Abstract:
The present invention relates to a photopolymerizable composition comprising a polymerizable, polyethylenically unsaturated compound, benzil and/or fluorenone, a specific biphenyl ketone such as para-phenyl benzophenone, and a reducing agent such as a tertiary amine. The present composition permits rapid and complete curing. Moreover, in the photopolymerization of compounds sensitive to air inhibition non-tacky surfaces are obtained. The effect observed is based on a synergism between the present photoinitiators. The advantages of the invention are most manifest in curing relatively thick layers of materials.

Description:
This is a division of application Ser. No. 315,799, filed Oct. 28, 1981, now U.S. Pat. No. 4,442,022. 
    
    
     BACKGROUND OF THE INVENTION 
     Prior art photoinitiator systems comprising an aromatic carbonyl compound and a reducing agent are known from U.S. Pat. No. 3,754,807. In it are enumerated a great many aromatic carbonyl compound, including acetophenone, 4-tolyl acetophenone, benzophenone, 3-tolyl benzophenone, fluorenone, antraquinone, xanthone and thioxanthone. Reducing agents mentioned includes amines, viz, tertiary amines such as triethanolamine and methyldiethanolamine. Photopolymerizable compositions are also known from British Patent Specification No. 1,408,265, which also mentions a great many aromatic carbonyl compounds, including benzil, benzil derivatives, naphthyl, phenanthraquinone, benzophenone, benzoin, benzoin ethers and fluorenone. 
     Although these prior art photoinitiator systems may be satisfactorily applied for various purposes, a particular problem exists in completely and rapidly curing material having a thickness of 1-20 mm. Moreover, in the case of polymerizable, polyethylenically unsaturated compounds such as methacrylate resins that are sensitive to air inhibition, there is the problem of insufficient surface hardening, which manifests itself in a tacky surface. For optimum properties, there are two requirements: the material should be both thoroughly cured and of a good surface hardness. 
     Often the known photoinitiator systems satisfy only one of the two requirements. In actual practice, it has therefore often been found necessary to isolate the surface to be cured from the ambient air by covering it with a transparent film to obtain a satisfactory surface hardness and/or to use prolonged exposure times for thorough curing. 
     SUMMARY OF THE INVENTION 
     The photopolymerizable composition according to the invention is non-tacky, rapid setting, and hard curing, and comprises: 
     a. a polymerizable, polyethylenically unsaturated compound; 
     b. benzil and/or fluorenone; 
     c. a biphenylyl ketone of the formula: ##STR1## wherein: R 1  =hydrogen, an alkyl group having 1-8 carbon atoms, an alkoxy group having 1-10 carbon atoms, an alkyl carbonyl group having 2-12 carbon atoms or a halogen atom; and 
     R 2  =an alkyl group having 1-12 carbon atoms, phenyl, naphthyl, furyl or thiophenyl, which groups may be substituted or not; and 
     d. a reducing agent capable of reducing the aromatic carbonyl compounds when they are in the excited state. 
     It has been found that use of the above-mentioned composition permits rapid and complete curing of relatively thick layers of the polymerizable polyethylenically unsaturated compound. In the photopolymerization of compounds sensitive to air inhibition it is possible, moreover, to obtain non-tacky surfaces. The use of only benzil and/or fluorenone generally leads to better curing but to a lower surface hardness than the sole use of a corresponding amount of the present biphenylyl ketones. 
     As far as these aspects are concerned, it was found that a corresponding amount of a mixture of these aromatic carbonyl compunds results in both rapid curing and high surface hardness of the polymerizable compound. However, it has been surprisingly found that the result is not merely cumulative but is synergistic, and that this synergistic effect is not produced by other combinations of the above-mentioned initiators. 
     The present composition contains a polymerizable, polyethylenically unsaturated compound. Examples thereof include polymethacrylates and polyacrylates, the acryl being built in as reactive end group in a polymer chain, via hydroxy, amino, carboxy, isocyano or epoxy groups. Examples of this last mentioned type of compound include polyacryl-modified polyesters, polyamides, polyethers, polyurethanes and polyvinyl resins. Optionally, the polyethylenically unsaturated compound may be mixed with a co-polymerizable unsaturated monomer such as acrylic esters and methacrylic esters, acrylic and methacrylic amides and acrylic and methacrylic nitriles, for instance acrylonitrile, methyl methacrylate and 2-ethylhexyl acrylate. To that end, use may further be made of vinyl esters and vinylidene esters, vinyl ethers and vinyl ketones, such as vinyl acetate, vinyl propionate, N-vinyl-pyrrolidone and vinylbutyl ether. 
     Moreover, monomers may be added that have more than one unsaturated terminal group. Examples thereof include diallyl phthalate, diallyl fumarate, ethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylol propane triacrylate, neopentyl glycol dimethacrylate and polyethylene glycol diacrylate. The monomers that may be used include suitable copolymerizable hydrocarbons, such as styrene, vinyl toluene and divinyl benzene. 
     The present composition also may contain a mixture of an unsaturated polyester resin and a monomeric compolymerizable compound, such as styrene. The unsaturated polyester resins may be prepared in a known manner from unsaturated polycarboxylic acids or their anhydrides, such as maleic anhydride or fumaric acid, and generally in the presence of aromatic and/or saturated aliphatic dicarboxylic acids such as phthalic anhydride, tetrahydrophthalic anhydride, adipic acid and the like and polyols, such as ethylene glycol, diethylene glycol, propylene glycol and the like, and after the polyester preparation the terminal carboxylic groups may be further reacted to completion with reactive epoxides, such as phenylglycidyl ether. 
     The present photoinitiator mixture contains a mixture of aromatic carbonyl compounds which at least consists of: 
     a. benzil and/or fluorenone; and 
     b. a biphenyl ketone of the formula: ##STR2## wherein: R 1  =hydrogen, an alkyl group having 1-8 carbon atoms, an alkoxy group having 1-10 carbon atoms, an alkyl carbonyl group having 2-12 carbon atoms or a halogen atom; and 
     R 2  =an alkyl group having 1-12 carbon atoms, phenyl, naphthyl, furyl or thiophenyl, which groups may be substituted or not. 
     The group R 2  may be substituted, for instance with the groups denoted by R 1 . 
     Examples of suitable biphenylyl ketones include: para-phenyl acetophenone, para-phenyl benzophenone, para-tolyl benzophenone, para, para&#39;-diacetyl biphenyl, para-(para-chlorophenyl)-benzophenone, para-(para-methoxyphenyl)-benzophenone, α-furyl biphenylyl ketone, α-naphthyl biphenylyl ketone, para-tertiary butyl phenyl biphenylyl ketone, para-methoxy phenyl biphenylyl ketone and 2,4-dichlorophenyl biphenylyl ketone. 
     As biphenylyl ketone the composition preferably contains para-phenyl benzophenone. As regards benzil and fluorenone it should be noted that both have a triplet energy of 53-54 kcal/mole, whereas p-phenyl benzophenone has a triplet energy of about 60 kcal/mole. 
     The present composition generally contains 0.1-1.5% by weight and preferably 0.5-1.0% by weight of the aromatic ketone mixture. The molar ratio of the biphenylyl ketone to the benzil and/or fluorenone is generally in the range of from 0.25 to 9 and preferably in the range of from 0.5 to 3.0. 
     The present photopolymerizable compositions should also contain a reducing agent. It should be capable of reducing the aromatic ketones when they are in the excited state and moreover, after oxidation thereof, of initiating the polymerization of the polyethylenically unsaturated compound via intermediately formed radicals. 
     Suitable reducing agents are described in, int.al., British Patent specification No. 1,408,265. The compounds described have the formula ##STR3## where M is an element of group Vb of the Periodic Table of the Elements and the groups R, which may be the same or different, are hydrogen atoms, hydrocarbon groups, substituted hydrocarbon groups or groups in which two groups R together with the element M form a cyclic ring system, no more than two of the groups R being hydrogen atoms. Where the element M is attached directly to an aromatic group R, at least one of the other groups has an ##STR4## group attached to M. 
     It is preferred that as reducing agent there should be used an amine, more particularly a tertiary amine. Examples of suitable amines include triethanolamine, triisopropanolamine, N-methyl diethanolamine, N,N-dimethyl ethanolamine, N,N-dimethyl isopropanolamine, N-hyroxyethyl piperidine, N-hydroxyethyl morpholine, bis(2-hydroxymethyl) oleylamine, N,N,N&#39;,N&#39;-tetramethyl-1,3-diaminopropane, N,N-dimethyl benzylamine, N,N-dimethyl aniline, 4-dimethyl aminobenzoate, dimethyl aminoethyl acrylate and dimethyl aminoethyl methacrylate. 
     The present composition generally contains 0.1-4.5% by weight, preferably 0.25-2.0% by weight of reducing agent. The weight ratio between the mixture of aromatic ketones and the reducing agent is generally in the range of 1:3 to 3:1, preferably 2:1 to 1:2. 
     The present compositions are cured by exposure to radiation in a known manner. To that end use is generally made of a radiation source emitting radiation having a wave length in the range of 200 to 500 nm. Suitable radiation sources include medium-pressure mercury lamps. 
     The invention also relates to the curing of relatively thick layers of material (i.e., having a thickness of 1-20 mm, more particularly 4-10 mm) based on the present photopolymerizable compositions. When the photopolymerizable compositions according to the invention are treated in this way their advantages will be the most manifest. Cured reinforced laminates based on the present composition and having a thickness of 4-10 mm possess excellent properties. 
     As reinforcing material there may be used glass fibers in the form of bundles (rovings), glass mats, glass fibers, or glass webs, optionally in combination with layers of other (textile) materials. 
     DESCRIPTION OF PREFERRED EMBODIMENTS 
     The invention is further described in the following examples. Measures of the surface hardness and the degree of curing of the laminates were the non-tackiness of the boundary surfaces and the Barcol indentation hardness (type 934-1). 
     The maximum possible indentation hardness depends on type of resin, degree of curing, type of reinforcement and degree of reinforcement. All amounts are expressed in percentage by weight. 
    
    
     EXAMPLES 1 THROUGH 6 
     A resin solution was prepared consisting of 97% of technical 4,4&#39;-isopropylidene bis(phenylene oxyethyl methacrylate), 2% of triisopropanolamine and 1% of aromatic ketone(s). The solution obtained was used for preparing glass-reinforced laminates. They were built up of the resin and four layers of glass fiber mat. The thickness of the laminates was about 4 mm and the glass content 54%. The material was cured with a Philips medium-pressure mercury lamp of the HTQ-4 type having an intensity of radiation of 20 W per cm. The distance between the lamp and the laminate was 20 cm and the curing time four minutes. 
     The Examples 1 through 4 in Table 1 show the results obtained with benzil, para-phenyl benzophenone and mixtures of these carbonyl compounds. The Examples 5 and 6 are for comparison, use being made of a resin solution composed of 98.5% of said bis-methacrylate, 1% triisopropanolamine and 0.5% of aromatic ketone. 
     
                                           TABLE 1__________________________________________________________________________               state of laminate surface                         indentation               tackiness hardnessExamplePercent Aromatic ketone(s)               upper                    under                         upper                             under__________________________________________________________________________1    1.00% p-phenyl benzophenone               tack-free                    tack-free                         47.5                             37.3*2    0.66% p-phenyl benzophenone               tack-free                    tack-free                         51.1                             52.40.33% benzil3    0.50% p-phenyl benzophenone               tack-free                    tack-free                         48.4                             47.60.50% benzil4    1.00% benzil   tacky                    tack-free                         46.7                             48.95    0.50% benzil   tacky                    tacky-free                         30.9                             39.9*6    0.50% p-phenyl benzophenone               tacky                    wet  33.8                             not                             measur-                             able__________________________________________________________________________ *insufficiently cured 
    
     The examples 2 and 3 show the synergistic effect which results from the use of the present photoinitiator system. 
     EXAMPLES 7-12 
     For comparison the experiments of the Example 1 through 4 were repeated except that use was made of different aromatic carbonyl compounds. 
     The results are summarized in Table 2. 
     
                                           TABLE 2__________________________________________________________________________               state of laminate surface                        indentationAromatic carbonyl compound               tackiness                        hardnessExample(%)            upper                   under                        upper                            under__________________________________________________________________________7    1.00% benzophenone               tacky                   wet  41.3                            not                            measur-                            able*8    1.00% benzoin  tacky                   wet  45.7                            not                            measur-                            able*9    1.00% benzil dimethyl ketal               tacky                   tack-free                        47.8                            34.6*10   0.33% benzophenone               tacky                   tacky                        41.2                            23.0*0.66% p-phenyl benzophenone11   0.33% benzoin  tacky                   tack-free                        50.2                            40.3*0.66% p-phenyl benzophenone12   0.33% benzil dimethyl ketal               tacky                   wet  40.3                            not0.66% p-phenyl benzophenone measur-                            able*__________________________________________________________________________ *insufficiently cured 
    
     The results in Table 2 demonstrate that the combination of para-phenyl benzophenone and other known photoinitiators such as benzophenone, benzoin, and benzil dimethyl ketal does not produce any synergistic effect at all. 
     EXAMPLES 13 THROUGH 22 
     Laminates were prepared that were made up of the resin described in the Examples 1 through 6 and four layers of glass mat. The laminate thickness was 4 mm, the glass content 26%. Curing was effected in the manner indicated in the Examples 1 through 6 in the presence of 2% of triisopropanolamine, as was the testing of the laminate properties. Table 3 shows the results. 
     
                                           TABLE 3__________________________________________________________________________               state of laminate surface                         indentationAromatic carbonyl compound               tackiness hardnessExample(%)            upper                    under                         upper                             under__________________________________________________________________________13   0.50% benzil   tack-free                    tack-free                         35.1                             36.40.50% p-phenyl benzophenone14   0.50% fluorenone               tack-free                    tack-free                         40.5                             39.00.50% p-phenyl benzophenone15   0.50% benzil   tacky                    tack-free                         34.1                             37.10.50% fluorenone16   0.50% benzil   tacky                    tack-free                         35.6                             39.80.50% benzophenone17   0.50% benzil   tacky                    tack-free                         33.3                             37.30.50% benzil dimethyl ketal18   0.50% benzil   tacky                    tack-free                         42.0                             39.50.50% benzoin butyl ether19   0.50% benzil   tacky                    tack-free                         35.5                             38.40.50% acetophenone20   0.50% benzil   tacky                    tack-free                         40.1                             42.20.50% l-phenyl propane1,2-dione-2-oxime-o-benzoate21   0.50% benzil   tacky                    tack-free                         36.8                             41.40.50% 2-hydroxy-2-benzoylpropane22   0.50% benzil   tacky                    tack-free                         39.9                             42.50.50% 2-hydroxy 2(p.iso-propyl benzoyl)propane__________________________________________________________________________ 
    
     Only the compositions of the Examples 13 and 14 are the ones according to the invention. The others serve for comparison. The data show that satisfactory results are only obtained with the photoinitiator system according to the invention. Combinations of benzil with aromatic carbonyl compounds other than the present biphenyl ketones lead to insufficient surface hardening. 
     EXAMPLES 23 THROUGH 30 
     The procedure used in the Examples 13 through 22 was repeated, with the exception that as aromatic carbonyl compound there was used a mixture of 0.5% of benzil and 0.5% of the biphenylyl ketones mentioned in Table 4 and the distance between the lamp and the laminate was 15 cm. The results are given in Table 4. 
     
                       TABLE 4______________________________________            state of laminate surface                    indentation                    hardnessEx-                    tackiness   up-  un-ample biphenylyl ketone                  upper   under per  der______________________________________23    p-phenyl acetophenone                  tack-   tack- 38.3 35.6                  free    free24    p,p&#39;diacetyl biphenyl                  tack-   tack- 38.0 38.8                  free    free25    α-furyl biphenylyl ketone                  tack-   tack- 35.6 37.4                  free    free26    α-thiophenyl biphenylyl                  tack-   tack- 40.3 35.1 ketone           free    free27    α-naphthyl biphenylyl                  tack-   tack- 43.0 42.8 ketone           free    free28    p-tolyl benzophenone                  tack-   tack- 38.3 35.6                  free    free29    p-methoxyphenyl  tack-   tack- 34.3 40.7 benzophenone     free    free30    p-chlorophenyl benzo-                  tack-   tack- 37.3 36.1 phenone          free    free______________________________________ 
    
     The above results show that the above-described synergism also occurs in the case of biphenylyl ketones other than paraphenyl benzophenone. 
     EXAMPLES 31 THROUGH 39 
     Glass-reinforced laminates were constructed from twelve layers of glass fiber mat and from the resin described in Examples 1 through 6. The laminate that was formed had a thickness of about 10 mm and a glass content of 55%. 
     In the resin there was dissolved a mixture of aromatic ketones made up of 45% of benzil and 55% p-phenyl benzophenone. As a reducing agent there was added triisopropanolamine in an amount such that the weight ratio of the amine to the ketone mixture was 2. 
     The laminates were exposed to radiation from a Philips medium-pressure mercury lamp of the HTQ-4 type. The distance between the lamp and the laminate was 20 cm, and the radiation times were 8, 10 and 12 minutes, respectively. The results are shown in Table 5. 
     
                       TABLE 5______________________________________Amount     radi-   state of laminate surface of       ation               indentationEx-   ketone   time    tackiness   hardnessample mixture  (min.)  upper  under  upper under______________________________________31    1.00%     8      tack-free                         tack-free                                45.2  47.032    1.00%    10      tack-free                         tack-free                                46.1  44.133    1.00%    12      tack-free                         tack-free                                45.9  44.834    0.50%     8      tack-free                         tack-free                                42.7  46.735    0.50%    10      tack-free                         tack-free                                43.1  43.936    0.50%    12      tack-free                         tack-free                                45.6  45.637    0.20%     8      tack-free                         tacky  38.4  0.038    0.20%    10      tack-free                         tack-free                                37.6  47.139    0.20%    12      tack-free                         tack-free                                43.1  49.7______________________________________ 
    
     The above data show that satisfactory results can be obtained within acceptable radiation times even with the use of (very) small amounts of the photoinitiator system. 
     EXAMPLES 40 THROUGH 43 
     Glass-fiber reinforced tubes having a diameter of 88 mm and a wall thickness of 4 mm were made by passing a bundle of glass fibers through an impregnating bath containing 4,4&#39;-isopropylidene-bis(phenylene oxyethyl-methacrylate) in which there had been dissolved 1% of aromatic ketone(s) and 2% of triisopropanolamine and winding said bundle onto a rotary steel cylinder. 
     Subsequently, the impregnated product was exposed to 15 minutes&#39; radiation from a Philips HTQ-4 lamp positioned at 15 cm above the rotating tube. The tubes obtained had a glass content of 70%. The results are given in Table 6. The Examples 40 through 42 serve for comparison. 
     
                                           TABLE 6__________________________________________________________________________               state of boundary surfaces                         indentation               tackiness hardnessExampleAromatic ketone(s) %               upper                    under                         upper                             under__________________________________________________________________________40   1.0% benzil dimethyl ketal               tacky                    tack-free                         45.9                             50.3                    loose                    fibers41   1.0% benzil    tacky                    tack-free                         49.5                             53.642   1.00% p-phenyl benzophenone               tack-free                    tacky                         40.2                             49.0                    loose                    fibers43   0.50% benzil   tack-free                    tack-free                         44.8                             53.00.50% p-phenyl benzophenone__________________________________________________________________________ 
    
     EXAMPLES 44 THROUGH 56 
     An unsaturated polyester resin was obtained by polycondensation of a molar mixture of phthalic anhydride and maleic anhydride with the equivalent amount of propylene glycol up to an acid number of 45 and dissolution in styrene to a content of 34% styrene. In the resin there were dissolved 1% of aromatic carbonyl compound(s) and 2% of triisopropanolamine. Subsequently, laminates were formed that were made up of this resin and four layers of reinforcing glass mat. The laminate thickness was about 4 mm and the glass content 26%. Radiation was done with a Philips HTQ-4 lamp. The distance between the laminate and the lamp was 20 cm. The results are summarized in Table 7. The Examples 44 through 53 serve for comparison. The Examples 54 through 56 serve to illustrate the invention. 
     These data, too, demonstrate the synergistic effect of the present initiator system. They further show the favorable results that may be obtained by the present invention. 
     
                                           TABLE 7__________________________________________________________________________               state of laminate surface           expo-         indentationaromatic carbonyl           sure               tackiness hardnessExamplecoumpound(s) (%)           (min.)               upper                    under                         upper                             under__________________________________________________________________________44   1% benzil dimethyl           5   tack-free                    tacky                         47.3                             0.0ketal45   3% benzil dimethyl           5   tack-free                    tacky                         46.8                             0.0ketal46   1% benzoin butyl           5   tack-free                    wet  50.7                             0.0ether47   3% benzoin butyl           5   tack-free                    wet  45.2                             0.0ether48   1% benzil  3   tack-free                    tacky                         52.5                             0.049   1% benzil  4   tack-free                    tack-free                         49.5                             7.550   1% benzil  5   tack-free                    tack-free                         51.2                             21.751   1% p-phenyl benzo-           3   tack-free                    wet  0.0 0.0phenone52   1% p-phenyl benzo-           4   tack-free                    wet  0.0 0.0phenone53   1% p-phenyl benzo-           5   tack-free                    wet  0.0 0.0phenone54   0.5% benzil           3   tack-free                    tacky                         46.4                             0.00.5% p-phenyl benzo-phenone55   0.5% benzil           4   tack-free                    tack-free                         51.4                             35.90.5% p-phenyl benzo-phenone56   0.5% benzil           5   tack-free                    tack-free                         48.2                             53.10.5% p-phenyl benzo-phenone__________________________________________________________________________