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Patent US4272608 - Photosensitive compositions containing thermoplastic ionomeric elastomers ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsPhotosensitive, elastomeric compositions comprising (1) a high molecular weight carboxylated butadiene/acrylonitrile copolymer in which at least about 25% of the carboxyl groups are neutralized with a metal cation of Groups IIA or IIB of the Periodic Table, (2) an ethylenically unsaturated monomer, and...http://www.google.com/patents/US4272608?utm_source=gb-gplus-sharePatent US4272608 - Photosensitive compositions containing thermoplastic ionomeric elastomers useful in flexographic printing platesAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS4272608 APublication typeGrantApplication numberUS 06/027,445Publication dateJun 9, 1981Filing dateApr 5, 1979Priority dateApr 5, 1979Also published asDE3012841A1, DE3012841C2Publication number027445, 06027445, US 4272608 A, US 4272608A, US-A-4272608, US4272608 A, US4272608AInventorsStephen ProskowOriginal AssigneeE. I. Du Pont De Nemours And CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (6), Non-Patent Citations (1), Referenced by (59), Classifications (21) External Links: USPTO, USPTO Assignment, EspacenetPhotosensitive compositions containing thermoplastic ionomeric elastomers useful in flexographic printing plates
Carboxyl groups may be incorporated into the high molecular weight copolymer by addition to the polymerization process of a carboxyl-containing termonomer, e.g., methacrylic acid, or a termonomer which is convertible to a carboxyl-containing group, e.g., maleic anhydride or metal methacrylate. Such polymers are available commercially from several sources, e.g., from the B. F. Goodrich Company under the trade name Hycar®.
The third essential ingredient of the photosensitive compositions of this invention is a radiation-sensitive, free radical generating system. Practically any radiation-sensitive, free radical generating system which initiates polymerization of the unsaturated compound and does not excessively terminate the polymerization can be used in the photosensitive compositions of this invention. Because process transparencies transmit heat originating from conventional sources of actinic radiation, and since the photosensitive compositions are usually prepared under conditions resulting in elevated temperatures, the preferred free-radical generating compounds are inactive thermally below 85° C., and more preferably below 185° C. They should be dispersible in the composition to the extent necessary for initiating the desired polymerization or cross-linking under the influence of the amount of radiation absorbed in relatively short term exposures. These initiators are useful in amounts from about 0.001 to about 10% by weight, and preferably from about 0.1 to about 5% based on the total weight of the solvent-free photosensitive composition.
Solvent development may be carried out at about 25° C., but best results are obtained when the solvent is warm, e.g., 30°-60° C. Development time can be varied and preferably is in the range of 5-25 minutes.
The photosensitive compositions were generally prepared by mixing the ingredients under yellow light on a rubber mill at 100°-120°. The order of mixing was usually as follows:
The photosensitive compositions were prepared by pressing the milled compositions, supported on a 5-mil (127-μm) vinylidene chloride/vinyl chloride copolymer-subbed, oriented polyester film substrate or a 5-mil flame-treated oriented polyester film substrate, at 100°-120° and 15,000-20,000 psi (103,000-138,000 kPa) using 65-mil (1650-μm) or 112-mil (2840-μm) metal shims to control plate thickness. A polytetrafluoroethylene cover sheet was employed. A Pasadena press was employed for preparation of the plates. The polytetrafluoroethylene cover sheet was replaced with a 1-mil (25.4-μm) thick film of polypropylene before exposure.
The 65-mil (1650-μm) thick plate samples were exposed for 30 minutes in a vacuum frame at about 250 mm mercury pressure to a Black Light Eastern (BLE) Spectroline exposure source, Model XX15 (0.76 amp), containing two 15 W lamps (G.E. F15T8-BL) held 2 inches (5.1 cm) from the sample, unless otherwise specified. A sheet of standard antihalation material was placed on the underside of the samples during exposure. Standard negative resolution targets were used as process transparencies in contact with the photosensitive compositions. After exposure, the polypropylene cover sheet was removed and the images were developed mechanically by brushing the plate surfaces for 20 min at about 55° in a solution of 0.8% sodium carbonate in 2-(2-butoxyethoxy)ethanol/water (1/9 w/w). The development was conducted with a single-brush prototype of a commercial processor (Cyrel® Plate Processor; Model No. 2-1824; Du Pont Co.) which was modified with a heater to allow operation at elevated temperatures. After development, the plates were air-dried for 30 min at about 65°, further dried at 25° overnight, and finally post-exposed for 1 hr in air with the lamp source described. Plate clarity, flexibility, relief height and image quality were assessed for these plates.
The ink solvent resistance was determined by immersing 1in.×2 in. (2.5-5.1 cm) samples of the finished plates in various test solvents or solvent mixtures (in which proportions are by volume), and the percent volume swell after 24 hr was measured. Volume swell was calculated from the weight of sample in air (A) and weight in a buoyant liquid (L), usually 2-propanol, by the equation:
The following photosensitive composition was blended by milling at 100° following the general procedure described:
70 parts of Hycar® 1072-CG
Hycar® 1072-CG (B. F. Goodrich Company) is a high molecular weight (average Mooney Viscosity=45:Mn˜31,000) carboxylated butadiene/acrylonitrile copolymer (˜27% acrylonitrile content; carboxyl content˜3.38% based on an EPHR value of 0.075).
After milling, the slab was pressed into plates at 110°/20,000 psi (138,000 kPa) by the general procedure described. The 65-mil (1650-μm) plate was exposed to radiation for 30 min through a line process negative, and the exposed image was developed by the general procedure described. A relief image was obtained corresponding to the transparent areas of the process transparency. The plate after development was virtually unswelled, nontacky and showed very little image distortion because of the high elastic recovery of the plate. A 13.5-mil (340-μm) relief was measured after the plate was dried and post-exposed as described. The clear, nontacky plate was characterized by good flexibility and excellent image sharpness in the raised relief areas. It could be bent through a 180° angle without cracking of the image. Plate properties were further assessed as described below.
The following photosensitive composition was blended by milling at 120° following the general procedure.
This example demonstrates the improvement in physical properties obtained with a composition of the invention compared with a control without metal ion cross-links. Following the general procedure, photosensitive compositions were blended by milling at 110°, as follows:
______________________________________  Formulation A  70 parts of Hycar® 1072-CG  28 parts of 1,6-hexanediol diacrylate   1 part of benzil dimethyl ketal   6.92 parts of zinc acetylacetonate  Formulation B (Control)  70 parts of Hycar® 1072-CG  28 parts of 1,6-hexanediol diacrylate   1 part of benzil dimethyl ketal______________________________________
This example illustrates the addition of an optional component, i.e., a low molecular weight carboxylated butadiene/acrylonitrile copolymer, to a composition of the invention. Following the general procedure, photosensitive compositions were blended by milling at 110°, as follows:
______________________________________Formulation A60 parts of Hycar® 1072-CG20 parts of Hycar® CTBNX (1300 X 9) low molecular weight copolymer19 parts of 1,6-hexanediol diacrylate 1 part of benzil dimethyl ketal 7.91 parts of zinc acetylacetonateFormulation B (Control)60 parts of Hycar® 1072-CG20 parts of Hycar® CTBNX (1300 X 9)19 parts of 1,6-hexanediol diacrylate 1 part of benzil dimethyl ketal______________________________________
Hycar® CTBNX (1300×9) (B. F. Goodrich Company) is a low molecular weight (Mn˜3,400) liquid butadiene/acrylonitrile copolymer (˜18% acrylonitrile content) containing terminal and pendant carboxyl groups (EPHR=0.072; 3.24% carboxyl content).
74 parts of Hycar® 1072-CG
TABLE V______________________________________                               % Vol. SwellLow Molec-                    Impact                               After 24 Hrular Weight Shore A   Relief, Resil-                               Immersion.sup.(2)Ex.  Compound   Hardness.sup.(1)                     (&#956;m)                           ience A   B   C______________________________________5    Isostearic 56 (28)   458   32    8.1 1.7 20.5Acid6    Hycar® 60 (40)   458   27    6.6 1.5 15.01312.sup.(3)7    Dioctyl    60 (35)   305   28    6.0 2.1 15.2phthalate______________________________________ .sup.(1) Number in parentheses is hardness value for corresponding unexposed plate. .sup.(2) A = ethanol; B = nheptane; C = ethanol/nheptane (50/50). .sup.(3) Hycar® 1312 (B. F. Goodrich Company) is a low molecular weight (--- Mn &#732; 1200) liquid butadiene/acrylonitrile copolymer (33 acrylonitrile content).
This example illustrates neutralization of approximately one-half of the available carboxyl groups of the binder with zinc cations. The following photosensitive composition was blended by milling at 110° following the general procedure:
______________________________________Examples 9-1070 parts of Hycar® 1072-CG28 parts of ethylenically unsaturated compound 1 part of benzil dimethyl ketal 7.88 parts of zinc acetylacetonate dihydrate.Examples 11-1374 parts of Hycar® 1072-CG25 parts of ethylenically unsaturated compound 1 part of benzil dimethyl ketal 7.38 parts of zinc acetylacetonate______________________________________
TABLE VII______________________________________   Ethylenically Shore A   ReliefExample  Unsaturated Compound                 Hardness.sup.(1)                           (&#956;m)______________________________________ 9     14 Parts 1,6-hexane-                 55     (45) 470  diol diacrylate + 14  parts Hycar® VTBNX  (1300 × 19).sup.(3)10     Triethylene glycol                 75     (45) 458  dimethacrylate11     Poly(ethylene glycol)                 61     (42) 318  diacrylate12     1,10-Decanediol                 64     (36) 424  diacrylate13     5 Parts trimethylol-                 57     (46) 280  propane triacrylate  + 20 parts Hycar®  VTBNX (1300 × 19).sup.(3)______________________________________                           % Vol. Swell 24  Ethylenically  Impact    Hr Immersion.sup.(2)Example  Unsaturated Compound                 Resilience                           A    B    C______________________________________ 9     14 Parts 1,6-hexane-                 33        6.4  2.2  17.5  diol diacrylate + 14  parts Hycar® VTBNX  (1300 × 19).sup.(3)10     Triethylene glycol                 28        5.0  2.1  12.4  dimethacrylate11     Poly(ethylene glycol)                 20        6.4  0.8  11.4  diacrylate12     1,10-Decanediol                 33        5.2  1.6  11.9  diacrylate13     5 Parts trimethylol-                 18        6.2  2.7  16.6  propane triacrylate  +  20 parts Hycar®  VTBNX (1300 × 19).sup.(3)______________________________________ .sup.(1) Number in parentheses is hardness value for corresponding unexposed plate. .sup.(2) A = ethanol; B = nheptane; C = ethanol/nheptane (50/50). .sup.(3) Hycar® VTBNX (1300 × 19) (B. F. Goodrich Company) is a low molecular weight (Brookfield Viscosity = 490,000 cps at 27°, ---Mn &#732; 3000-4000) liquid butadiene/acrylonitrile copolymer (&#732;16- 17% acrylonitrile) containing pendant and terminal vinyl groups (EPHR vinyl group content = 0.07).
These examples illustrate the use of magnesium and calcium ions to form metal ion cross-links. Following the general procedure, photosensitive compositions which included the ethylenically unsaturated compound specified in Table VIII were blended by milling at 110°, as follows:
______________________________________Examples 14 and 1570 parts of Hycar® 1072-CG28 parts of ethylenically unsaturated compound 1 part of benzil dimethyl ketal 5.85 parts of magnesium acetylacetonatedihydrateExamples 16 and 1770 parts of Hycar® 1072-CG28 parts of ethylenically unsaturated compound 1 part of benzil dimethyl ketal 6.27 parts of calcium acetylacetonate______________________________________
Plates were pressed from the slabs, and the plates were exposed and developed by the general procedures described. Physical property data of the post-exposed plates are summarized in Table VIII. The clear flexible plates possessed imaging characteristics similar to those of the plates of Example 1; however, the background areas were generally less smooth for these plates. The plates could be bent through a 180° angle without cracking of the images.
TABLE VIII______________________________________  Ethylenically   Shore A   ReliefExample  Unsaturated Compound                  Hardness.sup.(1)                            (&#956;m)______________________________________14     1,6-Hexanediol di-                  72    (40)  463  acrylate15     14 Parts 1,6-hexane-                  68    (45)  399  diol diacrylate + 14  parts Hycar® VTBNX  (1300 × 19)16     1,6-Hexanediol  75    (49)  419  diacrylate17     14 Parts 1,6-hexane-                  60    (42)  394  diol diacrylate + 14  parts Hycar® VTBNX  (1300 × 19)______________________________________            Impact                  % Vol. SwellEthylenically      Resil-  24 Hr Immersion.sup.(2)Example  Unsaturated Compound                  ience   A    B    C______________________________________14     1,6-Hexanediol di-                  32      6.4  0.7  13.5  acrylate15     14 Parts 1,6-hexane-                  24      8.1  3.0  19.2  diol diacrylate + 14  parts Hycar® VTBNX  (1300 × 19)16     1,6-Hexanediol  31      5.2  1.4  12.1  diacrylate17     14 Parts 1,6-hexane-                  28      6.4  1.8  16.7  diol diacrylate + 14  parts Hycar® VTBNX  (1300 × 19)______________________________________ .sup.(1) Number in parentheses is hardness value for corresponding unexposed plate. .sup.(2) A = ethanol; B = heptane; C = ethanol/nheptane (50/50).
This example illustrates the use of zinc acetate dihydrate to form the metal ion cross-links. The following photosensitive composition was blended by milling at 110° following the general procedure:
56 parts of Hycar® 1072-CG,
28 parts of Hycar® CTBNX (1300×9) low molecular weight copolymer,
The composition also contained 0.1 part of a thermal inhibitor source, 1,4,4-trimethyl-2,3-diazabicyclo-[3.2.2]non-2-ene-N,N'-dioxide, which was premixed with the Hycar® CTBNX (1300×9) prior to addition to the mill.
After milling, the slab was pressed into plates at 110°/20,000 psi by the general procedure described. Both plates in this example were exposed to radiation by the bank of lights described for the 112-mil plates. The 65-mil plate was exposed for 15 minutes (top blanket exposure) and the 112-mil plate was exposed for 4 minutes (back-exposure) and 15 minutes (top exposure). These plates were subsequently postexposed for 15 minutes (65-mil plate) and 10 minutes (112-mil plate) respectively after the development and drying steps.
Following the general procedure, photosensitive compositions which included the high molecular weight carboxylated butadiene/acrylonitrile copolymers listed in Table X were blended by milling at 110°, as follows:
28 parts of Hycar® CTBNX (1300×9) low molecular weight copolymer, Example 4,
Each composition also contained 0.1 part of 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N'-dioxide which was premixed with the Hycar® CTBNX (1300×9) before addition to the mill.
TABLE X______________________________________  Carboxylated Zinc  Butadiene/   Acetyl-  Acrylonitrile               acetonate,                         Shore A ReliefEx.    Copolymer    (parts)   Hardness.sup.(1)                                 (&#956;m)______________________________________19     Hycar® 1072-CG               8.17      63 (30) 50820     Krynac® 221               8.44      68 (34) 28021     Krynac® 211               10.00     60 (34) 68522     Krynac® 211 HV               10.00     65 (37) 63523     Hycar® 1072-CG               7.91      63 (30) 508  Dusted Crumb______________________________________CarboxylatedButadiene/                % Vol. SwellAcrylonitrile   Impact    24 Hr Immersion.sup.(2)Ex.    Copolymer    Resilience                         A    B    C______________________________________19     Hycar® 1072-CG               27        6.1  6.2  21.520     Krynac® 221               24        5.9  4.8  19.621     Krynac® 211               19        7.2  4.5  22.322     Krynac® 211 HV               21        6.7  4.6  20.223     Hycar® 1072-CG               27        6.3  6.5  22.1  Dusted Crumb______________________________________ .sup.(1) Number in parentheses is hardness value for corresponding unexposed plate. .sup.(2) A = ethanol; B = nheptane; C = ethanol/nheptane (50/50).
Krynac® 221 (Polysar, Inc.): Mooney Viscosity=50; acrylonitrile content, ˜25-30%; carboxyl content, ˜3.5%.
Krynac® 211 (Polysar, Inc.): Mooney Viscosity=55; acrylonitrile content, ˜31-34%; carboxyl content, ˜4.5%.
Krynac® 211 HV (Polysar, Inc.): Mooney Viscosity=75; acrylonitrile content, ˜31-34%; carboxyl content, ˜4.5%.
Hycar® 1072-CG dusted crumb was obtained from B. F. Goodrich Company. It was prepared by cutting Hycar® 1072-CG into 3/8 in pieces and dusting with 16 weight percent of an 85/15 vinyl chloride/vinyl acetate copolymer dust (VYHH) obtained from Union Carbide Corp. The crumb rubber was sifted through a 30-mesh screen prior to use which reduced the amount of copolymer dust to ˜8%.
Following the general procedure, photosensitive compositions which included the low molecular weight butadiene/acrylonitrile copolymers of Table XI were blended by milling at 110°, as follows:
65 parts of Hycar® 1072-CG Dusted Crumb, Example 23,
Plates were pressed from the slabs (110°/20,000 psi) and the plates were exposed to radiation by the bank of lights described for the 112-mil plates for the following times:
TABLE XI______________________________________                Zinc Low Molecular  Acetyl Weight         acetonate                         Shore A2                                 ReliefEx.   Copolymer      (parts)  Hardness.sup.(1)                                 (&#956;m)______________________________________24    Hycar® CTBNX                8.17     58      432 (1300 × 9), Example 425    Hycar® 1312                6.06     51      330 Example 626    12 parts Hycar®                7.12     54-56   407 CTBNX (1300 × 9) + 12 parts Hycar® 131227    12 parts Hycar®                6.06     54      330 VTBNX (1300 × 23) + 12 parts Hycar® 131228    12 parts Hycar®                7.12     59-60   330 CTBNX (1300 × 9) + 12 parts Hycar® VTBNX (1300 × 23)______________________________________Low Molecular          % Vol. SwellWeight           Impact    24 Hr Immersion.sup.(2)Ex.   Copolymer      Resilience                          A     B______________________________________24    Hycar® CTBNX                23        5.6   4.7 (1300 × 9), Example 425    Hycar® 1312,                17        5.9   2.3 Example 626    12 parts Hycar®                19        5.7   3.1 CTBNX (1300 × 9) + 12 parts Hycar® 131227    12 parts Hycar®                17        5.8   3.0 VTBNX (1300 × 23) + 12 parts Hycar® 131228    12 parts Hycar®                19        5.9   4.2 CTBNX (1300 × 9) + 12 parts Hycar® VTBNX (1300 × 23)______________________________________ .sup.(1) Hardness was measured with a Shore Conveloader®, Type A2 Durometer. .sup.(2) A = ethanol; B = nheptane.
Hycar® VTBNX (1300×23) (B. F. Goodrich Company) is an improved shelf-stable version of VTBNX (1300×19), Example 13.
These examples illustrate the use of a carboxylated butadiene/acrylonitrile copolymer crumb dusted with a silica powder. Following the general procedure, photosensitive compositions which included the low molecular weight butadiene/acrylonitrile copolymers of Table XII were blended by milling at 110°, as follows:
61 parts of Hycar® 1072-CG Dusted Crumb,
Hycar® 1072-CG dusted crumb was obtained from the B. F. Goodrich Company. It was prepared by cutting Hycar® 1072-CG into 3/8 in pieces and dusting with 3 weight percent of a very fine fumed silica (Cab-o-Sil® M-5) obtained from Cabot Corporation. The crumb rubber was sifted through a 30-mesh screen prior to use which reduced the amount of dust to ˜1 percent.
Plates were prepared from the slab at 130°/20,000 psi, and the plates were exposed and developed by the procedure described in Examples 24-28. The properties of the postexposed, 112-mil plates are summarized in Table XII. The 65-mil plates possessed imaging characteristics similar to those of the plates of Example 1. The plates of these examples were slightly hazy because of the presence of the small amount of dusting agent in the compositions.
TABLE XII______________________________________                Zinc Low Molecular  Acetyl- Weight         acetonate                         Shore A2                                 ReliefEx.   Copolymer      (parts)  Hardness.sup.(1)                                 (&#956;m)______________________________________29    Hycar® CTBNX                8.56     52-53   482 (1300 × 9)30    14 parts Hycar®                7.25     52      560 CTBNX (1300 × 9) + 14 parts Hycar® 131231    Hycar® 1312                6.06     50-51   432______________________________________Low Molecular          % Vol. SwellWeight           Impact    24 Hr Immersion.sup.(2)Ex.   Copolymer      Resilience                          A      B______________________________________29    Hycar® CTBNX                27        6.5    6.6 (1300 × 9)30    14 parts Hycar®                26        6.4    4.7 CTBNX(1300 × 9) + 14 parts Hycar® 131231    Hycar® 1312                21        6.8    3.6______________________________________ .sup.(1) Hardness was measured with a Shore Conveloader®, Type A2 Durometer. .sup.(2) A = ethanol; B = nheptane.
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