flexibility and adhesion when bent.

The invention also relates to certain new polyenes and polythiols which are useful as components of the curable compositions in the method of the invention for coating wires. The new polyenes are reaction products of N, N ^t -bis (2-hydroxyethyl) dimethylhydantoin or their ethoxylated derivatives and of at least one un-

409847/0890

- 33 -

saturated organic compound such as an ethylenically unsaturated one Acid or an isocyanate. The new polythiols are the reaction products of N, N'-bis (2-hydroxyethyl) -dimethylhydantoin and a mercaptocarboxylic acid.

The invention encompasses polyene-polythiol compositions, in in which the polyene component contains such polyenes and / or in which the polythiol component contains such polythiols. The preferred Compositions contain both the new polyenes and the new polythiols. These compositions can by actinic radiation in the presence of a UV sensitizer hardened to form a polythioether-containing material that is excellent physically and chemically Has properties. For example, coatings made from the cured compositions on wire are capable of over to withstand high temperatures for long periods of time. The cured composition is also resistant to strong acidic corrosives Solutions or highly alkaline conditions. Likewise, she knows. remarkable flexibility and high extension in the event of failure as will be shown in an example below. These desirable yet surprising properties make the preferred curable compositions for training of coatings on wires and malleable metals.

The new polyenes and polythiols described above can

40 98 47/0890

can be referred to in a simplified manner, taking into account their origin, as hydantoinediol polyenes and polythiols. Your education is illustrated by the following reaction schemes:

I. Polyene from the reaction of a hydantoin diol with an ethylenically unsaturated isocyanate, which is the reaction product of 1 mole of 2 _s 4-toluene diisocyanate with 1 mole of allyl alcohol:

HIGH ₂ CH ₂ N

Il O

NCH ₂ CH ₂ OH

NHCOCH ₂ CK = CH ₂

Il

CH ₂ CH ₂ -OC-NH

CH ₂ CK ₂ -OC-HH

Il
NHCOCH ₉ CH = CH-

IiHCOCH ₂ CH = CH ₂

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Il.Polythiole from the reaction of a hydantoinediol with ß-mercaptopropionic acid (as mercaptocarboxyl reaction partner):

CH _n

ι ³ °

⁰ H ₃ -? - = ο

Il H

HIGH ₂ CH ₂ N NCH ₂ CH ₂ OH 4- 2 HOCCH ₂ -CH ₂ ^ SH

Il ο

Il

CH ₂ CH ₂ -OC-CH ₂ -CH ₂ -SH 0

Il

C - N ^

I .C = O +

CH ₃ - CN ^

CH ₃ ^ CH ₂ CH ₂ -OC-CH ₂ -CH ₂ -SH

The hydantoinediols are generally commercially available. Suitable hydantoinediols include not only N _a N'-bis (2-hydroxy-ethyl) -dimethylhydantoin ₃ but also its polyethoxylated derivatives. These polyethoxylated derivatives are obtained by adding the desired number of moles of ethylene oxide to the N, N'-bis (2-hydroxyethyl) dimethylhydantoin, as is the case, for example, by

409847/0830

a conventional ring-opening addition reaction of the epoxide can take place. The polyethoxylated derivatives preferably have at least one ethoxy group added to each of the two OH groups, the total number of ethoxy groups im generally does not exceed 22.

One group of the polyenes which can be used according to the invention and which have a hydantoin diol skeleton include the unsaturated urethane derivatives. They satisfy the general formula:

0-C-KH-A-

"r

in which Q is the hydantoin diol moiety that remains after the two hydroxyl groups of the hydantoin diol are formed of the urethane, i.e. the -0-CO-NH bond, have reacted; A. and B are polyvalent organic groups without reactive carbon / carbon unsaturated bonds and contain Groups such as aryl, substituted aryl, aralkyl, substituted aralkyl, cycloalkyl, substituted cycloalkyl, Alkyl or substituted alkyl groups containing 1 to 36 carbon atoms and their mixtures.

These groups can be linked by chemically compatible, such as -0-, -S-, carboxylate, carbonate, carbonyl, urethane or substituted urethane, urea or substituted urea

409847/0890

substance, amide or substituted amide, amine or substituted amine and hydrocarbon. Z is a divalent one chemically compatible bond, such as -NH-COO-, -0- and -S-, preferably -NH-COO-.

Preferred examples of the aryl groups are either phenyl or naphthyl groups and suitable cycloalkyl groups are those which have 3 to 8 carbon atoms. Preferred substituents on the substituted groups are chlorine, bromine, Nitro, acetoxy-i acetamido, phenyl, benzyl, alkyl and / or alkoxy groups with 1 to 9 carbon atoms and cycloalkyl groups with 3 to 8 carbon atoms.

X is (a) - (CH ₂ ) _d -CR ^? = CHR, (b) -0 (CH ₂ ^ -CR '= CHR, (c) -S- (CH ₂ ^ -CR' = CHR, (d) - (CHg ^ -CSCCR, (e) -0- (CH ₂ ^ -CE-LCR, (f) -S- (CH ₂ ) _d -C = CR and / or mixtures ^{thereof; and R and R 1} are each independently either hydrogen or methyl groups, preferably hydrogen; d, ρ and q are each 0 or 1; y is an integer from 1 to 10, preferably 1 to 5; r is an integer of at least 1, preferably from 1 to ¹ J and in particular 1 or Preferred polyenes of the urethane hydantoinediol type include reaction products of the hydantoinediol of the formula

CH ₃

II £ OCH ₂ CH ₂ -J ^ - N .N- (CH ₂ CH ₀ O-) H

409 ^ 47/0890

- - 38 -

in the m and η each at least 1 and m + η 2 to 22 are, with at least one reactively unsaturated monoisoeyanate, wherein the polyene has at least two reactive carbon / carbon unsaturated bonds per molecule owns.

The reactive unsaturated carbon / carbon bonds are preferably terminal or in the side chain arranged. Terminal is understood to mean that the functional unsaturated group is at one end of the Main chain of the molecule is arranged. The formulation, arranged in the side chain, is understood to mean that the reactive unsaturated carbon / carbon bond is arranged terminally in a side chain on the main chain and is thus in contrast to positions at or near the end of the main chain.

The unsaturated carbon / carbon bonds (groups) are reactive in the sense that they form thioether bonds with thiol groups under suitable conditions described (-C-S-C-) react, and are in contrast to the non-reactive, unsaturated carbon / carbon bonds, which occur in aromatic nuclei (illustrated by the example of benzene, pyridine, anthracene and the like), which do not lead to thioether linkages under the same conditions with thiols.

409847/0890

_ 39 -

A general method for the formation of urethane-containing hydantoinediol polyenes is that the hydantoin of the general formula Q- (OH) _? , in which Q has the meaning given above, is reacted with at least one reactive unsaturated isocyanate of the general formula NCO-A - / _ ~~ Z -B - (X) D , in which the groups A, Z, B, X and the numbers Ps Qj Υ ^{and r have} the meaning given to them before. (The reactive unsaturated isocyanate is hereinafter referred to as en isocyanate or as in isocyanate).

The reaction may be in a moisture-free atmosphere at normal pressure and temperatures in the range of about 30 to 100 ⁰ C, preferably from about ¹ JO to 80 ° C can be performed in about 10 minutes to about 2k hours. The reaction is preferably a one-step reaction in which all reactants are brought together at the same time. The en isocyanate or isocyanate is added in stoichiometric amounts for reaction with the hydroxyl groups of the hydantoinediol. If necessary, the reaction can be carried out in the presence of a catalyst and an inert solvent. Suitable catalysts include tin catalysts such as dibutyltin dilaurate, tin octoate, tertiary amines such as triethylenediamine or Ν, Ν, Ν ', Ν'-tetramethyl-1,3-butanediamine, etc. Suitable inert solvents include aromatic hydrocarbons and halogenated saturated aliphatic ones or aromatic hydrocarbons and their mixtures. These include in particular benzene, chlorine

A 0 9 8 k 7/089 0

benzene, chloroform, l, l ₃ l-trichloroethane ₃ 1,2-dichloroethane and the like.

Suitable en- or in-isocyanates of the general ones given above Formula are, for example, simple monounsaturated isocyanates, such as allyl isocyanate, 2-methallyl isocyanate, crotyl isocyanate usii.

The suitable monounsaturated isocyanates satisfy the above formula for en- or in-isocyanates, with the whole Numbers ρ and q are 0 and r 1. Accordingly, the urethane hydantoinediol polyenes from these reactive unsaturated isocyanates by the simplified formula

. | j

Q [0-C-HH-A-

are described, in which preferably y = 1, and the other symbols have the meanings given to them above.

Other suitable en- or in-isocyanates include Reaction products of polyisocyanates of the general formula A- (NCO), in which χ at least 2 and A the above have given meaning, with an unsaturated reactive alcohol of the general formula / T (X) -B7-0H, in where B, X and y have the meaning given above.

4098Λ7 / 0890

The polyisocyanates and alcohols are stoichiometric in such Amounts added that χ - 1 isocyanate groups react to x-1 urethane linkages.

Suitable examples of the starting polyisocyanates include hexamethylene diisocyanate, toluene diisocyanate, xylene diisocyanate, methylene bis (phenyl isocyanate), 4,4'-methylene (cyclohexyl isocyanate), 1-methoxy-2,4,6-benzene triisocyanate, 2,4, 4 · triisocyanate diphenyl ether, diphenylmethane tetraisocyanates, polyisocyanates with various functional groups, such as N, N ^f , N "-tris- (isocyanatohexyl) -biuret or adducts of polyalcohols and diisocyanates which have at least 2 free isocyanate groups. An adduct is also suitable from trimethylolpropane and 3 moles of toluene diisocyanate.

Among the examples of suitable reactive unsaturated alcohols, which react with the polyisocyanates to form the desired en isocyanates include allyl and methally alcohol, Crotyl alcohol, 60-undecylinyl alcohol, 2-vinyloxyethanol, Vinyl hydroxyethyl sulfide, propargyl alcohol, 1-allylcyclopentanol and 2-methyl-3-buten-2-ol. Reactive unsaturated derivatives of polyhydric ones are also suitable Alcohols such as glycols, triols, tetraols, etc. Corresponding examples include trimethylolpropane and trimethyloläthandiallylather, Pentaerythritol triallyl ether and the like.

A0 9847/0890

Mixtures of various reactive unsaturated alcohols are also suitable. A suitable ene isocyanate can be prepared by reacting one mole of trimethylbenzene triisocyanate with 2 moles of trimethylolpropane diallyl ether. The urethane-containing en isocyanate is a polyene with h reactive allyl ether groups per molecule. Mixtures of different en- or in-isocyanates are also suitable.

Particularly preferred are unsaturated isocyanates, those of toluene diisocyanate with various unsaturated alcohols can be obtained in a molar ratio of 1: 1.

Another group of hydantoin polyenes according to the invention are Esters of the general formula:

S 0

Ο— [o ~ c-ö

in which Q is the hydantoin diol which remains after removal of zv / ei hydroxyl groups from the hydantoin diol with the formation of an ester linkage. The groups A, B and X and the numbers p, q, y and r have those assigned to them in the case of the urethane-containing hydantoinediol polyene
Meaning, and k is an integer from 0 to 1.

A general procedure for the formation of these esters consists in the hydantoinediol of the general formula Q- (OH) ₂ with at least one reactive unsaturated mono-

409847/0890

carboxylic acid of the general formula

■ E- (CO) _p -B _q - (x) _y ] _r

implement, in which the groups A, B and X and the numbers k, ρ q _} y and r have the meaning given to them before. The unsaturated reactive carboxylic acid is referred to below as en or in acid.

The esterification can be carried out in a customary manner in the presence of an acidic catalyst, the during water formed during the reaction can be removed as an azeotrope.

Suitable en or in acids include simple, monounsaturated acids such as acrylic acid, methacrylic acid, vinyl acetic acid, 5-hexenic acid, 6-heptinic acid, propiolic acid and others These monounsaturated acids correspond to the given general formula for suitable en- or in-acids, in which the numbers ρ and q are O and r 1. Accordingly, the ester halt igen hydantoinediol polyenes, which are formed from these reactive unsaturated acids, by the simplified formula

are described, in which y is preferably 1, and the

409847/0890

other groups have their previously assigned meaning.

Other suitable acids include those that have more than one contain terminally arranged, reactive, unsaturated groups per molecule. These can be produced by the reaction of a polycarboxylic acid of the general formula A- (COOH), in which χ at least 2 and A have the meaning given above, with a reactive unsaturated alcohol of the general formula Z ~ (X) -E7-0K, in which B, X and y have their previously given meaning.

These polycarboxylic acids and alcohols can be used in such stoichiometric amounts are added that χ carboxyl groups react to x-1 ester linkages.

Suitable polycarboxylic acids include the carboxylic acids such as adipic, tartaric, _3- suecic, terephthalic acids and others.

Suitable unsaturated alcohols include the same which have been described as being suitable for the formation of monounsaturated isocyanates. For example, a suitable en-acid can be prepared by one mole of trimethylolpropanäiallylether with one mole of succinic anhydride in

A09847 / 0890

Reacts the presence of pyridine as a solvent. The succinate product contains a free carboxyl group as well as 2 reactive allyl ether groups.

The new hydantoinediol polythiols are mercaptoesters with at least 2 thiol groups per molecule. The polythiol is a reaction product of hydantoinediol and at least one mercaptocarboxylic acid. In general, the polythiols have only 2 thiol groups per molecule and correspond of the following general formula:

Il

in which E is the hydantoinediol radical that remains after the two hydroxyl groups have been removed from the hydantoinediol, wherein two ester linkages are formed; R, is a polyvalent one organic group without reactive unsaturated carbon / carbon bond and contains aryl, substituted aryl, aralkyl, substituted aralkyl, especially benzyl and substituted benzyl, cycloalkyl, substituted cycloalkyl, alkyl and substituted alkyl groups of 1 to 16 carbon atoms.

Preferred suitable aryl groups include either phenyl or naphthyl groups and are examples of suitable ones Cycloalkyl groups have 3 to 8 carbon atoms

4098 4 7/0890

own. In these groups, in turn, as a sub substituents chlorine, bromine, nitro, acetoxy, acetamido, phenyl, benzyl, alkyl and alkoxy groups having 1 to 9 carbon atoms and cycloalkyl groups having 3 may be located to 8 carbon atoms.

A preferred group of hydantoin polythiols include the reaction products of a hydantoin diol general formula:

CH-;

HfOCH ₂ CH ₂ J _n -N N- (CH ₂ CH ₂ O ^ -H

in which m + η = 2 to 22 and m and η each at least are rait at least one mercaptocarboxylic acid, the polythiol having at least two thiol groups per molecule contains.

Suitable mercaptocarboxylic acids include thioglycolic acid (Mercaptoacetic acid), OC-mercaptopropionic acid, ß-mercaptopropionic acid, 4-mercaptobutyric acid, mercaptovaleric acid, Mercapto-undecyclic acid, mercaptostearic acid and o- and p-mercaptobenzoic acids. Preferably thioglycolic acid or ß-mercaptopropionic acid is used. Mixtures of different mercaptocarboxylic are also Suitable for acids.

4098A7 / 0890

- hl -

The polythioesters can by esterification of the hydantoinediol be prepared with mercaptocarbocyclic acid in the presence of an acidic catalyst, the during water formed during the reaction is removed as an azeotrope in a suitable solvent.

The reaction is ⁰ to 110 C, carried out for about 30 minutes to about 24 hours at atmospheric pressure and temperatures in the range of 60 to about 150 ° C, preferably 60th

Suitable acidic catalysts include p-toluenesulfonic acid. Sulfuric acid, hydrochloric acid and the like. Suitable inert solvents include saturated aliphatic ones Hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, ethers, ketones, etc. are examples of these are toluene, benzene, xylene, chloroform, 1,2-dichloroethane, etc.

By mixing the new hydantoinediol polyenes and polythiols and then subjecting them to a generator more freely Free radicals under normal conditions on the mixture will form a solid hardened insoluble polythioether product get a high percentage of elongation. In such curable compositions, the hydantoin diol skeleton be identical or different for both polyene and polythiol components.

409847V0890

- H 8 -

Before curing, the polyene and polythiol components
suitably to form a homogeneous solid
curable mixture mixed. Polyenes and polythiols can therefore at room temperature or at slightly elevated temperatures up to about 80 C if one of the components is solid
ist3 can be mixed without the use of a solvent, or if necessary they can be dissolved in a suitable solvent, after which the solvent is removed in a suitable manner such as by evaporation.

For maximum strength, solvent resistance against creep., Heat resistance, and to obtain Nichtklebrigkeifc _9, the reactive polyenes and
Polythiols, reacted with one another in such proportions,
that check comprising curing _s fixed three-dimensionally crosslinked PoIythioätherpolymere yield = To the formation of such infinite networks reach su, the individual must polyenes and polythiols each having a functionality of at least 2 aufweisenjs the sum of the functionalities of the polyenes and polythiols always greater than k must be. Mixtures of different polyenes and polythiols which have this functionality can also be used according to the invention. Functionality is the total number of reactive unsaturates
Carbon / carbon ^ bonds in the polyenes and the
Understood the number of thiol groups in the polythiols.

409847/0890

-U ₉ -

The curable compositions according to the invention can, if necessary, contain the following and similar additives: antioxidants, Accelerators, dyes, inhibitors, activators, fillers, thickeners, pigments, antistatic agents, Flame retardants, surfactants, extender oils, plasticizers and similar. These additives are usually mixed with the polyene or polythiol prior to curing. she can be in amounts up to 500 or more parts by weight, based per 100 parts by weight of the curable composition, and preferably from 0.005 to 300 parts.

The polythioether-forming components and compositions can be mixed with other monomeric or polymeric prior to curing Materials such as thermoplastic resins, elastomers or thermosetting resins are mixed in monomeric or polymeric form will. The mixtures can be subjected to conditions in which curing or simultaneous co-curing The various components of the mixture enter, resulting in hardened products with unusual physical properties and chemical properties.

As can other polyene / polythiol compositions the compositions containing hydantoinediol polyenes and / or polythiols are cured by curing by virtually any free radical generator that dissociates hydrogen atoms from the SH groups

4 0984 7/0890

or split off or trigger similar effects, be initiated. In general, the cure rate can be can be increased by increasing the temperature of the composition during the initiation of cure. In general, however, the hardening will take place in a convenient and economical manner at room temperature.

As described, the free radical generator for polyene / polythiol compositions is preferably actinic radiation (for example the wavelength from 2000 to 7500 2), in particular UV light (wavelength preferably 2000 to 4000 S); but just as can laser radiation, ionizing radiation, such as Gamma rays, X-rays, corona discharge, etc. as well as chemical compounds that generate free radicals, such as Azo and peroxy compounds can be used. These azo and peroxy compounds and their quantitative use have already been described in the cited patents.

The actinic light can be sunlight or come from artificial sources, such as RS elevation lamps, carbon arc lamps, Xenon arc lamps, mercury vapor lamps, tungsten halide lamps and the like.

The curing time can be accelerated to less than 1 minute or delayed to 30 days and more. In the already mentioned patents were conventional hardening

409847/0890

retarders and accelerators and their quantitative use described. The hardening can be carried out in a very short and therefore economically interesting time, by carefully selecting the UV light source, the accelerator for the photocuring speed and its concentration, Temperature, molecular weight and reactive functionality of polyene and polythiol. Curing times of less than 1 second are possible, especially when producing or using thin films - such as coatings, adhesives and surfaces of photographic image carriers.

It is desirable that the photo-curable composition a photo-curing accelerator (photosensitizer) in amounts of 0.005 to about 50 parts by weight based on 100 parts polyene and polythiol, contains when actinic light is used for curing. When using other Energy sources, such as ionizing radiation, accelerators are generally not used. That Molar ratio of en groups to thiol groups for making the curable composition is in the range from about 0.2: 1 to about 8: 1 and preferably from 0.5: 1 'to about 2: 1. The curable compositions containing hydantoinediol polyenes and polythiols can be used for preparation of solid, hardened, crosslinked, insoluble polythioether products for a wide variety of applications, e.g. for coatings, adhesives, foils and films,

4098 4 7/0890

molded articles, image-bearing surfaces, e.g. solid photoresists, solid printing plates, e.g. for offset and lithographic plates, letterpress and copier printing plates, gravure plates etc. as well as for non-silver photographic material and the like.

They are particularly suitable for producing coatings.

A general procedure for making coatings consists in applying the curable composition to the solid surface of a substrate such as plastic, rubber, glass, Ceramic, metal, paper, and the like apply them directly exposure to radiation, e.g. UV light, until the curable composition cures and crosslinks in the exposed areas. This results in cured coatings on suitable substrates or carriers.

The curable compositions according to the invention, which contain hydantoinediol polyenes and / or hydantoin polythiols, are of course particularly suitable for the method according to the invention for coating wires. Using of UV radiation for curing is usually one

Dose in the range from 0.000 * 1 to 6.0 watt / cm is suitable.

The new hydantoinediol polyenes and polythiols are described in more detail using the following examples. In all cases,

409847/0890

Unless otherwise stated, parts and percentages relate to weight.

example Ik

In a three-liter resin kettle equipped with a stirrer, thermometer, nitrogen inlet and outlet and vented addition funnel, 959 » ¹ ^ g of commercially available trimethylolpropane diallyl ether and 0.98 g of tin octoate catalyst were added under nitrogen. 1000 g of commercially available isophorone diisocyanate were placed in the addition funnel and added dropwise to the kettle over a period of k 1/2 hours at temperatures below 70 ° C. with stirring. After complete addition of the isophorone diisocyanate, the temperature to room temperature (2H ^O C) was dropped and stirred for 48 hours, not nitrogen.

In another 1 liter resin kettle equipped with a stirrer, thermometer, nitrogen inlet and outlet, and vented addition funnel, 535 g of the above reaction product with 16 drops of tin octoate were added. 301 g of commercial pentaäthoxyliert es.N, N'-bis (2-Hydroxyäthy1) dimethylhydantoin were added to the addition funnel and at temperatures below 70 ⁰ C with stirring was added dropwise into the Harskessel. The polyene product conformed to the formula

409847/089

NS.

* Il

(CH ₀ CK ₀ O) CNH
δ Ζ. τι

(CH ₀ CH ₀ O) CNH

* · /. Itlii

• CH

H !

CH ₂ NHCOCH ₂ CCH ₂ Ch ₃

CH ₂ OCH ₂ CH = CH ₂

CH ₂ OCH ₂ CH = CH ₂

CH ₀ NHCOCK ₀ CCH ₀ CH-, ^ Il ² | ^{2 3}

0 CH ₂ OCH ₂ CH = CH ₂

in which m + η = 7 is ₃ , the polyene product having a content of unsaturated carbon / carbon bonds of 2.9 mmol per g.

This polyene is referred to as polyene C in the following.

Example 15

261 g of commercially available toluene diisocyanate were added under nitrogen to a three liter resin kettle equipped with a stirrer, thermometer , nitrogen inlet and outlet and a vented addition funnel. 87 g of hand-made

409847/0890

Common allyl alcohol is introduced and then added dropwise to the resin kettle at temperatures below 85 ° C. while stirring. The addition was complete after 1 1/2 hours; for '^ urther 1 1/2 hours, the reaction was stirred and then the Isoeyanat analyzed _s with a value of ¹ J, 26 milliequivalents per gram resulted.

325 g of the reaction product were transferred to a 200 ml resin kettle which was equipped in the same way as described above and which contained 400 ml of chloroform and 0.25% tin octoate. 151.3 g of commercially available N, N ^f -Bis (2-hydroxyäthyD-dimethylhydantoin were added to the resin kettle, a clearly exothermic reaction being observed. The HCO band in the IR spectrum was followed until it disappeared. The material was placed in a mixer Then petroleum ether was added to separate the product as a fine white powder. The powder was filtered and dried in vacuo. The concentration of carbon / carbon unsaturated bonds was 2.7 mmol per g. The polyene corresponded to the formula

CH-

³ .0

CH ₂ = CHCH ₂ OCNH-JO-Hi ^ HCOCH ₂ CH ₂ N

This polyene is referred to as polyene D in the following.

409847/0890

Example 1β

29 * 1.8 g of commercially available toluene diisocyanate were added to a 1 liter resin kettle equipped with a stirrer, _{a thermometer, nitrogen inlet and outlet and a ventilated addition funnel.} 35.2 g of trimethylolpropane diallyl ether were placed in the addition funnel and then added dropwise to the resin kettle at temperatures below 28 ° C. under nitrogen. After the addition had ended, the material was stirred for 4 hours and had an NCO content of 2.7 milliequivalents per g.

In another 1 liter _{resin kettle with a stirrer s} thermometer ₃ nitrogen inlet and outlet and an addition funnel, 200 g of commercially available pentadecaethoxylated N, N ^! -Bis (2-hydroxyäthyD-dimethy! Hydantoin with an OH content of 1.95 milliequivalents per g was added simultaneously with 3 drops of tin octoate = 157 ₂ 2 g of the reaction product of toluene diisocyanate and trimethylolpropane diallyl ether were added to the addition funnel and then added dropwise to the resin kettle sugesstst. during the H1 / 2 hour addition the temperature was kept below 58 ⁰ C. the reaction was _s stirred for an additional 21 hours rfolgt during which the NCO content Biittsls IR Y ^ was "Bas furs containing 2 _S 35 millimoles per 3 unsaturated carbon / carbon bonds and corresponded to the formula

fs e \ β ■ / π ι π Q t \ Π

η Γ ³ O CH ₂ OCH ₂ CH = CH ₂

II ί, Ο 4-NHCOCH ₉ CCH ₀ CH, (CH ₂ CH ₂ O) CMT <^ * \

^Δ * ^η CH ₂ OCH ₂ CH = CH ₂

CH ₀ OCH ₀ CH = CH

in which m + η is 17. This polyene is hereinafter referred to as Denoted polyene E.

Example 17

Example 16 was repeated with the difference that 226 g of the reaction product of toluene diisocyanate and trimethylolpropane diallyl ether, 200 g of commercially available decaethoxylated N, N ¹ -bis (2-hydroxyethyl) -dimethylhydantoin, were added. The polyene had a content of unsaturated carbon / carbon bonds of 2.72 milliequivalents per g and corresponded to the formula

409847/0890

3 ₀ CH ₂ OCH ₂ CH = CH ₂

Hi

NHCOCH ₂ CCH ₂ Ch ₂

CH ₂ OCH ₂ CH = CH ₂

CH,
^ H ₃ -I HI I "" Q CH ₂ OCH ₂ CH = CH ₂

ii I

HHCOCH ₀ CCH ₀ CH ₀

CH ₂ OCH ₂ CH = CH ₂

in which m + η is 12. This polyene is hereinafter referred to as Polyene P denotes.

Example 18

Example 16 was repeated with the difference that 326 g of the reaction product of toluene diisocyanate and trimethylolpropane ^{diallyl ether were added to 200 g of commercially available pentaethoxylated N, N 1} -bis (2-hydroxyethyl) -dimethylhydantoin.

409847/0890

The polyene had a content of unsaturated carbon / carbon bonds of 3 _S 17 mmol per g and corresponded to the formula

■ ^H 3 _O CH ₂ OCH ₂ CH = CH ₂

U I

CH-

j (CH ₂ CH ₂ Oj

CH ₂ OCH ₂ CH = CH ₂

₀ CH ₂ OCH ₂ CH = CH ₂

it I

) _m CNH + O j HHCOCh ₂ CCH ₂ CH ₂

CH ₂ OCH ₂ CH = CH ₂

in which m + η = 7 »This polyene is referred to below as G designated"

Example 19

In a 3-liter resin kettle equipped with a stirrer thermometer _{s s} nitrogen inlet and outlet and addition funnel 250 g of commercial Toluoldiisoeyanat entered with 0 ₅ 28 g stannous octoate catalyst, under nitrogen. " 323Jl ¹ I g diallyl malate vmrden in the addition funnel and then introduced at temperatures below 58 ⁰ C, with stirring, added dropwise to the resin kettle. The reaction was continued ^l \ hours »529 g of the reaction product was placed in a

, 40984 // 08äU

- βο -

Transfer funnel and then added dropwise to a 2 liter resin kettle with 1 ^ 7.4 g of commercially available N, N ^f -Bis (2-hydroxy-Sthyl) -dimethylhyclantoin and 0.39 E tin octoate. As the addition progressed, the mixture thickened; the temperature could ^{rise to 100 °} C. in order to facilitate removal. A further 0.39 g of tin octoate were added to the reaction mixture and the reaction was carried out for a further 51 hours, after which no NCO content was found in the IR spectrum. The resulting polyene had a carbon / carbon unsaturation content of 4.06 mmol each

g and corresponded to the formula

. 0

CH,

O M

CH ₂ CH ₂ OCNFI

CH ₂ COCH ₂ CH = CH ₂

CH,

CH ₂ COCH ₂ CH = CH ₂

CH ₂ COCH ₂ CH = CH ₂

"CH ₂ CH ₂ OCKH-HD

0 f

Il ^!

HNCOCH

I! <

CH ₂ COCH ₂ CH = CH ₂

This polyene is referred to as polyene H in the following. The following examples illustrate the preparation of a polythiol described from a hydantoinediol.

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Example 20

^{432 g (2 mol) of commercially available N, N 1} -bis (2-hydroxyethyl) dimethyl hydantoin, 445 g of mercaptopropionic acid and 17.5 S of p-toluenesulfonic acid were placed in a 2 liter three-necked flask with a distillation attachment, stirrer and nitrogen inlet. 100 ml of ethylene dicloride was added to the flask. The mixture was heated with stirring for 8 hours, the water formed being continuously removed by azeotropic distillation at 71 to 75 ° C. and the ethylene dichloride being returned to the reaction flask. The solution in the flask was then washed once with about 1000 ml v / ater, twice with about 1000 ml 5% sodium bicarbonate and finally with about 1000 ml water. The solution was dried over anhydrous magnesium sulfate, mixed with 10 g of decolorizing carbon and filtered. The solvent was removed by vacuum distillation; 672 g (86 % yield) of the following polythiol were obtained

0 ti

CH

CH ₀

³ s?

obtain.

This polythiol is referred to as polythiol Z in the following

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Example 21

^{216 g of commercially available N, N I} -bis (2-hydroxyethyl) -diraethylhydantoin, 193 _S, 2 g of thioglycolic acid, 8.18 g of p-toluenesulfonic acid were placed in a 2 liter three-necked flask equipped with a stirrer, thermometer, Dean-Stark trap and reflux condenser and enter 500 ml of benzene. The mixture was refluxed with stirring. The water collected in the Dean-Stark trap was determined periodically and the reaction stopped after 39 »5 ml of water had been collected. The mixture was cooled to room temperature, washed with 500 ml of water and then twice with 500 ml of a 5% strength sodium hydrocarbonate solution and then with 500 ml of water. The benzene layer was removed and dried over 60 g of anhydrous magnesium sulfate. Then 2.5 g of decolorizing carbon were added and vacuum filtered through a frit. The benzene was removed under high vacuum to give 293 g of polythiol in 80.5% yield. Analytically, the SH content was determined to be 4.96 milliequivalents SH per g, the COOH content to 0.02 milliequivalents of COOH per g and the ester content to 6.07 milliequivalents of ester per g. The polythiol corresponded to the formula

after ₂ ch ₂ occh ₂ sh

It O

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^/ "■ - 63 -

The following examples describe the ability of the polyenes and polythiols to react to actinic exposure Radiation cured polythioethers to form. When the polyenes and polythiols are hardened together, hardened materials are produced with a high percentage of elongation before rupture compared to other commercially available polyenes and polythiols.

Example 22

The following compositions were taken in 200 ial brown sample bottles manufactured. In all cases, exactly weighed amounts of polyene, stabilizers, photosensitizers were used and polythiol added to the bottle and mixed homogeneously before use. The polyene C (which solidified at 25 ° C is used, it was heated to 80 ° C to facilitate weighing and handling.

Bottling A
Weight (g) component

71, ¹ I. Polyene G

28.6 pentaerythritol tetrakis (mercaptopro

prionate) - a commercial polythiol from Cincinnati Milacron Chemicals, Inc., Trade name "Q-43".

'' 2.0 benzophenone (photosensitizer)

0.05 H PO, (stabilizer)

0.2 octadecyl-ß - (* i-hydroxy-3,5-di-t-buty! Phenyl) -

propionate - commercial stabilizer from Geigy-Ciba under the trade name "IRGANOX 1076 "

0.1 2,6-di-tert-butyl-il-methylphenol, commercial

common stabilizer from Shell under the trade names "lonol" 409847/0890

Bottling B

Weight (g)

72.3 27.7

2.0 0.05 0.2 0.1

component

Polyene G

Ethylene glycol bis (mercaptoproprionate) -

commercial polythiol from Cincinnati

Milacron under the trade name "E-23",

Benzophenone

H ₃ PO ₃

"IRGANOX IO76"

"Ionol"

Bottling C

Weight (g)

69.2 30.8

2.0

component

Polyene G

Triinethylolpropane-tris- (mercaptopropionate),

a commercial polythiol available from Cincinnati

Milacron under the trade name "P-33 ¹¹

Benzophenone

0.05 H ₃ PO ₃ component Polyene G 0.2 "IRGANOX 1076" Polythiol Z according to Example 21 ο, ι "Ionol" Benzophenone Bottling D H ₃ PO ₃ Weight (g) "IRGANOX IO76" 60.75 "Ionol" 39.25 2.0 0.05 0.2 0.1

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Bottling E

weight (ff) component 79.5 7th Polyene C 30.0 "Q-43" 2.19 Benzophenone 0.054 H ₃ PO ₃ 0.219 ■ "IRGANOX 1076" 0.109 "Ionol"

Bottling F

Weight (g) component 65.2 Polyene C 22.5 "E-23" 1.95 Benzophenone 0.048 H ₃ PO ₃ 0.195 IRGANOX 1076 " 0.097 "Ionol" Bottling G Weight (g) component 71.3 Polyene C 30.0 , P-33 " 2.02 Benzophenone 0.050 H ₃ PO ₃ 0.202 "IRGANOX IO76" 0.101 "Ionol"

Bottling H

Weight (g)

Component Polyene C Polythiol Z Benzophenone

^H 3 ^P0 Ü
"IRGANOX IO76"

"Ionol"

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Each filling was placed on a glass plate and drawn out into a 500 µm thick film. This film was 2 minutes

at a surface intensity of 7000 microwatts / cm with UV radiation exposed from a UV ferro lamp. The cured samples were rated for percent elongation up to examined for tearing. The results are given in Table I.

Table I. Bottling % Stretchy A. 76 B. 84 C. 66 D. 154 E. 90 F. 75 G 63 H 133

The results show that mixtures D and H _5, which consist of polyene and polythiol, in which both components were obtained from a hydantoinediol, resulted in cured polythioethers which had very high elongation values compared to those used with those used herein Polyenes and commercially available mercaptoate esters can be achieved,

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Claims (8)

Claims i ·) A method for producing a solid coating on a wire, wherein the wire with a material which is curable liquid at the coating temperature and a solid plastic, is coated at temperatures up to 90 ⁰ C and cured coating to a solid plastic is, characterized in that a liquid material is used which is curable by the action of ultraviolet or high-energy radiation, and that it is exposed to such radiation for curing. 2. The method according to claim 1, characterized in that the wire through a coating form after the coating and leads before the irradiation step. 3. The method according to claims 1 and 2, characterized in that the coating is carried out by the wire immersed in a bath of the liquid material. 4. The method according to claim i to 3j, characterized in that that the wire is passed through the bath practically parallel to the surface of the liquid in the bath. 409847/0890 5. The method according to claim 1 to 4j, characterized in that that the wire through the bath and in a substantially vertical direction out of the bath for uniform Distribution of the liquid coating on the wire leads, and that the irradiation is carried out while the wire is in a substantially vertical position. 6. The method according to claim 1 to 5> characterized in that a liquid composition is used as the radiation-curable material which (1) contains a polyene containing at least 2 unsaturated carbon / carbon bonds per molecule, which under the action of ultraviolet or high-energy Radiation are reactive with a polythiol, and (2) contains a polythiol containing at least 2 thiol groups per molecule, the total functionality of unsaturated carbon / carbon bonds per molecule of polyene and thiol groups per molecule of polythiol being greater than k . 7. The method according to claim 1 to 6, characterized in that one veri ^ ends a composition which is an accelerator the photo-curing rate, and that curing is carried out by means of UV radiation. 409847 / 089G 8. The method according to claim 1 to J _3, characterized in that a liquid composition is used as the radiation-curable material which (1) at least one ethylenically unsaturated component capable of addition polymerization which, in the presence of an initiator for addition polymerization, enables photoinitiated polymerization and by ultraviolet Light can be initiated, and (2) contains an addition polymerization initiator. ugs: rew: kö / cm 409847/0890