JPH0139570B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to photosensitive compositions containing unsaturated polymeric mercapto acids and radical initiation systems, elements made from said compositions, and methods for photoimaging said elements. The technical background of the invention includes the following. U.S. Pat. No. 4,179,531 discloses a monoalkenyl aromatic diene copolymer resin, optically cross-linking C=
A curable composition is disclosed that includes a C-containing monomer, a polythiol, and a photoinitiator. U.S. Pat. No. 4,234,676 discloses unsaturated polymers,
A curable composition containing a monomer, a thiol, and a curing agent is disclosed. U.S. Pat. No. 4,248,960 discloses a relief-forming laminate in which the lower laminate composition is preferably a photocurable polymer composition. US Pat. No. 4,266,004 discloses a method for photoimaging certain organic sulfide-containing polymers in the presence of oxygen and a photosensitizer. UK Patent No. 1390711 and US Patent No. 3767398
Each specification describes a curable composition comprising a polymer having monoallyl ester repeating units of a methyl vinyl ether/maleic anhydride copolymer and a polythiol and containing or not containing a photocuring rate accelerator. is disclosed. US Pat. No. 3,809,633 discloses chain-extended polythioether-containing polymer compositions containing reactive unsaturated carbon-carbon functional groups and/or reactive thiol groups within the molecule. U.S. Pat. No. 3,660,088 discloses a metal etching process using a photocurable composition comprising a polyene, a polythiol, and a photocure rate accelerator. U.S. Pat. No. 3,936,530 discloses curable coating compositions comprising polyene and polythiol components based on styrene-allylic alcohol copolymers. U.S. Pat. No. 3,627,529 discloses a method of making lithographic plates from a photocurable composition of an ethylenically unsaturated polyene, a polythiol, and a photocure rate accelerator. U.S. Pat. No. 4,179,295 discloses that the organopolysiloxane contains an aliphatic unsaturated bond-containing organopolysiloxane and a mercapto-containing organopolysiloxane in the molecule, and that the organopolysiloxane is cured by ultraviolet irradiation to cause cross bond formation. A photosensitive composition is disclosed. US Pat. No. 4,130,469 discloses curable coating compositions containing a polymer containing pendant mercaptan groups and a bismaleimide crosslinker. GB 1179252 discloses the use of butadiene polymers containing carboxyl groups in the production of thermoplastic elastic compositions. U.S. Pat. No. 2,589,151 discloses a thioglycolic acid adduct of a butadiene polymer prepared in solution using a free radical initiator, and the structure of the adduct is "J.
Am.Chem.Soc.” Vol. 70, pp. 1804-1808 (1948)
It is further discussed inside. Ind.Eng.Chem., Vol. 45, pp. 2090-2093 (1953) describes the modification of polybutadiene by the addition of polar group-containing thiols, such as mercaptoacetic acid, to produce polymers with improved oil resistance. Disclosed. Research Disclosure, Vol. 143, p. 24 (1976) discloses the use of unsaturated polymeric mercapto acid derivatives as components in liquid electrographic developers. The present invention comprises the following components: (i) about 10 to 90% of the total weight of components (i), (ii) and (iii);
(ii) components (i), (ii) and (iii) having a number average molecular weight of from about 1,000 to 1,000,000 and containing from about 20 to 1,800 milliequivalents of reactive unsaturated carbon-carbon groups per 100 g; ) Approximately 1 to 70% of the total weight of
of reactive mercapto acid, and (iii) from about 0.001 to the total weight of components (i), (ii) and (iii).
50
% actinic radiation to initiate the addition of mercapto acid to a polyene. The present invention also relates to a photosensitive element comprising a substrate coated with a layer of a photosensitive composition having a thickness in the range of about 0.1 μm to 7600 μm or more. Preferred photosensitive elements are used in photoresists and proofing systems. The substrate can be any natural or synthetic support, preferably in the form of a flexible or rigid film or sheet. The present invention also provides an image-containing transparent body with
It also relates to a photoimaging method comprising imagewise exposing a photosensitive element to actinic radiation containing a wavelength of 5000 Å and processing the image. A "reactive" unsaturated carbon-carbon group refers to a thioether bond that reacts with the thiol group of a mercapto acid in the presence of a photosensitizer under actinic radiation.

[Formula] refers to a group that produces the formula, which is found in a cyclic structure such as an aromatic nucleus such as benzene, pyridine, naphthalene, etc.
"Non-reactive" groups that do not react with thiol groups to form thioether bonds under the same conditions

It is the opposite of [formula]. The term "unsaturated carbon-carbon group" is and It means. The polyene may contain one type of such unsaturated groups, or it may contain two
It may contain one or more such types. These groups can be independent of each other or conjugated, e.g. 1,3-diene, or conjugated with adjacent non-reactive groups e.g. - | C = | C -, carbonyl, sulfonyl, phosphonyl, etc. It can be something. The polyene of component (i) of the photosensitive composition is about 5000
It has a preferred number average molecular weight of ˜100,000 and contains a preferred degree of reactive unsaturated carbon-carbon groups of about 50 to 1000 milliequivalents per 100 grams of polyene. The preferred amount of polyene is about 40-80% of the total weight of components (i), (ii) and (iii). Preferably, the reactive unsaturated carbon-carbon groups of the polyene are located terminally in the main polymer, near the end and/or pendant from the main polymer chain. The term "terminal" means that the reactive group is at the end of the main chain in the molecule, while "near the end" means that the reactive group is located a carbon atom from the end of the main chain in the molecule. This means that there are no more than 16 points apart. The term "pendant" means that the reactive group is located at or near the end of a branch of the main chain, as opposed to being located at or near the end of the main chain. For convenience, unsaturation at either of these positions is referred to herein as "terminal" unsaturation. The preferred polyene is

[Method A]

Methyl methacrylate/n-butyl methacrylate/cinnamyl methacrylate (45:45:10)
A random copolymer was produced by the following method. All glassware for this polymerization was oven dried at 150°C for 4 hours before use. The apparatus was assembled hot and purged with argon until cooled. The reaction was carried out under positive pressure of argon.
Tetrahydrofuran (THF) was freshly distilled from benzophenone/sodium under nitrogen. Freshly distilled cinnamyl methacrylate (bp79 ~
80°/0.005mm, 5.06g, 25mmol), n-butyl methacrylate (16.00g, 112mmol) and methyl methacrylate (11.26g, 112mmol)
mixed and passed through neutral alumina, and
Degassed with argon for 15 minutes. THF (300 ml) and diphenylethylene (redistilled, bp 90°/1 mm, 0.44 g, 2.5 mmol)
I prepared it. The solution was cooled to 0° and n-
Butyl lithium (1.7 ml, 2.5 mmol in 1.6 M hexane) was added. The blood red solution was cooled to -78° and the monomer mixture (25.9 g, 0.2 mol) was added at such a rate (10 minutes) that the temperature did not exceed -70°. After 15 minutes, acetic acid (0.2 ml, 3 mmol) was added.
The warmed solution was then poured into water (2). The particulate solid copolymer was isolated and dried in a vacuum desiccator overnight to yield cinnamyl methacrylate copolymer (25.8 g, 100%) as a fine white powder. The 90MHZ ¹ H NMR spectrum is above all 4.5 (broad, dJ about 6, OC H ₂ =
CHC ₆ H ₅ ), 3.8 (broad, t, J approx. 6, OC H
₂ CH ₂ CH ₂ CH ₃ ) and 3.5(s,OCH ₃ ) bands in a ratio of 3:15:21, which represents 9% cinnamyl, 47% butyl, and 44% methyl in the copolymer. Corresponds to the composition of methacrylate. Gel permeation chromatography (GPC): _o 9700, _w 10000.
T _g (DSC) 54° by scanning differential calorimetry. [Method B] A (40:40:20) random copolymer of methyl methacrylate/butyl methacrylate/allyl methacrylate was produced by the following method. All glassware and reagents were prepared as in Method A. Allyl methacrylate (15.14 g, 0.12 mol), butyl methacrylate (34.13 g, 0.24 mol) and methyl methacrylate (24.03 g, 0.24 mol) were mixed, passed through alumina (10 g) and degassed with argon. A 500 ml flask set up as in Method A was charged with THF (300 ml) and potassium tert-butoxide (5.61 g, 0.05 mole). The monomer mixture (61.1 g, 0.5 mol) was added dropwise over 23 minutes. During this period, the temperature rose from 25° to 53°,
Then it decreased to 25°. Acetic acid (4 ml, 70 mmol) was added and the reaction mixture was poured into water (4) in a blender. The isolated copolymer was dried in a vacuum desiccator to yield allyl methacrylate copolymer (59 g, 97%) as a fine white powder. MMR analysis shows that the copolymer composition is 2.1% allyl, 44% butyl, and 35%
It was shown to be methyl methacrylate.
GPC: _o 6000, _w 10000. Other unsaturated copolymers made by Method A and Method B are shown in Table 1, where
MMA is methyl methacrylate and BMA is n-butyl methacrylate.

[Table] Related

Table: Example 1 A 20% solids coating solution of a photosensitive composition was prepared by mixing the following ingredients. Copolymer M 1.00g Mercaptosuccinic acid 0.150g Ethylene glycol dicaprylate plasticizer
0.100g Benzophenone radical generator 0.072g 4-Methyl-2,6-ditertiary-butylphenol inhibitor 0.010g Methylene chloride/methanol (95/5) solvent
This solution was coated onto a freshly pumice polished blank copper laminate using a 5.328 g 8 mil (200 μm) doctor knife. The coated laminate was dried in air at room temperature to yield a clear, smooth, non-tacky film approximately 25 μm thick. This coated laminate was placed in a glass vacuum frame (Nuark Co., Ltd.) at a pressure of approximately 250 mmHg with an exposure source Model B-100A/X made by Ultraviolet Products Co., which includes a 100W lamp (Sylvania Flat Lamp, H-44-JM-100). Imagewise exposure was carried out for 8 minutes in a medium (product). The lamp was operated at a distance of 7 inches (17.8 cm) from the board without an infrared filter.
The process transparency was held in close contact with the plate during exposure. After exposure, the plate was developed at room temperature by immersing it in a solution of 0.5% sodium hydroxide in water/isopropyl alcohol (approximately 1/1) and gently rubbing the surface with a soft brush. The film dissolved quickly in the exposed areas of the plate. When the image was completely developed on the copper surface of the laminate, development was stopped by washing with water. When the exposure time was increased to 12 minutes, a clean, sharp image was drawn on the copper surface that corresponded exactly to the transparent image of the process transparency. In this experiment, development was carried out at 35°C using a 0.8% sodium carbonate solution in an approximately 4.5/1 water/2-(2-butoxyethoxy)ethanol solvent mixture. Example 2 The coating solution prepared as described in Example 1 was coated onto a freshly pumice polished blank copper laminate using a 5 mil (125 μm) doctor knife. The coated board was allowed to dry and a portion of the board was exposed through a process transparency as described above. After exposure,
The plates were developed in a 0.8% sodium carbonate solution in water/2-(2-butoxyethoxyethanol (9:1)) with magnetic stirring at 30-35° for various times. The results were It is summarized in Table 2.

[Table] Image The remaining parts of the coated board were exposed under glass at atmospheric pressure in a vacuum frame for 12 minutes. The image was fully developed with a development time of 4 minutes. The rest of the coated board is placed in the air.
Exposure was made for 12 minutes. A fully developed image was obtained with a development time of 2 minutes. That is, oxygen does not have a significant adverse effect on the photographic speed of this photosensitive composition. The developed plate was baked in a draft oven for 30 minutes at 106°. It was then etched in a standard ferric chloride etching bath for 20-30 minutes at room temperature. The exposed image pattern was sharply etched to the backing of the laminate without affecting the unexposed photoresist or the underlying copper. Example 3 A coating solution of a photosensitive composition was prepared as follows. Copolymer M 1.00g Mercaptosuccinic acid 0.150g Ethylene glycol dicaprylate 0.143g Benzyl dimethyl ketal 0.027g 4-Methyl-2,6-ditertiary butylphenol 0.002g Benzotriazole 0.003g Methylene chloride/methanol (90/ 10) Solvent
This solution was coated onto a freshly pumice polished blank copper laminate using a 5.300 g 5 mil (125 μm) doctor knife. The coated board was allowed to dry and a portion of the board was exposed through a process transparency as described in Example 1.
After exposure, the plate was stirred with a magnetic stirrer at 30°-35° for various times in water/2
Developed in a 0.8% sodium carbonate solution in (2-butoxyethoxyethanol) (9:1). The results are summarized in Table 3.

[Table] Bright Image Example 4 A coating solution of a photosensitive composition was prepared as follows. Copolymer F 1.00g Mercaptosuccinic acid 0.100g Ethylene glycol dicaprylate 0.166g Benzyl methyl ketal 0.054g 4-Methyl-2,6-ditertiary butylphenol 0.002g Benzotriazole 0.003g Methylene chloride/methanol (90/ 10) Solvent
This solution was coated onto a freshly pumice polished blank copper laminate using a 5.300 g 5 mil (125 μm) doctor knife. This dry film is clear and slightly tacky, and approximately
It had a thickness of 25 μm. A clear 25 μm polypropylene cover sheet was applied to this coating to prevent it from sticking to the process transparency during exposure. using a rubber squeegee
This cover sheet was smoothed over the coating. This was then coated after exposure and removed without damage. A sample of the coated plate was imagewise exposed through this cover sheet as described in Example 1. After exposure, this plate
Water/while stirring with a magnetic stirrer at 32℃
2-(2-butoxyethoxy)ethanol (9/
Developed in 0.8% sodium carbonate solution in 1). The results are summarized in Table 4 below.

[Table] Sharp image This coated board showed excellent resolution. Comparable results were obtained when the coated plates were baked in a draft oven at 70° C. for 30 minutes and then exposed to light. Samples of the coated plates were also exposed through the cover sheet in a vacuum frame at atmospheric pressure. The exposure/development times required to obtain a fully developed sharp image were similar to those required for plates exposed in vacuum. Examples 5-9 5.0g in each solution as shown in Table 5
Coating solutions of five photosensitive compositions were prepared using different unsaturated copolymers and varying amounts of mercaptosuccinic acid and ethylene glycol dicaprylate.

[Table] Each coating solution contains 0.270 g of benzyl dimethyl ketal, 0.010 g of 4-methyl-2,6-
It contained ditert-butylphenol, 0.015g benzotriazole, and 26.66g 90/10 methylene chloride/methanol solvent. The solutions of Examples 5 and 9 were clear, but those of Examples 6, 7, and 8 were slightly hazy. They have been aged before use. This solution was coated onto a freshly pumice polished blank copper laminate using a 7 mil (180 μm) doctor knife and the board was allowed to dry. A polypropylene coversheet was applied to this coating and a sample of the plate was exposed imagewise through the coversheet as described in Example 1. After exposure, the plate was developed in a 0.8% sodium carbonate solution in water/2-(2-butoxyethoxy)ethanol (9/1) at 32° C. with magnetic stirring. Sharp, fully developed images were obtained under the exposure and development conditions summarized in Table 6. Table 6 Example Exposure Time (min) Development Time 5 1.0 1.5 6 6.0 8.0 7 2.0 4.3 8 1.0 2.5 9 1.0 2.5 The developed film of Example 9 was very soft and it gradually ran into the developed area on standing. Example 10 A coating solution of a photosensitive composition was prepared as follows. Copolymer L 1.00g Mercaptosuccinic acid 0.134g Ethylene glycol dicaprylate 0.140g Benzyl dimethyl ketal 0.054g 4-Methyl-2,6-ditertiary butylphenol 0.002g Benzotriazole 0.003g Methylene chloride/methanol (90/ 10) Solvent
5.332 g The amount of mercaptosuccinic acid used corresponded to about 0.56 moles per mole of carbon-carbon double bonds in the copolymer. This solution was coated onto a freshly pumice polished blank copper laminate using an 8 mil (200 μm) doctor knife and the board was allowed to dry. A polypropylene coversheet was applied to this coating and a sample of the plate was exposed imagewise through the coversheet as described in Example 1. After exposure, the plate was developed in a 0.8% sodium carbonate solution in water/2-(2-butoxyethoxy)ethanol (9/1) at 32° C. with magnetic stirring. Sharp, fully developed images with exposure times of 0.5 to 2 minutes and 2.5
Obtained with a development time of ~5 minutes. The unexposed and undeveloped areas were non-tacky and were not visibly affected by the developer solution. The sample plate, imagewise exposed for 1 minute and developed for 2.5 minutes, was allowed to dry at room temperature for 2 hours and then reexposed through a polypropylene cover sheet without a process transparency. This blanket exposure allowed the non-image areas to easily peel off the plate after 2.5 minutes in the developer solution. In contrast, the photosensitive composition of this non-imaging plate did not peel off even after 30 minutes in the developer solution under the same conditions. This experiment shows that the unexposed portions of the photosensitive composition can be removed (or further imaged) by additional exposure after primary development. A second sample plate, imagewise exposed for 1 minute and developed for 2.5 minutes, was baked at 110° C. in a circulating air oven. It was then immersed in a ferric chloride etching bath at room temperature. After 20 minutes, the copper had been etched away in the imaged portion of the plate without lifting or undercutting the unexposed portions of the resist.
Etching resistance is etching at 50℃ (8 minutes)
It wasn't something I was satisfied with. Example 11 A coating solution of a photosensitive composition was prepared as follows. Styrene/butadiene (28/72) linear ABA block copolymer (lactone 1102) 7.2g Mercaptosuccinic acid 1.5g Oleic acid 1.2g Benzyl dimethyl ketal 0.48g 4-Methyl-2,6-ditertiary butylphenol 0.02 g Benzotriazole 0.022g Methylene chloride/methanol (95.4/4.6)
Solvent 65g This solution was coated onto a freshly pumice polished blank copper laminate to produce a slightly sticky film with an odor after drying. Apply a polypropylene cover sheet to this coating,
The cover sheet was then exposed imagewise for 1 to 6 minutes as described in Example 1. After exposure, the plate was stirred with a magnetic stirrer at 32°C in a 0.8% sodium carbonate solution in water/2-(2-butoxyethoxy)ethanol (9/1) at 1.5%.
Developed. For all exposures tested, an image was drawn on the plate that corresponded to the transparent portion of the process transparency.
The material in the exposed areas swelled in the developer, but it had insufficient solubility to be washed away to the plate. Other coated plate samples were first baked in an air oven at 70°C for 15 minutes and then exposed for 6 minutes. Upon immediate removal of the cover sheet, the photosensitive composition in the unexposed areas was lifted from the plate along with the cover sheet and film in the exposed areas remaining on the plate. Thus, it can be seen that the compositions and elements of the present invention, which are normally used to give positive working images by solvent washing of the exposed areas, can also be used in the described peel-apart development process to give negative working images. . Example 12 A coating solution of a photosensitive composition was prepared as follows. Hiker 1072-CG [milled (20x) on a cold mill to improve solubility] 10.0 g Mercaptosuccinic acid 1.42 g Ethylene glycol dicaprylate 1.32 g Benzyl dimethyl ketal 0.54 g 4-Methyl-2,6-di Tertiary butylphenol 0.02g Benzotriazole 0.03g Methylene chloride/methanol (90/10) solvent
106.64g "Hycar" 1072-CG (product of BF Gutdrich) is a high molecular weight (average Mooney viscosity = 4.5, _o approx. 31000) carboxylated butadiene/acrylonitrile copolymer [approx. 27% acrylonitrile content, carboxyl content approx. 3.38%, rubber
The value is 0.075 based on the equivalent weight per 100 parts (EPHR) standard. This solution was coated onto a freshly pumice polished blank copper laminate to produce a dull film after drying. A polypropylene coversheet was applied to the coating and imagewise exposed through the coversheet as described in Example 1 for 1-10 minutes. After exposure, the plate was stirred at 32° with a magnetic stirrer and mixed with water/2-(2-
butoxyethoxy) in ethanol (9/1)
Developed in 0.8% sodium carbonate solution. An image corresponding to the transparent portion of the process transparency was drawn on the board for all times tested. Due to poor adhesion, the unexposed portions of this composition were lifted from the plate after 1 minute in the developer solution. Example 13 1.0 g Copolymer B, 0.1 g mercaptosuccinic acid, 0.075 g benzyl methyl ketal, 0.1 g ethylene glycol dicaprylate and 50μ
A solution was prepared by adding the additive solution to 4.3 ml of methylene chloride/methanol (9:1) solvent mixture. The additive solution consisted of 3 mg of benzotriazole, 2 mg of 4-methyl-2,6-di-tert-butylphenol, and 2 mg of CI Solvent Red Dy #109 dissolved in a methylene chloride/methanol solvent mixture. Ta. The resulting clear solution was coated onto a pumice polished copper substrate using an 8 mil (200 μm) doctor knife. The coated panels were allowed to dry at room temperature overnight. Place a polypropylene cover sheet on this panel and pass it through a √2 step wedge process transparency in a vacuum printing frame (Nuark product) at a distance of 38 cm.
A radiation dose of 100 units per cm ² and 580 mg associated with the radiation from a metal halide lamp covering the 3600-4500 Å spectral range on the exposed surface of the transparency.
was exposed for a time corresponding to an integrated light intensity of . Remove the cover sheet and expose the panel to 2588ml
of water, 27 g of sodium carbonate and 300 g of 2-
Developed in a solution made from (2-butoxyethoxy)ethanol. A magnetic stirrer was used for stirring. After 2 minutes at 35°, development of the exposed portion of the panel up to step 7 (32 mj/cm ² ) was completed down to the copper surface. The parts of the coating that were exposed to less radiation remained intact. Example 14 A mixture of 1.0 g of Copolymer C, 200 mg of 4-mercaptomethylbenzoic acid, 100 mg of benzyl dimethyl ketal, 75 mg of ethylene glycol dicaprylate and 50 μ of the additive solution of Example 13 was mixed in methylene chloride/methanol (9 /1) Solvent mixture
It was dissolved in 4.3ml. 8 mil (200μm) of this solution
The coating was applied onto a pumice polished copper substrate using a doctor knife. Place a polypropylene cover sheet over this panel and pass it through the √2 step wedge process transparency in the vacuum printing frame of Example 13.
It was exposed to a radiation dose of 100 units. The cover sheet was removed and the exposed panel was developed in the developer solution of Example 13 at 35° for 4 minutes. Development up to step 4 (132 mj/cm ² ) was completed up to the copper surface. The exposed copper was etched from the plate in a ferric chloride bath at room temperature. The etched plate was then re-exposed to an additional 290 mj/cm ² of radiation through a process transparency. The re-exposed plate was then developed as described for 4 minutes. Development of the second exposed area was completed to the copper surface. This example shows that this photosensitive element has add-on capability. The reason is that the unexposed composition is still functional after the development and etching steps. Examples 15-54 These Examples were performed using the method described in Example 13. In each case the solution is 1.0 of the stated copolymer
g, mercapto acid, photoinitiator, stated amount of ethylene glycol diacrylate plasticizer and 50μ additive package in 4.3ml methylene chloride/
Prepared by addition to methanol (9/1) solvent mixture. The resulting solution was coated onto a substrate using a doctor knife to produce the stated initial coating thickness. The substrates used were pumice polished copper (Cu) or oriented polyester film or polypropylene film (Film). If film is used,
The coating was transferred to the copper substrate by lamination before exposure. The dried coating was exposed to radiation as described for a time corresponding to the number of units required to give the stated integrated light intensity (mj/cm ² ). The exposed coatings were developed at 35° for the indicated times. The resolution of the images obtained in most examples was measured in μm. The developed image was inspected and the development type was recorded as follows. C Even the copper substrate was removed during development. Most of the S image has been removed. An R relief image was obtained, but it was not removed to the copper surface. V A visible image was obtained, but no relief was obtained. A summary of these examples is included in Tables 7 and 8. In Table 7, mercapto acids and radical generating initiators are referred to by the following symbols: Mercaptoic acid a 6-Mercaptocaproic acid b Mercaptosuccinic acid c Mercaptoitaconic acid d 2-Mercaptocaproic acid e 4-Mercaptomethylbenzoic acid f 4-Mercaptomethyldihydrocinnamic acid g Mercaptosuccinic acid monomethyl ester h Mercaptosuccinic acid monon- Hexyl ester i Mercaptosuccinic acid mono-2-ethoxyethyl ester j N-acetyl cysteine k 11-mercaptoundecanoic acid initiator aa benzyl dimethyl ketal bb benzoin methyl ether cc 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer dd methylbenzoin methyl ether ee methylbenzoin ff benzophenone gg pentylanthraquinone hh benzophenone/Michler's ketone (4/
1) ii Benzoin ethyl ether jj Desoxybenzoin kk Benzophenone/Michler's ketone (1/
1) ll 4-Phenylbenzophenone mm Benzoin isobutyl ether nn Michler's ketone

【table】

【table】

【table】

EXAMPLE 55 Preparation of positive-working litho film The following two solutions were prepared. A Carbon black 20g Methylene chloride 120g B Copolymer K 1g 11-mercaptoundecanoic acid 0.20g Benzyl dimethyl ketal 0.20g Methylene chloride/methanol (90/10) solvent
Pressurize solution A through a 4.3 g 10 μm Millipore filter and filter the solution to 4 mil (100 μm).
m) 5 mils (125 μm) using a doctor knife
was coated on a gelatin-coated oriented polyester film substrate. This coated film was dried. It had a transparency of 5.70. Solution B was coated onto the solution A coated substrate using the same doctor knife. This coated film was passed through a √2 step wedge and a silver negative with a transparency of 0.4%.
Exposures were made to a radiation dose of 67 units in 13 vacuum printing frames. The exposed film was developed using a 0.8% sodium carbonate solution in water/2-(2-butoxyethoxy)ethanol (9/1) in a spray developer for 2 minutes at 35°. The last step washed away corresponds to an energy of 0.13 mj/cm ² on the film surface. Examples 56-62 These examples were performed using the methods described in Examples 13 and 15-54. No further plasticizer was used. A coating thickness of 200 μm was used in each example. Oriented polyester or polypropylene film substrates were used. A summary of these examples is included in Tables 9 and 10. In Table 9, mercapto acids and radical-forming initiators not listed in the previous examples are referred to by the following symbols: Mercaptoic acid l 5-mercaptopentane phosphate m 2-mercaptohexadecanoic acid initiator oo 4-methyl-4-trichloromethyl-2,
5-Cyclohexadienone (TMCH)

【table】

【table】

【table】

Claims (1)

[Scope of Claims] 1st component, i.e. approximately 10 to 90% of the total weight of components (i), (ii) and (iii)
a polyene having a number average molecular weight of about 1,000 to 1,000,000 and containing about 20 to 1,800 milliequivalents of reactive unsaturated carbon-carbon groups per 100 g; about 1% to 70% by weight of the reactive mercapto acid, and about 0.001% to 50% by weight of the total weight of components (i), (ii) and (iii).
% of a radiation-sensitive radical-generating system that can be activated by actinic radiation to initiate the addition of mercapto acid to a polyene. 2. The composition according to claim 1, wherein the polyene contains at least one group selected from the formulas -CH=CH- and -CH= _CH2 . 3. The composition of claim 2 containing such a group in the alkyl portion of the substituted alkyl methacrylate copolymer. 4. A composition according to claim 3, wherein the polyene is selected from copolymers of methyl methacrylate and allyl methacrylate or undecenyl methacrylate and terpolymers of methyl methacrylate, butyl methacrylate and allyl methacrylate. 5. The composition of claim 1, wherein the polyene has a molecular weight of about 5,000 to 100,000 and there are about 50 to 1,000 milliequivalents of reactive unsaturated carbon-carbon groups per 100 grams of polyene. 6. The composition according to claim 1, wherein the mercapto acid is a mercaptocarboxylic acid. 7. The composition of claim 1, wherein the radical generating system includes benzoin ether. 8. Claim 1, wherein the mercapto acid is 11-mercaptoundecanoic acid and the radical generating system is a benzyl dimethyl ketal compound.
Compositions as described in Section. 9. The composition of claim 1, wherein the radical generating system comprises 4-methyl-4-trichloromethyl-2,5-cyclohexadienone.