Lithographic printing plate precursor and method of use
IR-sensitive lithographic printing plate precursors provide a stable print-out image using a unique IR-sensitive image-recording layer. The IR radiation-sensitive layer includes: (1) a free radical initiator composition with an electron-donating agent and one or more iodonium cations; (2) a free radically polymerizable composition; and (3) a color-changing compound of Structure (I) having an indene ring in the conjugated chain between the aromatic terminal groups. The IR radiation-sensitive composition and layer also contains one or more borate ions such that the molar ratio of one or more borate ions to the one or more iodonium ions is at least 0.5:1. After IR imaging, these precursors exhibit desirable printout images both fresh and after dark storage. The precursors can be developed on-press.
1. A lithographic printing plate precursor comprising:
a substrate, and
an infrared radiation-sensitive image-recording layer disposed on the substrate, the infrared radiation-sensitive image-recording layer comprising the following components (1), (2), and (3):
(1) a free radical initiator composition that is capable of generating free radicals upon exposure to infrared radiation, and which comprises an electron-donating agent and one or more iodonium cations;
(2) a free radically polymerizable composition; and
(3) a color-changing compound that is represented by the following Structure (I)
wherein:
Ar1, Ar2, and Ar3 independently represent the atoms necessary to complete substituted or unsubstituted aromatic rings or to complete substituted or unsubstituted heteroaromatic rings;
Y represents an oxygen atom, a sulfur atom, or a dialkylmethylene group represented by >C(R 4 R 5 ) wherein R 4 and R 5 are independently substituted or unsubstituted alkyl groups having 1 to 4 carbons;
R 1 and R 2 are independently substituted or unsubstituted alkyl groups;
X represents a single bond or a divalent linking group selected from —S—, —O—, and >N(R 6 ) wherein R 6 is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or L;
L represents a —C(═O)—OR 7 group, —SO 2 —R 3 group, or —SO 2 NR 8 R 9 group, wherein R 7 represents a substituted or unsubstituted alkyl group that has a secondary or tertiary connecting carbon that connects to the remainder of the —C(═O)OR 7 group; and R 3 , R 8 , and R 9 independently represent substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, or substituted or unsubstituted heteroaryl groups; and
Za represents one or more counter ions to balance the electric charge in the rest of the color-changing compound according to Structure (I),
wherein the infrared radiation-sensitive image-recording layer comprises one or more borate anions in an amount such that the molar ratio of the one or more borate anions to the one or more iodonium cations is at least 0.8:1 and up to and including 4:1, and the borate anions are represented by following Structure (IIIa):
B(R 10 R 11 R 12 R 13 ) − Structure (IIIa)
wherein R 10 , R 11 , R 12 , and R 13 are independently substituted or unsubstituted alkyl groups or substituted or unsubstituted aryl groups, provided that at least three of R 10 , R 11 , R 12 , and R 13 are the same or different substituted or unsubstituted aryl groups, and the substituted aryl groups each have no more than two halo substituents.
2. The lithographic printing plate precursor of claim 1 , wherein the (3) color-changing compound is represented by the following Structure (II):
wherein Ar1, Ar2, Ar3, R 1 , R 2 , R 3 , R 6 , Y, and Za are as defined above.
3. The lithographic printing plate precursor of claim 1 , wherein Ar1 and Ar2 are the atoms necessary to complete the same or different substituted or unsubstituted aromatic rings.
4. The lithographic printing plate precursor of claim 1 , wherein one or both of the aromatic rings completed by the atoms of Ar1 and Ar2 are substituted with one or two halo groups that can be the same or different.
5. The lithographic printing plate precursor of claim 1 , wherein R 3 is a trifluoromethyl group.
6. The lithographic printing plate precursor of claim 1 , wherein Za comprises a tetraaryl borate anion.
7. The lithographic printing plate precursor of claim 1 , wherein the electron-donating agent is an organic borate salt represented by the following Structure (III):
[B(R 10 R 11 R 12 R 13 ) − ] n M n+ Structure (III)
wherein R 10 , R 11 , R 12 , and R 13 are as defined for Structure (IIIa), n is an integer equal to or greater than 1, and M n+ is an n-valent cation.
8. The lithographic printing plate precursor of claim 7 , wherein all of R 10 , R 11 , R 12 , and R 13 in Structure (IIIa) and Structure (III) are the same substituted or unsubstituted phenyl groups.
9. The lithographic printing plate precursor of claim 1 , wherein the infrared radiation-sensitive image-recording layer further comprises a component (4) infrared absorbing material that is different from the component (3) color-changing compound.
10. The lithographic printing plate precursor of claim 1 , wherein the component (1) free radical initiator composition comprises a diaryliodonium tetraphenylborate salt.
11. The lithographic printing plate precursor of claim 9 , wherein the infrared radiation-sensitive image-recording layer further comprises a component (5) acid-sensitive dye precursor that is different from all of the components (1), (2), (3), and (4) defined above.
12. The lithographic printing plate precursor of claim 9 , wherein the infrared radiation-sensitive image-recording layer further comprises a component (6) non-free radically polymerizable polymeric material that is different from all of the components (1), (2), (3), and (4) defined above and is present in particulate form.
13. The lithographic printing plate precursor of claim 1 , wherein the component (3) color-changing compound represented by Structure (I) is present in the infrared radiation-sensitive image-recording layer in a coverage amount of at least 0.5 weight % and up to and including 15 weight %, based on the total weight of the infrared radiation-sensitive image-recording layer.
14. A method for providing a lithographic printing plate, comprising:
A) imagewise exposing the lithographic printing plate precursor according to claim 1 to infrared radiation, to provide exposed regions and non-exposed regions in the infrared radiation-sensitive image-recording layer, and
B) removing the non-exposed regions in the infrared radiation-sensitive image-recording layer from the substrate on-press using a lithographic printing ink, a fountain solution, or a combination of a lithographic printing ink and a fountain solution.
15. The lithographic printing plate precursor of claim 1 , wherein the molar ratio of the one or more borate anions to the one or more iodonium cations is at least 0.8:1 and up to and including 2.5:1.
16. The lithographic printing plate precursor of claim 1 , wherein the component (3) color-changing compound according to Structure (I), absent the counterion Za, is positively charged.
17. The lithographic printing plate precursor of claim 1 , wherein the infrared radiation-sensitive image-recording layer is capable of producing a color change when exposed to infrared radiation for 90 mJ/cm 2 and stored in the dark for 24 hours, and this color change in ΔE units is at least 3 or more than the color change in ΔE units of a reference infrared radiation-sensitive image-recording layer that is identical to the infrared radiation-sensitive image-recording layer except for substitution of hexafluorophosphate anion for all borate anions represented by Structure (IIIa).
18. The lithographic printing plate precursor of claim 1 , wherein the infrared radiation-sensitive image-recording layer is capable of producing a colored compound when exposed to infrared radiation, and the produced colored compound satisfies the following equation A:
FW3>FW1 (Equation A)
wherein FW1 is the formula weight in Daltons of the (3) color-changing compound according to Structure (I), absent the counter ion Za, and FW3 is the formula weight in Daltons of the produced colored compound, absent the counter ion Za.
19. The lithographic printing plate precursor of claim 1 , wherein the infrared radiation-sensitive image-recording layer is capable of producing a colored compound when exposed to infrared radiation and the produced colored compound satisfies at least one of the following equations B, C, D, and E:
FW1+FW21+2≥FW3≥FW1+FW21−2 (Equation B)
FW1+FW22+2≥FW3≥FW1+FW22−2 (Equation C)
FW1+FW23+2≥FW3≥FW1+FW23−2 (Equation D)
FW1+FW24+2≥FW3≥FW1+FW24−2 (Equation E)
wherein:
FW1 is the formula weight in Daltons of the (3) color-changing compound according to Structure (I), absent the counter ion Za,
FW21 is the formula weight in Daltons of R 10 in Structure (IIIa),
FW22 is the formula weight in Daltons of R 11 in Structure (IIIa),
FW23 is the formula weight in Daltons of R 12 in Structure (IIIa),
FW24 is the formula weight in Daltons of R 13 in Structure (IIIa), and
FW3 is the formula weight in Daltons of the produced colored compound, absent the counter ion Za.
20. The method of claim 14 , wherein when the imagewise exposing in A) is carried out with infrared radiation at 90 mJ/cm 2 , the imagewise exposing causes the infrared radiation-sensitive image-recording layer of the lithographic printing plate precursor to produce a color change which when stored in the dark for 24 hours, ΔE units is at least 3 or more than the color change in ΔE units of a reference infrared radiation-sensitive image-recording layer that is imagewise exposed in the same manner and is identical to the infrared radiation-sensitive image-recording layer except for substitution of hexafluorophosphate anion for all borate anions represented by Structure (IIIa).
21. The method of claim 14 , wherein the imagewise exposing in A) to infrared radiation causes the infrared radiation-sensitive image-recording layer of the lithographic printing plate precursor the infrared radiation-sensitive image-recording layer to produce a colored compound that satisfies the following equation A:
FW3>FW1 (Equation A)
wherein FW1 is the formula weight in Daltons of the (3) color-changing compound according to Structure (1), absent the counter ion Za, and FW3 is the formula weight in Daltons of the produced colored compound, absent the counter ion Za.
22. The method of claim 14 , wherein the imagewise exposing in A) to infrared radiation causes the infrared radiation-sensitive image-recording layer of the lithographic printing plate precursor to produce a colored compound that satisfies at least one of the following equations B, C, D, and E:
FW1+FW21+2≥FW3≥FW1+FW21−2 (Equation B)
FW1+FW22+2≥FW3≥FW1+FW22−2 (Equation C)
FW1+FW23+2≥FW3≥FW1+FW23−2 (Equation D)
FW1+FW24+2≥FW3≥FW1+FW24−2 (Equation E)
wherein:
FW1 is the formula weight in Daltons of the (3) color-changing compound according to Structure (I), absent the counter ion Za,
FW21 is the formula weight in Daltons of R 10 in Structure (IIIa),
FW22 is the formula weight in Daltons of R 11 in Structure (IIIa),
FW23 is the formula weight in Daltons of R 12 in Structure (IIIa),
FW24 is the formula weight in Daltons of R 13 in Structure (IIIa), and
FW3 is the formula weight in Daltons of the produced colored compound, absent the counter ion Za.