DE2256611A1 - RADIANT COMPOUNDS AND DIMENSIONS - Google Patents

Description

Patent attorneys'

Dr. Ing.Walter Abltz '

Dr.Dio.terF.Morf. _{17 # November 1972}

Dr. Hans-A. Brauns 9679-acs

8 Munich bü, Pienzenau & str. 23

SUN CHEMICAL CORPORATION

200 Park Avenue, New York, N * Y., Delaware, V.St.A.

Radiation-curable compounds and compositions

The present invention relates to radiation curable compounds and compositions, especially compounds, which have built-in sensitizers and are themselves photopolymerizable or can be used as phcto initiators for radiation-curable monomers.

The use of radiation-curable, ethylenically unsaturated, monomeric substances in coating compounds, adhesives, printing inks and the like is known. It is also known that such monomeric substances are converted into polymers by the action of radiation and that they are converted at an increased rate polymerize when irradiated in the presence of a photoinitiator and / or a photosensitizer will.

309821/1224

9679-ACS -

With the use of added photoinitiators or However, photosensitizers along with the monomer in a radiation curable system have numerous disadvantages tied together. In the first place it should be mentioned that photoinitiators are caused by radiation, such as ultraviolet light »electron radiation or gamma radiation, must be able to be activated. At the same time, they must also be inactive at ambient temperatures so that the storage and handling stability of the compositions containing them is guaranteed. Besides that the photoinitiator must be compatible with the monomer and the other components, if any, in the system be. For example, the initiator may only have limited solubility in the selected monomer is so that the rate of photopolymerization, which to some extent the concentration of the Initiator in the system '' is proportional, is reduced. It is also possible that the presence of an initiator limits the usability of other additives in the mass, so that the achievement of the physical properties necessary for optimal performance in use, the the product is ultimately to be added is prevented.

The photoinitiator can form undesirable by-products that are not bound to the polymer productj the photosensitizer usually does not go into the polymer chain as a component. As a result, education of a product, at least in part, possible that can be leachable by solvents.

In addition, many photoinitiators are crystalline and fail when left to stand. Also can if photoinitiators are added, the even distribution, the volatility and migration of the initiator material pose problems.

309821/1224

It has now been found that certain compounds polymerize by themselves when exposed to a radiation source and co-polymerize, d. H. they photopolymerize in the absence of a photoinitiator at a rate that of the corresponding rate of previously disclosed monomers in the presence of a photoinitiator is comparable or, in some cases, sogax * greater than that is.

Paints and coatings made from these fabrics are solvent-free, hydrophobic and almost dry instantly in air at ambient temperature when exposed to a radiation source, so the need the use of stoves is eliminated as well as air pollution, Fire hazards, odor nuisance, etc., which accompany the use of volatile solvents, be avoided. The inks can be processed excellently on offset printing. They form extremely hard ones and permanent films on a wide variety of substrates, such as newsprint, coated Paper supply, irregular, for example corrugated cardboard, metals, e.g. B. foils, braids, cans and bottle caps, woods, rubber, polyesters such as polyethylene terephthalate, glass, polyolefins such as treated and untreated polyethylene and polypropylene, cellulose acetate, fabrics such as cotton, silk and rayon, and the like. They show no change in color in the applied film, if they are exposed to the required curing conditions and they are resistant to peeling, smearing, Spraying with salt, wear and tear, rubbing and the corrosive effects of substances such as alcohols, oils and fats, resistant. The adhesives made with these substances have particularly good binding properties. Besides that the compounds and masses can withstand both heat and cold, which is what they do, for example, in printing inks or coatings for containers that have to be sterilized.

" ⁵ "
309821 / 122A

9679-ACS y

e for example at. Temperatures up to about 150 ° C under pressure, and / or needing to be cooled, for example below about -20 ° C ₁ , etc. makes useful.

The compounds according to the invention are preferably polyfunctional, Ethylenically unsaturated monomers and prepolymers, resins, polymers and mixtures thereof, the one Benzophenone or a substituted benzophenone component contain. As used herein, the term "polyfunctional, ethylenically unsaturated" relates to Compounds with two or more terminal or pendant ethylenic groups.

The novel compounds according to the invention can be prepared by the customary methods for ester preparation. In particular, the compounds according to the invention produced by using a hydroxy-containing, ethylenic-unsaturated Ester or such a resin is reacted with a benzophenone which has at least one carboxyl substituent or an ester-forming derivative thereof such as an anhydride or acid chloride. Examples of suitable carboxy-substituted benzophenones and ester-forming derivatives thereof are benzoylbenzoic acid, carbonyldibenzoic acid, Carboxybenzoylphthalic anhydride, benzophenone tetracarboxylic acid, Benzophenone tetracarboxylic acid dianhydride and halogen- and dialkylamino-substituted benzoylbenzoic acid and anhydrides.

The compounds according to the invention are represented by the following formula I

COOR

0 9 8 21/12 2

9679-ACS $

in which: X and Y are each hydrogen, 1 to 3 halogen atoms, ie. Cl, Br or J ₁ or a dialkylamino with 2 to 4 carbon atoms, Z,., Zg and Z, each hydrogen or COOR ^, in the. each B represents hydrogen, alkyl (1 to 18 carbon atoms), cycloalkyl, aryl or aralkyl, or E has the same meaning wxe R, but each R can be different from R, and R denotes the monovalent radical which, after removal of a QH- Group from the hydroxy-containing, ethylenically unsaturated ester or resin remains means, ie? it means the remainder that is linked to the alcoholic OH that is involved in the esterification reaction

Examples of such BTDA derivatives include esters of polyfunctional alcohols, esters of partial esters or ethers of polyfunctional alcohols, di- und.Triacryloxyäthylester and the like. So the carboxy-substituted benzophenones with, for example, monomeric, polyfunctional Esters or modified, monomeric, polyfunctional esters are reacted with monomers and prepolymers, d. H. Dimers, trimers and other oligomers or their mixtures or their copolymers, the general as acrylic acid, methacrylic acid, itaconic acid. and the like. Esters of aliphatic, polyhydric alcohols, e.g. B. di- and polyacrylates, di- and polymethacrylates and Di- and polyitaconates of A "ethylene glycol, triethylene glycol, Tetraethylene glycol,! Tetramethylene glycol, trimethylolethane, Trimethylolpropane, butanediol, pentaerythritol, dipentaerythritol, Tripentaerythritol, other polypentaerythrites, Sorbitol, d-mannitol, diols of unsaturated fatty acids and the like., Are described. -

Typical compounds include (but this list is not limiting) trimethylolpropane diacrylate, trimethylol ethane diacrylate, Trimethylol propane dimethacrylate, trimethylol ethane dimethacrylate, i-detramethylene glycol mono-

- 5 -309821/1224

9679-ACS ^

methacrylate, Ithylenglykolmonomethacrylat, Triäthylenglykolmonomethacrylat, Tetraäthylenglykolmonoacrylat, Tetraäthylenglykolmonomethacrylat, pentaerythritol diacrylate, Pentaerythrittriacjr / lat, pentaerythritol-3,5-acrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, Mpentaerythritpentaacrylat, Tripentaerythrithexacrylat, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, Mpentaerythrittetramethacrylat, Tripentaeyrthritlieptamethacrylat, pentaerythritol, Bipentaerythrittrisitaconat, dipentaerythritol, Dipentaerythritol 5,> - itaconate, ethylene glycol monomethacrylate, 1,3-butanediol monoacrylate, 1, J-butanediol monomethacrylate, 1, ^ - butanediol monoitaconate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol tetramethacrylate, Boritol pentaacrylate, sorbitol 5 »5-acrylate, and the like, and mixtures and prepolymers thereof.

These products with a built-in sensitizer can be used in leather any known and expedient manner produced be, for example by reacting the hydroxyl-containing Esters with the carboxy-substituted benzophenone in one such amount that the equivalents of benzoic acid or of the anhydride approximately equal to the equivalents of the hydroxyl groups of the compound with which the carboxy-substituted Benzophenone is reacted, are, at a temperature of about 50 to 150 ° C and preferably of about. 70 to 110 ° C, although these conditions are not critical.

The photocuring rate of the reaction is determined by affects the amount of benzophenone or substituted benzophenone moiety in the product. For the purposes of the present invention, the amount of the portion is generally about 3 to 50% by weight, based on the product, and is preferably about 15 to 40% by weight, based on the product, equivalent.

309821/1224

9670-ACS

The hy (* roxy-containing, ethylenically unsaturated ester corresponds to preferably of the formula

. OX HO-Y- (OCC = CH ₂ ) _n ,

in which X is hydrogen or an alkyl group with about 1 to 8 carbon atoms and Y is an alkylene group with about 1 to 12 carbon atoms, an aryl group, a cycloaliphatic group Represent a group or a substituted derivative thereof; and η is an integer from 2 to 5.

Although the novel products of the present invention can photopolymerize at satisfactory rates in the absence of photoinitiator additives, their photohardening rates can be increased by adding another photoinitiator. Examples of suitable photoinitiators include the following: acyloins; Acyloin derivatives, such as benzoin methyl ether, benzoin ethyl ether, desyl bromide, desylchloric, desylamine and the like \ ketones, such as benzophenone, acetophenone, ethyl methyl ketone, cyclopentanone, benzil, capron, benzoylcyclobutanone, dioctylacetone and the like; substituted benzophenones, such as Ν, Ν-dimethylaminobenzophenone and Michler's ¹ ketone; polynuclear quinones such as benzoquinone and anthraquinone; substituted, polynuclear quinones; halogenated aliphatic, alicyclic and aromatic hydrocarbons and their mixtures in which the halogen can be chlorine, bromine, fluorine or iodine; and the like; and mixtures thereof. Examples of halogenated photoinitiators include polyhalogenated hydrocarbons such as polychlorinated triphenyls; polyfluorinated phenyls (EI du Pont de Nemours &Co.); chlorinated rubbers such as Perlone (Hercules Powder Company); Mixed polymers of vinyl chloride and vinyl isobutyl ether, such as Vino flex MP-400. (BASF CoIc r _s and Chemicals, Inc.); chlorinated aliphatic waxes such as Chlorowax 70 (Diamond Alkali, Inc.); Perfluoropentacyclo-

- 7 - 309821/1224

9679-ACS

decan, such as Dechlorane ⁴ "(Hooker Chemical Co.); chlorinated paraffins, such as Chlorafin 40 (Hooker Chemical Co) and Unichlor-70B (Neville Chemical Co.); mono- and polychlorobenzenes; mono- and polybromobenzenes; mono- and polychloroxylenes; Mono- and polybromoxylenes dichloromaleic anhydride; 1- (chloro-2-methyl) naphthalene; 2,4-dimethylbenzenesulphonyl chloride; 1-bromo-3- (ni-phenoxyphenoxybenz jl); 2-bromo-methyl ether; chlorendinic anhydric anhydric; ; Hexachlorocyclopentadiene; hexachlorobenzene; and the like; and mixtures thereof. The quantitative ratio of benzophenone derivative to photoinitiator is generally about 99 J 1 to about 10:90 and preferably about JO: 70 to about 70:30.

In addition to being photopolymerizable in the absence or presence of other photosensitizers, the novel compounds of the invention can also be used as photosensitizers, as they increase the cure rate of a variety of polyethylene unsaturated esters, such as those listed above, modifications of these esters and mixtures thereof. The compounds according to the invention can also be used alone as photo-sensitizers or together with at least one other photosensitizing additive. When used as photosensitizers, the compounds according to the invention are used in a ratio to the polyethylenically unsaturated monomer of about 1:99 to about 90:10 and preferably from about JO : 70 to about 70: JO.

For example, when used in conjunction with a second initiator or sensitizer, such as those listed above 0.1 to 10 parts by weight of the second initiator per 100 parts of the carboxy-substituted benzophenone derivative.

- 8 3 0 9 8 21/12 2 4

Also falls within the scope of the present invention Division of resinous derivatives of carboxy-substituted ones Benzophenones, "e.g. from alkyds, polyesters, polyethers, polyamides, carbamates, epoxides, etc., the have built-in sensitizers and as such are useful for coatings, paints, adhesives and the like, or in various fields of application in connection with drying oils, alkyd resins, vinyl resins, monomers polyfunctional Ε-star, modified monomeric, polyfunctional Esters, etc. can be used with or without a second initiator.

Alkyd resins can be substituted by a car.boxy Benzophenone with, for example, iron glycol or a higher polyol together with or without other acids or anhydrides such as phthalic anhydride, isomeric phthalic acids etc., can be produced. These alkyd resins can be modified be used, for example with oils such as linseed oil, Safflower oil or thistle oil or with an isocyanate such as Tolylene diisocyanate or phenyl isocyanate.

Polyamides can be substituted by a carboxy one Benzophenone with, for example, a short-chain diamine or other polyamine and other dicarboxylic acids such as dinate. Fatty acids (dimers of linoleic acid) are produced.

Saturated and unsaturated polyesters can be prepared by reacting a carboxy-substituted benzophenone with, for example a polyol, such as a glycol or a pentaerythritol, and maleic or fumaric acid together with or without drying oils and acids such as coconut oil and lauric acid will. -

Mixed polymers of the compounds according to the invention with Ethylenically unsaturated monomers are the same

- 9 -309821/1224

within the scope of the present invention. For examples of such comonomers include styrene, α-methylstyrene, acrylic acid and methacrylic acid, acrylates and methacrylates, acrylamides, Acrylonitrile, bibutyl maleiite, dibutyl fumarate, biallnlphthalate, Vinyl acetate, vinyl chloride, vinyl fluoride, ethylene, propylene, butadiene, isoprene and the like, and mixtures thereof. These copolymers generally contain about 0.1 to 50% by weight of the carboxy-substituted ones described above Benzophenone derivatives.

Approaches which make use of these compounds and compositions can use well-known modifying agents be incorporated, e.g. B. Plasticizers; Wetting agent for the dye, such as Bi chlorate ethyl stearate and other chlorinated fatty acid esters; Leveling agents such as lanolin, paraffin waxes and natural waxes; and the like Such modifying agents are generally used in amounts up to about J% by weight, preferably about 1% by weight, based on the total weight of the batch.

The approaches can be of any convenient type Way according to known bispersion methods, for example in a pulp mill, a sand mill, a ball mill, a colloid mill or the like.

Variables that determine the rate of drying of a radiation curable compound or composition include the nature of the substrate, the special components in the mass, the concentration of the photoinitiator, the Bicke of the material, the nature and intensity of the radiation source and its distance from the material, the presence or absence of oxygen as well as the temperature of the surrounding atmosphere. Bie irradiation can be done after any or a combination of a variety of methods. The mass can, for example, contain actinic acid Exposed to light of any origin and any kind

- 10 309821/1224

9679-ACS Ai

provided that the light source provides an effective amount of ultraviolet radiation since the actinic Light activatable masses generally range from about 1800 S to 4000 S and their maximum sensitivity preferably from about 2000 S to 3000 S; she can Bundle electron beams, gamma emitters and the like and Combinations of these sources are exposed. Appropriate sources include (this list is not limiting) Charcoal arcs, mercury vapor arcs, fluorescent lamps with special, ultraviolet light emitting phosphors, argon glow lamps,. photographic floodlights, Van der Graaff accelerator etc.

The exposure time must be sufficient to be effective Dosage to give. The irradiation can take place at any convenient temperature; becomes most appropriate irradiated at room temperature for practical reasons. The distances between the radiation source and the workpiece can be from about 0.317 cm (1/8 inch) to 25.4 cm (10 inches) and preferably range from about 0.317 cm to 15/2 cm.

The compounds and compositions of the invention are absent of solvents and in the presence or absence of, oxygen as a carrier for paints, varnishes and printing inks that set or when irradiated able to harden, useful. They are also used as masses and basic components for the production of photographic Images, printing plates and rollers; as adhesives for foils, films, papers, fabrics and the like; as coatings for metals, plastics, paper, wood, foils, textiles, glass, cardboard, cardboard and the like; as markings for streets, parking lots, airfields and similar areas; etc useful.

When used as a carrier for inks, e.g. B. Printing inks, can connect to any of a variety of conventional organic or inorganic pigments,

3098217 ^ 2-24

9679-ACS st

ζ. B. molybdate orange, titanium white, chrome yellow, phthalocyanine blue and soot, pigmented and colored with dyes in a conventional manner. For example, the Carrier in an amount of about 20 to 99-9% by weight and the Dye can be used in an amount of about 0.1 to 80% by weight, based on the total mass.

Materials that can be printed on include paper, clay coated paper, and cardboard. The inventive Masses are also suitable for the treatment of textiles, both natural and synthetic, for example in carriers for textile printing inks or for special treatments of fabrics to produce water-repellent ones Properties, oil and stain resistance, khitter resistance, etc., are useful.

If the radiation-curable substances according to the invention are used as adhesives, at least one of the substrates must be translucent or translucent when using ultraviolet light. When the radiation source is on Electron beam or gamma radiation is must at least one of the substrates should be able to let through electrons of high energy or gamma radiation, and none the substrate is necessarily translucent. Typical layers include polymer-covered cellophane-on-with Polymer coated cellophane film; polymer-covered cellophane-on-plypropylene; Mylar on ~ a metallic material such as aluminum or copper, polypropylene-on-aluminum and the like.

The radiation-curable compounds according to the invention can be used for metal coatings and especially for metals that are to be subsequently printed. Glass and plastics can also be printed or coated, and the coatings are conveniently through Rolling or spraying applied. Pigmented coating

- 12 309821/1224

systems can be used for various polyester and vinyl films; Glass; polymer covered cellophane; treated and untreated polyethylene, for example in the form of disposable cups or bottles; treated and untreated polypropylene; and the like can be used. For examples of Metals that can be plated include sized and non-press finished tinplate. '

Photopolymerizable parts obtained from the inventive Fabrics to be made include a carrier, e.g. B. a foil or sheet metal, and an overlaid layer of the radiation-curable material described above. Suitable substrates and substrates include metals such as steel and aluminum plates; Sheets; and Foils; and foils or sheets made up of different Film-forming, synthetic resins or high polymers, such as addition polymers, and especially vinyl polymers, z. B. vinyl] chloride polymersj vinylidene chloride polymers; Vinylidene chloride copolymers with vinyl chloride, vinyl acetate or acrylonitrile5 linear condensation polymers, such as polyesters, e.g. B. Polyethylene terephthalate polyamides etc. »Fillers or reinforcing agents can be seen in the synthetic resin or polymer bases to be available. In addition, highly reflective substrates can be treated in such a way that they are exposed to ultraviolet light absorb, or a © light-absorbing layer " between the base and the outer photopolymerizable layers be pushed «,

Photopolymerizable part® can be produced by irradiating selected portions of the photopolymerizable layer of the photopolymerizable ropes until the addition polymerization is up to. the desired depth in the irradiated portions is finished. The non-irradiated portions of the layer are then removed, for example by means of solvents which dissolve the monomer or prepolymer but not the polymer.

309821/1224

When a carboxy-substituted, benzophenone-modified monomer or resin with a photosensitizer, which is im visible spectrum absorbed, e.g. B. an acyloin type photosensitizer such as benioin, is mixed a clear, liquid mass that can be poured in any thickness. The potted mass hardens when when exposed to actinic or ultraviolet radiation, it becomes a solid plastic useful as a building material, encapsulating electrical components, and the like is.

Oil-free polyester and polyurethane alkyd resins produced from a carboxy-substituted benzophenone are well suited for use as plasticizers for amino formaldehyde resins and vinyl resins. Isocyanate-terminated polyesters and polyethers which contain the benzophenone or substituted benzophenone moiety are available as foams and technical coatings useful. Polyamide resins that contain built-in sensitizers are particularly popular in Printing inks, coatings and adhesives are useful.

Polyesters which have been prepared from a carboxylic acid substituted benzophenone and a 1,2-disubstituted ethylene, such as maleic anhydride or fumaric acid, may be in monomers "such as styrene or Metliylmethacrylat dissolved and be reinforced with glass fibers to prepare a composition, the materials when exposed structural layer results that are suitable for boats, roofing materials and the like .

The compounds and compositions described here have many advantages over the conventional paints and coatings of the oil-resin type and solvent type . The substrate does not need to be pretreated or prepared in any way. The use of volatile solvents and the associated dangers and odor nuisances are eliminated. The colors and coatings show

- 14 -309821 / 1224

exhibits excellent adhesion to the substrate after irradiation. Their gloss. And their resistance to rubbing are good, and they hold high temperatures of around 150 ° C and. low from about -20 ° C. The printed or coated panels can be used immediately after being exposed to the energy source have been edited and rotated.

The invention and its advantages will be better understood from the following representative examples; however, the invention is not intended to be limited by these examples. Unless otherwise stated, parts in the examples are given as parts by weight. Venn the ingredient is solid at room temperature, the mixture may, unless otherwise indicated, are heated to melt the solid component, but generally in ^s are not used at above 100 ° C, or it may be in admixture with other liquid components. The atmospheric and temperature conditions were, unless otherwise noted, the ambient conditions.

example 1

A. A mixture of 7 ^ 7 parts of pentaerythritol 3,5-acrylate (1 equivalent of OH) and 120 parts of benzophenone tetracarbonic acid dianhydride (BTDA) was heated to 80 to 90 ° C. in the presence of phosphoric acid as a catalyst “The product was a half-ester adduct of the penta: rythritol-3i5-acrylate

and BTDA. ·.

B. The product from section (A) was coated on a slide glass with a wet film thickness of 0.3 microns applied and from a distance of 5 »08 cm (2 inches) irradiated with a 15> 2 cm 1200 watt mercury vapor lamp. The film dried in 0.95 seconds.

309821/1224

9670-ACS

C. For comparison purposes, a mixture of 90 parts Pentaerythritol-J, 5-acrylate and 10 parts of benzophenone such as dried above in section (B). The film dried in 25 seconds.

example 2

A mixture of 70 parts of the BTDA derivative of the example 1 (A) and 30 parts of a polychlorinated triphenyl, the Containing 60 wt% chlorine (polychlorinated hydrocarbon 5460 from Monsanto Chemical Co.) was prepared and under the conditions of Example 1 (B) in 0.6 seconds dried to a non-sticky film.

Example 3

A mixture of 30 parts of the product of Example 1 (A) and 70 parts of an isocyanate-modified pentaerythritol triacrylate dried according to the method of the example 2 (B) in 6.5 seconds.

example M-

A mixture of 15 parts of the BTDA derivative of the example 1 (A), 70 parts of an isocyanate-modified pentaerythritol triacrylate and 15 parts of the polychlorinated hydrocarbon 5 ^ 60 (Monsanto) under-dried in 2.4 seconds the conditions of Example 1 (B) to a non-tacky film. -

Example 5

The procedures of Examples 1 (A) and 1 (B) were repeated with each of the following monomers instead of pentaerythritol 3,5-acrylate: trimethylolethane diacrylate, trimethylolprop.ane diacrylate, trimethylolpropane dimethacrylate,

- 16 309821/1224

9679-AOS, *

Pentaerythritol trimethacrylate, pentaerythritol diitaconate, a mixture of dimers and trimers of pentaerythritol triacrylate and sorbitol tetracrylate. The results were comparable.

Example 6

The procedure of Examples 2 and 4 was carried out with each of the the following initiators instead of the polychlorinated hydrocarbon 5 ^ ° (Monsanto) repeated: chlorendic anhydride, Ν, Ν-Diraethylamino-benzophenone, 4-, 4 -'- bis- (Dimethylaminq) -benzophenone, Benzil, benzoin methyl ether, acetophenone and hexachlorobenzene. The results were comparable. ■ ""

Example 7

The procedures of Examples 1 (A) and 1 (B) were repeated with carbonyl dibenzoic acid instead of BTDA «. the Results were comparable »

Example 8

A. A mixture of 2-2 ropes of o-benzoylbenzoic acid (o-BBA), 85.6 parts propylene glycol, and 20 parts xylene was heated to 225 ° G under nitrogen. The reaction water distilled in the xylene azeotrope from ₉ on &'eii © temperature was kept at 225 to 230 ° G until the acid number was 2 (about 6 hours) "The xylene was removed by vacuum distillation". The product _s propylene glycol dibenzoyl benzoate _s is a viscous liquid with an acid number of 1.2.

B. A mixture of 0.6 parts of the product of section (A) and 10 parts of an isocyanate-modified pentaerythritol triacrylate was used as a coating on tin-free steel

- 17 _ 309 * 821 / 1224-

9679-ACS fi

applied to a thickness of 0.00254 mm (0.0001 inch) and 'Under a 100 watts / 2.54 cm (100 watts / inch) medium pressure mercury arc lamp irradiated. A hard, cured film was obtained in 5 seconds.

Examples 9 to 12

Each of the following connections was made in a thickness of 0.3 micron wet film coated on a slide glass applied and from a distance of 7 »62 cm with a 200 watt / 2.54 cm mercury vapor lamp irradiated. The length of time each product required to develop resistance to fingernail scratching is below specified:

Example connection curing time,

in seconds

9 bis (acryloxymethyl) ethyl ~ o-benzoyl-

benzoate 12

10 tris (acryloxymethyl) ethyl o-benzoyl benzoate 7

11 tris (acrylaoxymethyl) ethyl o- (p ~ chlorobenzoyl) benzoate 1.3

12 tri 8- (acryloxymethyl) -ethyl-o- (p-dimethylaminobenzoyl-benzoate K 0.1

The compound of Example 9 was made from o-BBA and trimethylolethane triacrylate manufactured; the compound of the example was prepared from o-BBA and pentaerythritol triacrylate j and the compound of Example 11 was converted from o- (p-chlorobenzoyl) benzoic acid and pentaerythritol triacrylate. The compound of Example 12 was prepared from o- (p-Dimethylaiainobenzoyl) benzoic acid and pentaerythritol triacrylate.

For comparison purposes, compounds outside the scope of the invention were identified in the same way as indicated above,

- 18 -

309821/1224

with the following results (curing time in seconds) checked:

(a) Acryloxybutyl O-benzoyl benzoate 30

(b) lauryl acrylate / 60

(c) 1,4-butanediol diacrylate 45

(d) Pentaerythritol tetraacrylate 31

(e) Pentaerythritol tetraacrylate / benzophenone (90/10 mix). 23

It is thus seen that the products of the reaction of polyfunctional, ethylenically-unsaturated esters ¹ with a carboxylic acid substituted benzophenone (Examples 9 to 12) solidify considerably faster than the product of the reaction of _s monofuntioneilen ethylenically-unsaturated esters and 0-BB4. (a), mixtures of polyfunctional, ethylenically unsaturated esters with benzophenone (e), and mono- and polyfunctional, ethylenically unsaturated esters without any added or built-in benzophenone (b, c and d)

Example 13

A. Benzoylbenzoic acid modified s polyamide r Resin made by adding 205.1 parts of dimeric fatty acids with 68.1 parts of o-benzoylbenzoic acid were reacted at 140 ° C. 31.5 parts of ethylenediamine were slowly added dropwise to the mixture, the exothermic reaction being caused by cooling at .etwa 140 to 150 ° C was maintained. After completing the addition of the dimer, the resulting polymeric salt was slowly dehydrated by heating to 200 ° C.

which melts at 92 ° C. It is soluble in lower alcohols

The product is an amber colored thermoplastic resin that melts at 92 ° C. It is in n: and compatible with nitrocellulose.

- 19 - ■ 309821/1224

B. A thin film of an alcohol solution of the polyamide of paragraph (A) above was exposed to ultraviolet Exposed to light and in 3 seconds to an insoluble, adhesive coating cross-linked.

Example 14

A. A non-drying alkyd resin was made by converting the following constituents at 200 to 230 ° C in 6% xylene as an azeotrope over the course of 10 hours were: 175 parts of pelargonic acid, 50 parts of o-benzoylbenzoic acid, 137 parts of phthalic anhydride, 2 parts of fumaric acid and 135 parts of pentaerythritol.

The product had an acid value of 5> 5 and its viscosity in xylene was about 6 to 9 poises at 50 %

B. A 65/35 mixture of the alkyd resin of section (A) and an isocyanate-modified pentaerythritol triacrylate was applied as a coating to tin-free steel and exposed to a 100 watt / 2.54 cm ultraviolet lamp. In A very good, crosslinked film was obtained in about 2.5 seconds.

Example 15

A benzoylbenzoic acid modified unsaturated polyester resin was prepared by heating the following ingredients to 198.9 ° C under nitrogen: 73.5 parts Maleic anhydride, 137 »9 parts propylene glycol, 103.6 Part of phthalic anhydride, 90.8 parts of benzoylbenzoic acid and 0.02 part of hydroquinone. The response has been so long carried out at 196.1 to 201.7 ° C until the product has an acid value of 40 to 45 and a viscosity of 11 poises at 70% in styrene. The batch was then on

- 20 309821/1224

9679-ACS 11

143 ti ° C cooled and added dropwise to 186 parts of styrene monomer. The product contained 70 % solids and had a Gardner viscosity of 11 Ms 15 poise.

The product dried in 2 seconds when exposed to ultraviolet light "was exposed.

Example 16

A benzoylbenzoic acid rosin modified phenolic resin was made by adding 800 parts of WW-Eolophonlum and 200 parts of o-benzoylbenzoic acid were heated to 248.9 ° C. 200 parts of liquid phenol-formaldehyde resin were slowly added. When the addition was complete, 10 £> Parts of 95% glycerine were added and the hate slowly increased to 271.1 ° C heated, at what temperature it was kept for so long, until an acid value of 14 to 20 was reached (about 4 to 6 hours).

The product was a hard, amber-colored resin that. at 154.4 to 160.0 ° G it melted »It x-rare in petroleum solvents soluble in drying oils. When exposed to ultraviolet rays, the product dried in 3 seconds »

Bei Piel 17

A. A benzoylbenzoic acid polyurethane ester was made like is made as follows: ^ O parts xylene, 425 parts dipropylene » glycol and 120 parts of trimethylolethane would be placed in a 3 liter resin flask fitted with a thermometer, stirrer, Inert gas inlet tube and heating mantle set up for Dean-Stark decantation of water of esterification. The mixture was heated to 75 ° C and then mixed with 454 parts of o-benzyolbenzoic acid. The temperature continued at 150 ° G under a nitrogen cushion

- 21 -

309821/1224

heated until esterification began. After 5 hours rose the reaction temperature to 217 ° C and it was 35 »5 B Water of reaction has been collected.

The acidity of the product was 3 »8 ^ g KOH ^ e grams of resin. The reaction mixture was stripped at 200 ° C and 20 mm Hg vacuum.

At 200 ° C. and 20 mm Hg vacuum, the remaining xylene

The reaction temperature was lowered to 110 ° C. and 253 parts of an 80/20 mixture of the 2,4- and 2,6-isomers of toluene diisocyanate were added via a dropping funnel over the course of 1 hour to raise the temperature of the exothermic reaction below 150 ° G. After all of the toluene diisocyanate had been added, the viscous reaction mixture was kept at 150 ° C. until all of the free NCO had been consumed at 4.45 A according to a control by means of an ultra-red decomposition of a product sample.

The product, a pale amber o-BBA polyurethane ester was applied at 75 to 100 ° C. He had one Melting point in the range from 45 to 54 ° C, measured according to the Durran mercury method. The resin was freely soluble in aromatic hydrocarbons, ketones and esters.

B. A solution of 30 parts of the product of the above Section (A) in 70 parts of pentaerythritol tetraacrylate was applied in a thin film to corona treated polyethylene film and coated with vinylidene chloride Cellophane laminated. The sample was blown with a 200 watt / 2.54 cm Hanovia lamp for 0.2 seconds exposed j what the complete hardening of the adhesive, and gave a laminate with excellent peel strength.

- 22 -

309821/1224

9679-ACS

Example 18

The products according to the invention were made up into colors and tested as follows:

A. A mixture of 85 parts of tris (acryloxymethyl) ethylo-benzoyl benzoate and 15 parts of phthalocyanine blue was printed on coated paper with the printing press and by passing under three 200 watt / 2.54 cm mercury vapor lamps at a speed of 366 m / min. (1200 feet per minute) dried.

B. A mixture of 68 parts of tris (acpyloxymethyl) ethylo-benzoyl benzoate, 15 parts of phthalocyanine blue and 17 parts of polychlorinated hydrocarbon 5460 (Monsanto) by web offset printing on coated paper (14 ^ 5 kg; 32 pounds). The color was determined by passing it under three 200 watt / 2.54 cm mercury Daia lamps with a Speed of 244 m / min, dried "

C. A mixture of 23 parts of a BBA modified, Oil-free alkyd resin, 59 parts isocyanate, anate-modified Pentaerythritol triacrylate, 15 parts of phthalocyanine blue and 3 parts of 4,4'-bis- (dimethylamion) -benzophenone was applied to clay-coated sulfite cardboard by web offset printing. prints and dried by printing at a speed of 168 m / min, on a lithographic sheet-fed machine that with two 200 watt / 2.54 cm reflector mercury vapor lamps was equipped, was promoted.

D. A mixture of 50 parts of BBA-modified linseed oil alkyd resin, J> 0 parts of isocyanate-modified pentaerythritol triacrylate, 15 parts of phthalocyanine blue and 5 parts of 4.4 ^l -bis- (dimethylamino) -benzophenone was printed onto clay-coated sulfite cardboard and dried by conveying it at a speed of 183 m / min on the system of the above section (C).

~ -2-3 309821 / 1 224

In each case, the sheets stood out freely without the use of spray powders and were scratch resistant.

E. A mixture of 85 parts of a 30/66/4 mixture of propylene glycol dibenzoyl benzoate (an isocyanate-modified pentaerythritol triacrylate / ^^ '- bis-id'imethylamino) benzophenone and 15 parts of phthalocyanine blue was from a distance of 5 »08 cm exposed with a 15/2 cm 1200 watt mercury vapor lamp and dried in 0.7 seconds to form a non-sticky film.

Example 19

The products of Examples 1 (A), 2, 3, 7, 8, 14 and 15 were made by offset engraving in film weights ranging from 0.227 to 1.36 kg per ream (ο 5 to 3-0 pounds per ream) applied to any of the following substrates: saran-coated cellophane, corona-treated polyethylene, polyvinylidene dichloride-coated polypropylene, and mylar. Laminations were made at 65.6 ° C and 22.7 kg / 2.54 cm (50 pounds / inch) pressure between cellophane and cellophane, cellophane and polyethylene, cellophane and polypropylene, and polypropylene and mylar, and the laminates were then cured , by

at a speed of 15.2 m / min, from a distance, 2.54 cm with a 1200 watt Hanovia ultraviolet lamp were exposed. The laminations were successful as evidenced by tearing seals that Bond strengths of at least 3OO g per 2.54 cm (3OO grams per inch).

Example 20

The procedure of Example f \ Q was repeated with each of the following dyes instead of phthalocyanine blue.

_ 24 309821/12 2 4

Benzidine Yellow, Lithol Ruby Red, Buss, Milori Blue, and Phthalocyanine Green. The results were comparable.

Example 21

The procedures of Examples 1 (B), 2-4, 8 (B) and 9 to 19 were 'repeated with the amendment that the samples, instead of being exposed to ultraviolet light, on a conveyor belt under the beam of a Dynacote 300,000 volt electron linear sole unigers at one speed and with a beam of rays that is like this was regulated so that a dose level of 0.5'Megarad resulted. .

These systems supplied resinous substances of varying degrees of hardness in 12.7 to 508 η (0.5 to 20 mils) thick films sticky surfaces.

Example 22

The procedure of Examples 1 (B), 2-4, 8 (B) and 9 "to 19 were repeated with the modification that the samples, instead of being irradiated with ultraviolet light, received a Combination of ultraviolet light and electron radiation in a variety of arrangements: ultraviolet light, then electron beam, then ultraviolet light; Ultraviolet light before and after the electron beam enbündel; Electron beams before and after the ultraviolet irradiation and simultaneous irradiation with Electron beams and ultraviolet light. The results were comparable.

- 25 -

309821/1 2 2 U

Claims (18)

9679-ACS 17 # November 1972 Patentana exam ehe 1. Radiation-curable compound obtainable by reacting at least one carboxy-substituted benzophenone or E3ter-forming derivative thereof with a hydroxy-containing, ethylenically unsaturated ester or resin. 2. connection nr.ch claim 1, characterized in that the carboxy-substituted benzophenone benzophenone tetracarboxylic acid dianhydride is. 3 · Connection according to claim 1, characterized in that the carboxy-substituted benzophenone benzoylbenzoic acid is. 4. A compound according to claim 1, characterized in that the carboy substituted benzophenone is carbonyl dibenzoic acid. >. Compound according to claim Ί, characterized in that it corresponds to the given formula Ϊ. 6. A compound according to any one of claims 1 to 5i, characterized in that that the ethylenically unsaturated ester consists of an ethylenically unsaturated acid and a polyhydric alcohol. 7 · Connection according to claim 6, characterized in that the acid is acrylic, methacrylic or itaconic acid. 8. A compound according to any one of claims 1 to 7> characterized in that the ethylenically unsaturated ester is an isocyanate-modified ester. - 26 - 309821/1224 9679-ACS j 9 · Connection according to one of claims 1 to 5 »thereby characterized in that the resin is an alkyd resin, an oil-modified one Alkyd resin, an isocyanate-modified alkyd resin, a polyamide, a polyester, a polyether, is an epoxy resin, a carbamate resin, a phenolic resin or a polyurethane resin. 10. A compound according to any one of claims' to 9> characterized in that it is polymerized with an ethylenically unsaturated comonomer. 11. A compound according to any one of claims 1 to 10, together with at least one photoinitiator in a radiation-curable Dimensions. ' 12. Composition according to claim 11, characterized in that the photoinitiator is at least one of the following is: a halogenated hydrocarbon, acyloin, an acyloin derivative or a ketone. 13 · Composition according to claim 11 or 12, characterized in that the quantitative ratio of compound to photoinitiator is about 99: 1 to 10:90. 1A-. Radiation-hardenable printing ink containing a compound according to any one of claims 1 to 11 and a dye. Λ5>. Coating composition containing a compound according to one of Claims 1 to 11. 16. A method for producing crosslinked polymers, characterized in that a mass according to exposing any one of claims 1 to 15 to a radiation source. - 27 - 3 0 9 8 2 1/1 2 2 9769-ACS if 17. The method according to claim 14, characterized in that the radiation source is ultraviolet light Is an electron beam or a combination thereof. 18. An adhesive compound containing a compound according to any one of claims 1 to 11. _ 28 - 309821/1 224