Polymerizable compositions.

0001The present invention relates to compositions with a content of cationically polymerizable material, a hydroxy compound and an aromatic iodosyl salt. It also extends to the polymerisation of such compositions by means of actinic radiation or heat and to the use of such compositions as surface coatings, in the manufacture of printing plates and printed circuit boards, and as adhesives.

0002As is known, it is desirable to initiate polymerization in organic materials by means of actinic radiation. Such processes can be used, for example, to avoid the use of toxic and / or flammable solvents with their environmental problems and costs for their recovery. Photopolymerization makes it possible to restrict the insolubilization of resin compositions to certain zones, ie on the irradiated areas, thus allowing the production of printed circuits and printing plates or making it possible to limit the adhesion to substrates to narrowly defined zones. Furthermore are_BRadiation procedures are often faster than those in which heating and possibly a cooling stage are required.

0003Photopolymerization compositions with a content of cationically polymerizable material, a hydroxy compound and an aromatic iodonium salt as photopolymerization catalyst are already known. The presence of the hydroxy compound improves the flexibility of the photopolymerized composition.

0004_So describes the U_S-A-4 256 828 photopolymerizable compositions with a content of polyepoxide, an organic material with a hydroxy functionality of at least 1 and an aromatic iodonium salt of the formula<chemistry id="chem0001" num="0001"><img file="EP0146501A2_D0001.tif" /></chemistry>as a photoinitiator, in which Ar¹ and Ar² aromatic groups with 4 to 20 carbon atoms in the form of phenyl, thienyl, furanyl or pyrazoyl groups, Z an oxygen or sulfur atom or a group of the formula <chemistry id="chem0002" num="0002"><img file="EP0146501A2_D0002.tif" /></chemistry> (wherein R represents an AryL group with 6 to 20 carbon atoms or an AcyL group with 2 to 20 carbon atoms), a carbon-carbon bond or a group of formulas <chemistry id="chem0003" num="0003"><img file="EP0146501A2_D0003.tif" /></chemistry> (wherein _R¹ and R² each represents a hydrogen atom, an ALkyL group with 1 to 4 carbon atoms or an ALkenyL group with 2 to 4 carbon atoms), represent n is 0 or 1 and X is a tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate anion.

0005US Pat. No. 4,090,936 discloses light-curable liquid compositions with a content of organic material with an average epoxy functionality of 1 to 1.3, a compatible organic polymer with a glass transition point in the range from -20 ° C. to 105 ° C. the organic polymer being an acrylic or methacrylic polymer, a copolymer made of styrene and ALLYLaLkohoL or a polyvinyl butyl and an aromatic KompLexsaLz as photoinitiator, for example, an aromatic iodonium salt of FormeL I known.

0006The use of aromatic iodonium salts as heat-activated hardeners for cationically polymerizable materials in the presence of certain catalysts is known, for example, from US Pat. No. 4,192,924, according to which the catalyst is a mixture of a copper salt and ascorbic acid, an ascorbate, tin salt or an activated one _a-Hydroxyverbindung is also from US-A-4 374 751, according to which the KataLysator is a peroxide.

0007An article by FM Beringer and P. BodLaender, J. Org. Chem., 1968, 33, 2981-4 describes a number of diaryl iodosyl salts and their preparation. However, this article gives no indication of how such salts behave under actinic radiation or when heated in the presence of other organic materials, or how they can be used.

0008Surprisingly, it has now been found that aromatic iodosyl salts act as photoinitiators for the polymerisation of compositions containing epoxides or other cationically polymerizable materials and hydroxy compounds, and that the salts act as heat-activable polymerisation agents for such compositions in the presence of certain catalysts. None of the prior art publications mentioned above suggested that an iodosyl salt would have such valuable properties.

0009The aromatic iodosyl salts of the compositions according to the invention are generally much more accessible than the aromatic iodonium salts of the previously known compositions, the production of the iodonium salts generally requiring complicated preparative steps under strict conditions. In the case of compositions with a content of certain types of cationically polymerizable material, in particular cycolo-aliphatic epoxy resins, the compositions according to the invention are faster photopolymerizable than the corresponding compositions with a content of iodonium salts and result in polymerized products of comparable flexibility. As for compositions that have been cationically polymerized using iodonium salts, those containing cyclo-aliphatic epoxy resins are usually more reactive than bisphenol-based epoxy resins. This difference in reactivity is even more pronounced in the compositions polymerized using aromatic iodosyl salts.

0010The present invention accordingly relates to polymerizable compositions with a content of<ul id="ul0001" list-style="none"><li>(A) cationically polymerizable material,</li><li>(B) an epoxy-free organic hydroxy compound with at least one alcoholic hydroxy group, exclusively those hydroxy compounds which form free radicals when heated to a temperature above 50 ° C., and</li><li>(C) an aromatic JodosyLsaLz of the formula<chemistry id="chem0004" num="0004"><img file="EP0146501A2_D0004.tif" /></chemistry>where R³ and _R⁴ may be the same or different and each represents a monovalent aromatic radical having 4 to 25 carbon atoms, x is 1, 2 or 3, and Z^x- an x-valent anion of a protonic acid means.</li></ul>

0011Another object of the invention is a method for producing a polymeric material, which comprises the following steps:<ul id="ul0002" list-style="none"><li>(i) Irradiation of (A) a cationically polymerizable material, (B) an epoxy-free organic hydroxy compound with at least one alcoholic hydroxyl group, exclusively those hydroxyl compounds that form free radicals when heated to a temperature above 50 ° C and (C) an iodosyl salt Form II containing composition with radiation of a wavelength activating the iodosyl salt, preferably in the range from 200 to 600 nm, and / or</li><li>(ii) heating the composition in the presence of (D) a salt or complex of a d-block transition metal, a tin-II salt, an organic peroxide or an activated α which forms free radicals when heated to a temperature above 50 ° C -Hydroxyverbindung, as KataLysator for the JodosyLsaLz, until the composition is polymerized. The cationically polymerizable material (A) can be, for example, a cyclic ether such as an oxetane or tetrahydrofuran, a cyclic ester such as a lactone or episulfide such as ethylene sulfide, a vinyl monomer such as a vinyl ether, StyroL, VinyLcarbazoL or a vinyl prepolymer. (A) is preferably a 1,2-epoxy such as_Eethylene oxide, propylene oxide or an epoxy resin, a PhenopLast, aminoplast, such as a urea / formaldehyde or MeLamin / formaldehyde resin or a cyclic vinyl ether. Particularly preferred cationically polymerizable materials are cycloaliphatic epoxy resins such as 3,4-epoxycyclohexanecarboxylic acid 3 ', 4'-epoxycyclohexyl methyl ester and its 6,6'-dimethyl derivative, ethylene glycol bis - (3,4-epoxycyclohexane carboxylate), bis (3, 4-epoxycycLohexyLmethyL) adipate, DicycLopentadieneioxid and VinyLcycLohexendioxid, optionally pre-elongated polyglycidyl ethers of polyhydric alcohols such as 1,4-butanediol and diethylene glycol and polyhydric phenols such as 2,2-bis (4-hydroxyphenyL) propane and phenol / aldehyde novolaks, cyclic vinyl ethers with a dihydropyran residue such as 3,4-dihydro-2H-pyran -2-carboxylic acid-3,4-dihydro-2H-pyran-2-yLmethyl ester and phenol / formaldehyde resols. Mixtures of two or more cationically polymerizable materials can also be used.</li></ul>

0012The hydroxy compound (B) is generally an epoxy-free organic material with one or more primary or secondary alcoholic hydroxy groups, which is not activated by other groups so that it forms free radicals when heated to above 50 ° C. Mixtures of hydroxy compounds can also be used. Monohydroxy compounds, especially those with a molecular weight of 60 to 250, are useful in certain applications, for example in the formulation of low viscosity coating compositions. Examples of suitable monohydroxy compounds are ALkanoLe such as 1-ButanoL, 1-Octanol, 1-DecanoL, CycLohexanoL and Cyclohexylmethanol, aralkyl alcohols such as benzyl alcohol, MonoaLkyLether from ALkyLengLykoLen such as 2-methoxyethanoL, 2-butoxyoxyethanol and 2-Ethoxyalkanol and 2-Ethoxyalkanol like and 2-Ethoxyalkanol like and 2-Ethoxyalkylene like and 2-Ethoxyalkylene like as well of PoLyoxyethyLen- and PoLyoxypropyLengLykoLen.

0013In general, hydroxy compounds having 2 or more alcoholic hydroxy groups, which may be primary or secondary, are preferred. Suitable polyhydroxy compounds are DioLe such as 1,4-butanedioL and TrioLe such as glycerin. Preferred polyhydroxy compounds have a molecular weight of at least 100 and in particular more than 500. Examples of suitable compounds with a MoLekuLarweight in this area are PoLyoxyaLkyLengLykoLe and triols such as PoLyoxyethyLen - ,. PoLyoxypropyLen and PoLyoxytetramethyLengLykoLe and -triols, PoLyepichLorhydrine, PolyLoylLoyl hydroxyls with Hydroxy and Loyl hydroxyls such as HydroxyLoxyL, HydroxyLylyl acrylates with Polycaprolactate and Polyolrolate groups, Polycaprolactates with Polyolrolate groups, and Polycaprolactones with Polycaprolactones and Polyolrolate groups such as , PoLyvinyLaLkohoLe, HydroxypropyLceLLuLose and hydroxyl-containing PoLyvinylacetale.

0014Other suitable polyhydroxy compounds are substances with a content of secondary alcoholic hydroxyl groups, which by reaction of an epoxy resin (which if necessary - by pre-extending an epoxy resin of low molecular weight, in particular a polyglycidyl ether of a polyhydric phenol, is obtainable, for example, by reaction with a dihydric phenol or a dicarboxylic acid) with an excess of a compound bearing one or more groups which are reactive with epoxy groups, such as, for example, phenolic hydroxyl, carboxyl, primary or secondary amino or mercapto groups. Other suitable polyhydroxy compounds are phenolic resols, ie resins produced by the reaction of a phenol with an excess of aldehyde, such as phenolformaldehyde resols. If a phenol formaldehyde resol is used as the cationically polymerizable material (A) in a composition according to the invention, the hydroxy compound (B) must be present in the form of a different ResoL or a compound other than a resol.

0015Particularly preferred hydroxy compounds are StyroL / ALLyLaLkohoLcopoLolymer, PhenoL / FormaLdehydresoLe and resins containing secondary alcoholic hydroxyl groups, which by reaction of a diglycidyl ether of 2,2-bis (4-hydroxyphenyL) propane, which in turn optionally 4 (with 2,2-bis) -hydroxyphenyL) -propane can be pre-extended with an excess of a mono- or dihydric phenol, in particular phenol or 2,2-bis- (4-hydroxyphenyl) propane.

0016The content of hydroxy compound (B) in the compositions according to the invention can vary within a wide range, depending on how compatible the hydroxy compound is with the cationically polymerizable material and the type of physical properties required in the polymerized product. If monohydroxy compounds are used, their content is generally such that it corresponds to 0.001 to 0.2 equivalents of the hydroxy compound per equivalent of the epoxide or another cationically polymerizable material, and when using polyhydroxy compounds the latter are present in an amount of 0.001 to 10 equivalents of the hydroxy compound per equivalent of the cationically polymerizable material. Particularly suitable compositions with a content of preferred polyhydroxy compounds have 0.8 to 1.2 equivalents of the hydroxy compound per equivalent of the cationically polymerizable material.

0017In the diaryl iodosyL salts according to formula II, the residues R³ and R⁴ preferably identical and optionally substituted mono-, di- or trihomocyclic or heterocyclic aromatic groups. Examples of suitable heterocyclic aromatic groups are thienyl, FuryL, PyridyL and pyrazolyl groups. Examples of suitable tricyclic aromatic groups are anthryL, phenanthryL and FLuorenyL groups, suitable mono- and dicyclic aromatic groups being phenyl and naphthyl radicals and groups of the formula<chemistry id="chem0005" num="0005"><img file="EP0146501A2_D0005.tif" /></chemistry>where Y¹ a carbon-carbon bond, an ether oxygen atom or a group of the FormeL -CH₂- or -CCCH₃)₂- is, mean. Each of these aromatic groups can optionally be substituted by one or more atoms or groups which do not impair the release of an acid type when the salt is irradiated or heated. Typical representatives of these substituents are ALkyL and ALkoxy groups with 1 to 4 carbon atoms, nitro groups and halogen atoms. Preferably R³ and R⁴ each optionally substituted phenyl, in particular phenyl, or phenyl substituted by an alkyl group having 1 to 4 carbon atoms, in particular a methyl or isopropyl group, a halogen atom, in particular a fluorine atom or a nitro group.

0018Suitable anions Z^x- Derived from organic carboxylic acids, such as acetate and trifluoroacetate, or from organic sulfonic acids Y-SO₃H, in which Y is an aliphatic, aromatic or aliphatic-substituted aromatic group which is optionally mono- or polysubstituted by halogen atoms and preferably has 1 to 20 carbon atoms, such as methanesulfonate, benzol-sulfonate, ToLuoL-p-sulfonate or trifluoromethanesulfonates, and in particular of inorganic acids, in particular of inorganic acids such as FLuorid, ChLorid and Bromid, HaLogenaten such as iodate, PerhaLogenaten such as PerchLorat, as well as nitrate, SuLfat, HydrogensuLfat, Phosphates, hydrogen phosphates and complex anions such as pentafluorohydroxoantimonate and those of the FormeL MQ_w, where M stands for a MetaLL or MetaLLoid atom and Q for a HaLogenatom and w is an integer from 4 to 6 and one greater than the value of M.

0019The anions of the FormeL MQ_w are preferably polyhalogenides of antimony, arsenic, _Bismuts, iron, tin, boron and phosphorus, such as hexafluoroantimonate, hexachloroantimonate, hexafluoroarsenate, pentachlorobismutate, tetrachloroferrate, hexachlorostannate, tetrafluoroborate or hexafluorophosphate, the latter two being particularly preferred.

0020Any cationically polymerizable material can be polymerized by irradiation or heating in the presence of a suitable diaryl iodosyL salt of form II. However, not every such material is polymerized by each of these salts; the exact nature of the material and that of the anion Z^x- is critical and must be selected to achieve effective polymerisation results. The coordination of a cationically polymerizable material with a suitable anion is definitely part of the specialist knowledge in the field of curing or polymerizing cationically polymerizable compositions. Examples are salts with a content of anions which are derived from organic carboxylic acids, organic sulfonic acids and inorganic acids, in particular acetates, trifluoroacetates, methanesulfonates, benzosulfonates, toluo-o-sulfonates, trifluoromethanesulfonates, perchloride, perchloride, FL , Nitrates, sulfates, hydrogen sulfates, Phosphates or hydrogen phosphates, capable of curing phenolic loads such as phenol / formaldehyde resins and aminoplasts such as urea / formaldehyde and melamine / formaldehyde resins. Salts containing a MetaLL or metalloid halide anion are capable of curing epoxy or episulfide resins or polymerizing mono-1,2-epoxides, monoepisulfide or vinyl ether. Other materials which can be polymerized in the presence of an iodonium salt by heating or irradiation can be polymerized by irradiation in the presence of a suitable diaryl iodosyL salt of form II or by heating in the presence of such a salt and a catalyzer (D) therefor.

0021The amount of diaryl iodosyL salt in the compositions is usually not critical, since only catalytic amounts are required to initiate curing or photopolymerization. In general, 0.01 to 10 to 10% by weight, preferably 0.5 to 5% by weight, based on the weight of the cationically polymerizable material (A), will be used.

0022Diaryl iodosyl salts of Form II II can be prepared analogously to a process as described by FM Beringer and P. BodLaender, loc. Cit. An iodarene of formula IV is oxidized to the corresponding iodine oxyar of form L V using peracetic acid. Treatment of iodine oxyarenes or a mixture of two iodine oxarenes with an ALkaLimetaLLhydroxid gives the JodosyLhydroxide of the form VI, which can be converted into the carbonate of the form VII by treatment with carbon dioxide. This hydroxide or carbonate is mixed with an acid of FormeL H_xZ (if such acids exist) to form the desired salt. (Immediate neutralization of the iodosyl hydroxide sometimes leads to lower yields of the desired salt as if it is first converted into the carbonate). If such acids do not exist in the free state or are difficult to handle, the hydroxide or carbonate can be treated, for example, with acetic or trifluoroacetic acid to form the corresponding acetate of formula VIII or trifluoroacetate of formula IX. Such a SaLz is mixed with an alkali metal or ammonium salt of acid H_xZ, for example a phosphate, hexafluorophosphate, tetrachloroferrate or hexafluoroantimonate, to obtain the desired product of the formula II, treated with double decomposition.

0023These reactions are illustrated by the following scheme:<chemistry id="chem0006" num="0006"><img file="EP0146501A2_D0006.tif" /></chemistry>

0024Hexafluoroantimonates can be prepared by adding solid sodium or potassium hexafluoroantimonate to an aqueous solution of iodosyl acetate or trifluoroacetate: If the sodium or potassium salt is first dissolved in water, the isolated product is the hydroxopentafluoroantimonate due to HydroLysis (Z^x- = SbF₅(OH)^-).

0025If the compositions according to the invention are to be photopolymerized, they may also contain a photochemical free radical generator or a photosensitizer. It has now been found that the incorporation of such suitable accelerators further increases the speed of curing, which allows the use of shorter exposure times and / or weaker radiation sources. Aromatic carbonyl compounds are particularly preferred radical formers. Although these have already been used for the radical polymerization of ethylenically unsaturated compounds, it is surprising that they accelerate the cationic polymerization.

0026Suitable aromatic carbonyl compounds include ketals of aromatic diketones, especially compounds of the formula<chemistry id="chem0007" num="0007"><img file="EP0146501A2_D0007.tif" /></chemistry>one in which R⁵ a hydrogen atom, an ALkyL group with 1 to 5 carbon atoms, an ALkenyL group with 2 or 3 carbon atoms, an AraLkyL group with 7 to 9 carbon atoms or one. Aralkenyl group with 8 or 9 carbon atoms, or a group of the formula L -CH) -_mR⁷ means R⁶ a group of FormeL -CH₂CH (R⁹) - or -CH₂CH (R⁹) CH₂-, R is a halogen atom or a group of formulas -_OR , -SR⁸, -OR¹², -SR¹², -OCOR⁸ or -COOR⁸, m 1, 2 or 3, row⁸ an ALkyL group with 1 to 4 carbon atoms, R⁹ are a hydrogen atom or an ALkyLgruppe with 1 to 18 carbon atoms and _R¹⁰, _R¹¹ and R¹² independently of one another in each case mean a given case with up to 3 substituents from the series of halogen atoms, ALkyL or alkoxy groups with 1 to 4 carbon atoms and phenyl groups substituted by phenyl groups.

0027EXAMPLES of compounds of formula X are BenziLdimethyLketaL, BenziLdiethylketal, BenzildI- (2-methoxyethyl) -ketal and BenziLdi- (2-chLorethyL) -ketaL. Examples of compounds of the formula XI are 2-phenyl-2-benzoyL-4-methyl-1,3-dioxolane and 2-phenyl-2-benzoyL-1,3-dioxane. A particularly preferred aromatic carbonyl compound of this type is BenziLdimethyLketaL.

0028Compounds of FormeL X or FormeL XI are known from US-A-4 190 602, where they are used for the photopolymerization and photocrosslinking of ethylenically unsaturated compounds such as methyllacrylate, styrofoam-containing polyesters based on maleic acid and diaLLyLphthaLatpräpoLymeren.

0029Other substances suitable as photo accelerators include aromatic-aliphatic ketones in one of the formulas<chemistry id="chem0008" num="0008"><img file="EP0146501A2_D0008.tif" /></chemistry><chemistry id="chem0009" num="0009"><img file="EP0146501A2_D0009.tif" /></chemistry><chemistry id="chem0010" num="0010"><img file="EP0146501A2_D0010.tif" /></chemistry>and<chemistry id="chem0011" num="0011"><img file="EP0146501A2_D0011.tif" /></chemistry>one in which R¹⁰ has the meaning given above, R¹³ and R¹⁴ each represent a monovalent aliphatic, cycLoaLiphatic or araliphatic group or together with the carbon atom linking them form a CycLoaLkyLengruppe, R¹⁵ is a carbon-carbon bond or a divalent organic radical, R¹⁶ represents a hydroxy or amino group or a monovalent etherified or silylated such group, R¹⁷ a divalent amino, ether or SiLoxy group, R¹⁸ a direct chemical bond or -CH₂- and R¹⁹ -0-, -S-, -SO₂-, -CH₂-or -C (CH₃)₂- mean.

0030These compounds, of which preferred representatives include 2-ALLyLoxy-2-methyLpropiophenon, 2-Benzyloxy-2-methyl-propiophenone, 2-Hydroxy-2-methyL-p-phenoxypropiophenone, 1-BenzoyLcycLohexanoL, 1-Benzoylcyclopentanol and bis- (4th - (α-Hydroxyisobutyryl) phenyl) ethers are also known from US Pat. No. 4,308,400 as photopolymerization catalysts for ethylenically unsaturated compounds and as light crosslinkers for polyolefins.

0031Other compounds which can optionally be used to increase the rate of photopolymerization of the salts of the FormeL II are 2-substituted thioxanthones of the FormeL<chemistry id="chem0012" num="0012"><img file="EP0146501A2_D0012.tif" /></chemistry>where R²⁰ is either a chlorine atom or an ALkyL group with 1 to 6 carbon atoms, such as an isopropyl or tert-butyl group. Compounds of Formula XVI, in particular the 2-chlorine compound, are used industrially as photopolymerization catalysts for ethylenically unsaturated compounds and as light crosslinkers for PoLyoLefins.

0032We preferably use 30 to 125% by weight, in particular 50 to 100% by weight, of photo accelerator, based on the weight of the diaryl iodosyl salt of formula II.

0033The compositions can also include photosensitizers such as polyaryls (e.g. perylene and 9,10-di- _ethoxyanthracen), PoLyaryLpoLyene, 2,5-DiaryLisobenzofurane, 2,5-DiaryLfurane, 2,5-Diarylthiofurane, 2,5-Diarylpyrrole, 2,5-DiaryLcycLopentadiene, Polyarylphenylene, Coumarin or PoLyaryL-2-pyrazoLine contain.

0034If the compositions according to the invention are to be polymerized essentially solely by heat, they also contain (D) a salt or a complex of a d-block transition metal, a tin-II salt, an organic one _Poxide or an activated α-hydroxy compound that forms free radicals when heated to a temperature above 50 ° C as a catalyst for the iodosyl salt.

0035Organic peroxides which can optionally be used as catalyst (D) in the curable compositions according to the invention include dicumyl peroxide, tert-butyl perbenzoate, tert-butyl peroxide and in particular benzoyl peroxide. A preferred tin-II salt is tin-II chloride.

0036The KataLysator (D) is preferably a SaLz or KompLex of a d-BLock transition metal or an activated α-hydroxy compound. D-BLOCK transition metals are those of the first transition series from scandium to zinc and those of the second transition series from yttrium to cadmium. Zinc, cobalt, chromium, iron and particularly preferred copper are the preferred d-block transition metals, the salts or complexes of which are used as catalysts (D). The salts can optionally be derived from organic acids or mineral acids, such as chlorides, acetates, trichloroacetates, naphthenates, octanoates and oxalates. Suitable complexes are π-orbital complexes and those which are formed from ligands forming inner complexes, such as aldehydes, ketones, carboxamides or aliphatic aminomono- and polycarboxylic acids. Particularly preferred complexes are those which are formed from 1,3-diketones such as acetylacetone, or its homologs such as benzoylacetone and its derivatives such as ethyl acetoacetate.

0037The activated a-hydroxy compound is a compound having a hydroxy group attached to a carbon atom in an α-position to an activating group such as a carbonyl group or a carbon atom bearing a hydroxy group, the compound providing free radicals when heated. Suitable activated α-hydroxy compounds include ascorbic acid, ketones such as AcyLoine and Benzoine as well as activated DioLe such as PinakoL and its HomoLogen, in particular BenzpinakoL.

0038If desired, certain catalysts (D) can be used together, such as a SaLz or KompLex of a transition metal such as copper acetylacetonate or copper benzoate together with ascorbic acid or benzpinakoL.

0039The amount of catalyst (D) is not critical, but will generally be in the range from 10 to 150% by weight, based on the weight of the diaryl iodosyl solution used.

0040Other substances which may be incorporated into the compositions according to the invention include diluents and FULL substances, such as silicic acid, talc, _Glasmic balloons, clays, metal powder or zinc oxide, viscosity regulators such as asbestos, rubber grades, tackifiers and pigments.

0041When a composition according to the invention is exposed to radiation with a suitable wavelength, the iodosyl salt acting as a photoinitiator is obviously activated by releasing a type of acidic compound, which causes the polymerisation and, if the composition contains a curable cationically polymerizable material such as an epoxy or phenolic resin, also the crosslinking of the composition brings about. The radiation used in the method according to the invention can be exclusively ultraviolet radiation or, if appropriate, radiation with wavelengths both in the ultraviolet and in the visible spectra range. The compositions can also contain dyes to respond to visible spectra ranges. Suitable dyes are known for example from US-A-4 026 705; these are generally cationic dyes such as acridine gel, acridine orange, phosphine R, benzoflavin, setoflavin T and their mixtures.

0042The preferred WAVELENGTH of the radiation used in the process according to the invention is in the range from 200 to 600 nm, in particular 200 to 400 nm. The selection of the suitable RADIATION SOURCE among the commercially available devices which emit radiation within the above-mentioned WAVELENGTH range is a routine measure for specialists Field of photopolymerization.

0043The compositions according to the invention containing a catalyst (D) are rapidly polymerized when heated to a temperature above 50 ° C., preferably to a temperature in the range from 80 ° to 180 ° C. The compositions are optionally heated for 1 to 200, preferably 1 to 30, minutes.

0044If the compositions according to the invention contain a curable, cationically polymerizable material, in particular an epoxy resin or a phenolic resin, they can be pre-cured by irradiation and then cured by heating. For a two-stage hardening process, the composition contains either a catalytic converter (D) which accelerates the hot hardening with the iodosyl salt or another heat-activatable hardener for the hardenable material. Such heat-activated hardeners are known, and it is part of the routine knowledge of the person skilled in the art in the field of hardening processes to select a hardener suitable for the specific hardenable material. If it is desired to store the pre-hardened material for a subsequent heat hardening process, it is of course important to carry out the exposure at a temperature which is below the temperature at which substantial heat hardening of the photopolymerized product by means of the heat hardener would occur.

0045Thus, the compositions according to the invention with a content of epoxy resins or phenolic loads can be hardened in two stages. If PhenopLast is a NovoLak that cannot be polymerized under the influence of iodosyl salt, it is used together with a material that can be polymerized under its influence, such as an epoxy resin or a cyclic vinyl ether. The composition is first brought into the precured B-state by actinic radiation in the presence of a latent, heat-activated crosslinker for the epoxy resin or PhenopLast (optionally if the PhenopLast is a ResoL), and in a second stage the precured composition is used to complete the curing warmed up. Accordingly, a liquid or semi-liquid preparation can be produced, which can then be shaped or used to impregnate a substrate to be solidified under exposure; the solidified body can then, if desired, be heated to cure the resin.

0046Suitable heat-activated crosslinkers for epoxy resins include polycarboxylic acid anhydrides, amine complexes, in particular those of primary or tertiary aliphatic amines such as ethylamine, trimethylamine or n-octyl dimethyl amine with boron trifluoride or boron trichloride, and latent boron fluoride. Aromatic polyamines and imidazoles are generally not preferred because moderate results are obtained, possibly due to a reaction between the acid catalyst released and the amine. Dicyandiamide can be used successfully, provided that it is in relatively large particles.

0047Suitable heat-activatable crosslinkers for NovoLake include hexamethylatedetramine and paraformaldehyde.

0048The temperature and heating duration required for the heat curing after the photopolymerization, as well as the proportions of heat-activable hardener, are easy to find out by routine testing and can be derived in a simple manner from the state of the art in the field of heat curing epoxy and phenol / aldehyde resins.

0049Compositions containing resins containing epoxy groups or phenolic hydroxyl groups, by means of which they can be heat-cured after photopolymerization, are particularly useful in the production of multilayer printed circuits.

0050The compositions according to the invention can be used as surface coatings. They can be applied to a base such as steel, aluminum, copper, cadmium, zinc, paper or wood, preferably as a liquid, and then exposed or heated. With section-wise photopolymerization of the coating such as when exposed through a mask, the unexposed areas can be washed out with a solvent to remove the unpolymerized parts, the photopolymerized insoluble parts remaining in place. Accordingly, the compositions according to the invention can be used in the production of printing plates and printed circuits. The processes for making printing plates and printed circuits from photopolymerizable compositions are well known.

0051The compositions can also be used as adhesives. A layer of the composition can be placed between two surfaces of articles and then the assembly can be exposed and / or heated to complete polymerization. In photopolymerization, it is of course necessary that at least one of the objects consists of glass or another material that is transparent to actinic radiation.

0052The compositions are also useful in the manufacture of fiber reinforced composites including molding compounds.

0053They can be applied directly, continuously or in batches in liquid form to reinforcing fibers (including spinning or end loose threads and whiskers), which as woven or non-woven fabrics, unidirectional lengths, cut spun threads, in particular made of glass, boron, stainless steel, tungsten, aluminum oxide, silicon carbide, Asbestos, potassium titanate whiskers, aromatic polyamide such as poly (m-phenyLenisophthaLamid), poly (p-phenyllenerephthalamide) or poly- (p-benzamide), polyethylene, Polypropylene or carbon can be present. If the composition contains a thermosetting material such as an epoxy resin, the impregnated fiber material can be exposed for photopolymerization and in this way the composition solidified with the formation of a prepreg and, if necessary, heated under pressure optionally together with other prepregs or fiber layers to produce a hardened fiber-reinforced composite become.

0054The compositions according to the invention can be used in the production of kittens and fillers. They can be used for dip coatings, whereby an object to be coated is immersed in the liquid composition, removed again and then the adhering coating for photopolymerization (and thus for solidification).^GU.N^G) irradiated and then optionally heated.

0055In another application, a layer of the composition is irradiated in liquid form until it solidifies to form a adhesive film, which is then placed between two surfaces to be bonded and in contact with them, whereupon the structure is heated to completely crosslink the composition. The film can be provided on one side with a removable protective film, for example made of a PoLyoLefin or PoLyester or made of paper containing cellulose, with a silicone release agent coating. The structure is often easier to handle if the film has a sticky surface. This can be achieved by coating the film with a substance which is sticky at room temperature, but which, under the heating conditions used for complete crosslinking, crosslinked to form a hard, insoluble and infusible resin. However, there is often a sufficient level of residual tissue without additional treatment, especially if the polymerisation of the composition has not progressed too far. Suitable adhesive substrates include metals such as iron, zinc, copper, nickel and aluminum, ceramics, glass and types of rubber.

0056The following examples explain the invention, parts being always parts by weight.

0057Iodine salts are produced as follows:<ul id="ul0003" list-style="none"><li>IodoxybenzoL (4.72 g) is added to 1 normal aqueous sodium hydroxide solution (40 mL) at 0 ° C with vigorous stirring. After 2 hours the precipitated sodium iodate is removed by filtration and carbon dioxide is bubbled through the filtrate until the solution is neutral. Slowly add 1-normal acetic acid to release the carbon dioxide in a slight excess. Diphenyl iodosyl acetate monohydrate is filtered off as a white solid with a melting point of 105-110 ° C. (decomposition); 2.76 g are obtained.</li></ul>

0058The monohydrate (1.87 g) thus obtained is dissolved in boiling water (25 ml). The solution is treated with decolorizing charcoal and filtered hot. A saturated aqueous potassium hexafluorophosphate solution is then slowly added until no more precipitation occurs. The mixture is then cooled and filtered. The residue is dried over phosphorus pentoxide in vacuo at room temperature and diphenyl iodosyl hexafluorophosphate (0.87 g) is obtained with a melting point of 120-130 ° C. (decomposition).

0059Add iodoxybenzoL (35.4 g) at 0 ° C with vigorous stirring to 1-normal sodium hydroxide solution (300 mL). After 2 hours the mixture is filtered and carbon dioxide is bubbled through the filtrate until the solution is neutral. A portion of this carbonate solution (100 mL) is slowly mixed with fluoroboric acid (40%) until the evolution of carbon dioxide stops. A further amount of acid (2 mL) is then added and the precipitate is filtered off. This is washed with ice water and then dried; DiphenyLjodosyLtetrafLuoroborat (2.4 g) is obtained with a melting point range of 110-120 ° C (decomposition).

0060Bis- (4-methylphenyl) iodosyl trifluoroacetate (1.16 g; prepared according to the instructions of FM Beringer and P. Bodlaender, op. Cit.) Is dissolved in boiling water (10 mL) and filtered; the filtrate is washed with potassium hexafluorophosphate ( 0.49 g) treated as a saturated aqueous solution. The mixture is concentrated to about half its volume and the precipitate is filtered off. This is then dried and gives bis (4-methylphenyl) iodosyl hexafluorophosphate (0.68 g) with a melting point of 125 ° C. (decomposition).

0061Bis- (2-methylphenyl) iodosyl trifluoroacetate (0.7 g; according to the instructions of FM Beringer and P. BodLaender aaOhergestLLt) is dissolved in boiling water (25 mL) and with potassium hexafluorophosphate (0.45 g) in water (5 mL) transferred. The solution thus obtained is cooled and the precipitate which forms is collected by filtration and dried; bis (2-methylphenyl) iodosylhexafluorophosphate (0.4 g) with a melting point of 148-150 ° C. (decomposition) is obtained.

0062Diphenyliodosyltrifluoroacetate (1.2 g; according to FM Beringer and P. BodLaender loc. Cit., Produced) is dissolved in hot water, treated with activated charcoal and filtered hot. An aqueous solution of potassium hexafluoroarsenate (0.7 g) is added to the filtrate and the solution obtained is cooled. The white precipitate that forms is collected by filtration and air dried; diphenyliodosylhexafluoroarsenate (0.64 g) with a melting point of 135-138 ° C. (decomposition) is obtained.

0063The resins used in the examples are the following:<ul id="ul0004" list-style="none"><li>Resin 1 is 3,4-epoxy-cyclohexane carboxylic acid 3 ', 4'-epoxy-cyclo-hexy-methyl ester with a 1,2-epoxy content of 7.3 vaL / kg.</li><li>Resin 2 is a styrene / allyl alcohol copolymer with a molecular weight of 2340 and a hydroxy content of 3.56 vaL / kg; The latter is commercially available as "RJ 100" from Monsanto ChemicaL Company.</li><li>Resin 3 is 3,4-dihydro-2H-pyran-2-carboxylic acid-3,4-dihydro-2H-pyran-2-ylmethyl ester.</li><li>Resin 4 is a diglycidyl ether of 2,2-bis (4-hydroxyphenyL) propane with a 1,2-epoxy content of 5.2 eq / kg.</li><li>Resin 5 is a 1,4-butanediol diglycidyl ether with a 1,2-epoxy content of 9.3 vaL / kg.</li><li>Resin 6 is a resin having bisphenol end groups, which is obtained by reacting a diglycidyl ether of 2,2-bis (4-hydroxyphenyl) propane with 2,2-bis (4-hydroxyphenyl) propane to an average molecular weight of 1820.</li><li>Resin 7 is bis (3,4-epoxicyclohexylmethyl) adipate with a 1,2-epoxy content of 4.8 vaL / kg.</li><li>Resin 8 is a phenol / formaldehyde resol neutralized with 4-toluenesulfonic acid with a phenol: formaldehyde ratio of 1: 1.14, a viscosity of 0.7 Pa.s at 25 ° C and a solids content of 76%.</li></ul>

EXAMPLE 1

0064White sheet is coated with a mixture of resin 1 (100 parts), resin 2 (100 parts) and diphenyl iodosyl hexafluorophosphate (6 parts) in a layer thickness of 8-10 μm. Irradiation of the film for 2 seconds with an 80 W / cm medium pressure mercury lamp at a distance of 20 cm results in a tack-free coating.

EXAMPLE 2

0065Resin 1 (30 parts), resin 2 (100 parts), resin 4 (50 parts), resin 5 (20 parts) and diphenyl iodosyl hexafluorophosphate (6 parts) are mixed and the mixture is spread on tinplate in a layer thickness of 6-8 μm. It is irradiated as indicated in Example 1 and a tack-free coating is obtained within 3 seconds.

EXAMPLE 3

0066White sheet is coated with a mixture of resin 2 (100 parts), resin 3 (100 parts) and bis- (4-methylphenyl) iodosylhexafluorophosphate (6 parts) in a layer thickness of 6-8 μm. It is irradiated as indicated in Example 1 and a tack-free surface is obtained within 25 seconds.

EXAMPLE 4

0067White sheet is coated with a mixture of resin 6 (37.5 parts), resin 1 (62.5 parts) and diphenyl iodosyl hexafluoroarsenate (2 parts) in a layer thickness of 8-10 μm. It is irradiated as indicated in Example 1 and a tack-free coating is obtained within 3 seconds.

EXAMPLE 5

0068White sheet is coated with a mixture of resin 6 (50 parts), resin 7 (50 parts) and diphenyl iodosyl tetrafluoroborate (5 parts) in a layer thickness of 6-8 μm. It is irradiated as indicated in Example 1 and a tack-free coating is obtained within 30 seconds.

EXAMPLE 6

0069White sheet is coated with a mixture of resin 7 (50 parts), resin 8 (50 parts) and diphenyl iodosyl hexafluorophosphate (3 parts) in a layer thickness of 6-8 μm and irradiated in the same manner as indicated in example 1. A tack-free coating is obtained within 8 seconds.

EXAMPLE 7

0070A mixture of resin 1 (100 parts), resin 2 (100 parts), diphenyl iodosyl hexafluorophosphate (6 parts) and copper (II) trichloroacetate (2 parts) is heated on the Kofler bench. It takes 15 minutes at a temperature of 120 ° C until gelation occurs.

EXAMPLE 8

0071A mixture of Resin 2 (100 parts), Resin 4 (50 parts), Resin 1 (30 parts) and Resin 5 (20 parts) with DiphenyLjodosyLhexafLuorophosphat (3 parts) and copper-II-acetyLacetonate (1 part) is on the KofLerheizbank heated at 120 ° C. A gel time of 3 1/2 minutes is observed.

EXAMPLE 9

0072A mixture of resin 1 (62.5 parts) and resin 6 (37.5 parts) with diphenyl-iodosylhexafluoroarsenate (3 parts) and tin-II-chloride is heated at 180 ° C. on the case heating bench. A gel time of 6 minutes is observed.

EXAMPLE 10

0073A mixture of resin 6 (50 parts), resin 7 (50 parts), diphenyl iodosyltetrafluoroborate (5 parts) and benzoyl peroxide (1 part) is heated on the case heating bench at 150 ° C. The gel time is 90 seconds.

EXAMPLE 11

0074White sheet is coated with a mixture of resin 2 (50 parts) and resin 3 (50 parts) with bis (4-methylphenyl) iodosylhexafluorophosphate (3 parts) and 2-isopropylthioxanthone (1 part) in a film thickness of 6-8 µm. Irradiation of the film with an 80 W / cm medium pressure mercury lamp at a distance of 20 cm results in a non-stick surface within 15 seconds.

EXAMPLE 12

0075White sheet is coated with a mixture of resin 2 (50 parts), resin 3 (50 parts), bis- (2-methylphenyl) -iodosylhexafluorophosphate (3 parts) and 2-isopropylthioxanthone (1 part) in a layer thickness of 6-8 μm . It is irradiated as indicated in Example 11 and a tack-free surface is obtained within 20 seconds.