USE

FIELD OF THE INVENTION

This invention relates to infrared radiation-sensitive lithographic printing plate precursors that can be imaged using infrared radiation to provide imaged lithographic printing plates. Such precursors include unique infrared radiation-sensitive compositions that provide a stable printout image between exposed and non-exposed regions in the imagewise exposed infrared radiation- sensitive image-recording layer. This invention also relates to methods of using these precursors to provide lithographic printing plates having excellent printout images.

BACKGROUND OF THE INVENTION

In lithographic printing, lithographic ink receptive regions, known as image areas, are generated on a hydrophilic surface of a planar substrate such as an aluminum-containing substrate. When the printing plate surface is moistened with water and a lithographic printing ink is applied, hydrophilic regions retain the water and repel the lithographic printing ink, and the lithographic ink receptive image regions accept the lithographic printing ink and repel the water. The lithographic printing ink is transferred to the surface of a material upon which the image is to be reproduced, perhaps with the use of a blanket roller in a printing press.

Negative-working lithographic printing plate precursors useful to prepare lithographic printing plates typically comprise a negative-working radiation-sensitive image-recording layer disposed over the hydrophilic surface of the substrate. Such an image-recording layer includes radiation-sensitive components that can be dispersed in a suitable polymeric binder material. After the precursor is imagewise exposed to suitable radiation to form exposed regions and non-exposed regions in the image-recording layer, the non-exposed regions are removed by suitable means, revealing the underlying hydrophilic surface of the substrate. The exposed regions of the image-recording layer that are not removed are lithographic ink-receptive, and the hydrophilic substrate surface revealed by the developing process accepts water and aqueous solutions such as a fountain solution and repels lithographic printing ink.

In recent years, there has been an increased desire in the lithographic printing industry for simplification in making lithographic printing plates by carrying out development on-press (“DOP”) using a lithographic printing ink or fountain solution, or both, to remove non-exposed regions of the image-recording layer.

Thus, on-press developable lithographic printing plate precursors have gained increasing attention in the printing industry in recent decades due to their many benefits over conventionally processed (“off-press” processed or developed) lithographic printing plate precursors, including less environmental impact and savings on processing chemicals, processor floor space, operation and maintenance costs. After laser imaging, on-press developable precursors can be taken directly to the printing press without any prior wet chemical step of removing the imageable coating on the precursors in the non-printing regions.

Therefore, it is highly desirable that such imaged lithographic printing plate precursors have different colors in the exposed regions and the unexposed regions. The color difference or “contrast” between the exposed and unexposed regions is typically called “printout” or a “printout image.” A strong printout will facilitate the operator's visual assessment and identification of the imaged printing plate precursors so that the printing plate precursors can be properly attached to printing press units.

Many approaches have been taken to strengthen the printout of on- press developable printing plate precursors. It has been observed that they all have weaknesses of some kind.

For example, the printout on printing plate precursors having imaging compositions that comprise an acid generator and an acid-sensitive color precursor such as lactone based leuco dyes, is often not strong enough due to the limited efficiency of acid generation in imaging compositions designed for infrared radiation imaging and on-press development. Furthermore, the concentration of protons generated during infrared radiation imaging often decreases after imaging through chemical equilibration or other post-imaging chemical reactions. As a result, the printout based on proton-induced color change often fades after imaging.

Co-pending and commonly assigned U.S. Patent Application Publication 2021/0078350 (Viehmann et al.) describes efforts to increase printout by incorporating more sensitive color-forming compounds that switch from colorless forms to colored forms at lower acid concentrations into the infrared radiation-sensitive imaging compositions. Background color formation is suppressed by a special additive to stabilize the good contrast. The initial printout achieved is quite high but there remains a need to improve the printout and the printout stability obtained using the described chemistry.

A different approach to generating printout is based on the use of infrared (IR) decomposable dyes that comprise a thermal labile group and are capable of losing the thermal labile group upon exposure to infrared radiation or heat to form compounds of different colors having absorption spectra in the visible spectral region. Examples based on this approach are described in U.S. Patents 8,148,042 (Callant et al.) and 8,178,282 (Callant et al.) and U.S. Patent Application Publication 2010/0274023 (Callant et al.). Such IR decomposable dyes typically should be present in relatively large amounts in the imaging composition, or at lower amounts and high exposure infrared radiation energy is needed in order to generate sufficient printout.

Furthermore, some IR decomposable dyes used in such chemistries produce gaseous materials upon decomposition, which gaseous materials are often harmful for negative working compositions based on crosslinking of free radical polymerizable compounds in the presence of a suitable free radical initiator, resulting in poor image durability during printing operations. Moreover, the heat pulse generated from high energy levels of exposing infrared radiation can often damage the physical integrity of the imaging compositions according to a process commonly referred to as ablation or partial ablation. Ablation or partial ablation typically results in poor image durability. For example, in U.S. Patent 8,148,042 (noted above), described printing plate precursors PPP34 and PPP35 comprising IR decomposable dyes within imaging compositions required 275 mJ/cm ² imaging energy in order to generate a cyan printout (ΔOD) of 0.43 and 0.60. There is no teaching that such imaging compositions are useful to form a printing plate having adequate durability of the infrared radiation exposed regions after development of any kind.

The inability for the IR decomposable dyes taught in U.S. Patent 8,148,042 (noted above) to form strong printout under more practical exposure energy such as 120 mJ/cm ² or less when incorporated directly within the polymerizable composition was demonstrated in U.S. Patent Application Publication 2020/0147950 (Billiet), where PPP04 using IR decomposable dye IR02 combined with the IR01 as used in PPP03 produced a very small printout benefit over PPP03 (a DE value at 120 mJ/cm ² of 2.99 vs 2.12). The parameter DE of Billiet is similar to the DE parameter (or value) described below.

In order to avoid ineffectiveness as well as the undesirable effects of the IR decomposable dyes on negative-working printing plate precursors having polymerizable imaging compositions, WO 2019/219560 (Billiet et al.) teaches placing IR decomposable dyes into the protective overcoat applied on top of an imageable layer comprising an IR imageable composition. However, the presence of a protective layer in a lithographic printing plate precursor requires an extra step during manufacturing and when present, its removal reduces the speed of development. Additionally, it can release polymeric or other materials into the fountain solution and cause malfunction of the lithographic printing operation when the printing plate precursors are developed on press. Furthermore, the printout generated with typical exposure dose of infrared radiation suitable for such IR-sensitive imageable compositions is still far less than desired.

U.S. Patent Application Publication 2019/0329545 (Shibamoto et. al.) teaches the use of certain IR decomposable dyes that, in their excited state, are capable of accepting an electron from an electron-donating type initiator upon exposure to infrared radiation to form a first wave of free radicals from the electron-donating initiators and further capable of forming a second wave of free radicals from the IR decomposable dyes through further decomposition on their own or through further reaction with electron-accepting type initiators. The reference suggests color formation capabilities of such imaging compositions containing IR decomposable dyes under the demonstrated exposure conditions. While this publication describes certain infrared dyes that are considered IR decomposable therein, none of the working examples used any IR decomposable dyes as taught in either of U.S. Patent 8,148,042 (noted above) and U.S. Patent Application Publication 2010/0274023 (noted above). On the other hand, the teaching in U.S. Patent Application Publication 2019/0329545 (noted above) considers, as IR decomposable infrared dyes, those taught in U.S. Patent 8,632,941 (Balbinot et al.).

U.S. Patent Application Publication 2020/0117086 (Nogoshi et al.) describes a combination of certain IR decomposable dyes with certain color developers. In the absence of the specified color developer, the specified IR decomposable dyes of this teaching do not have adequate printout as illustrated by its Comparative Examples 1 and 2.

U.S. Patent 8,084,182 (Munnelly et al.) teaches the use of certain IR decomposable dyes within IR-sensitive polymerizable compositions. In its Examples 1-3, Munnelly et al. demonstrated good printout (DE values of 13.8 to 17.4) at high exposure dose of 300 mJ/cm ² in imageable compositions containing IR decomposable dyes that contain an alkoxycarbonylamino group combined, used in combination with a traditional acid-sensitive dye precursor. Without that acid-sensitive dye precursor present, however, Example 4 of Munnelly et al. showed much lower printout (a DE value of 6.6). The use of a comparative IR decomposable dye from the teaching of U.S. Patent 8,148,042 (noted above), not containing an alkoxycarbonylamino group, also provided a low printout at 300 mJ/cm ² imaging energy even in the presence of an acid-sensitive dye precursor (a DE value of 4.6). Moreover, Munnelly et al. only demonstrated a short press run for 200 copies, and it is not apparent whether the printing plates derived from the precursors of Munnelly et al would have sufficient image durability during printing to satisfy customers in the industry who typically need to print many more than 200 copies in a typical press run.

Despite all of the efforts described in the known literature about providing adequate printout for on-press developable lithographic printing plates with exceptional press run durability, there is an ongoing need to provide on-press developable lithographic printing plate precursors that not only have essential properties required such as fast imaging speed, good on-press developability, good lithographic printing durability, and good shelf life, but that also exhibit an adequate and stable printout using lower exposure energy as required for high productivity and thus are compatible with typical cameras and other reading devices used in press automation.

SUMMARY OF THE INVENTION

The present invention provides 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;

(2) a free radically polymerizable composition; and

(3) a color-changing compound that is represented by the following Structure (I) wherein:

Arl and Ar2 independently represent the atoms necessary to complete substituted or unsubstituted aromatic rings or to complete substituted or unsubstituted heteroaromatic rings; R is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl groups;

R'and R ² are independently substituted or unsubstituted alkyl groups;

R ³ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group;

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;

A ¹ and A ² independently represent substituted or unsubstituted alkyl groups, or together they represent the two or three carbon atoms necessary to form a substituted or unsubstituted 5- or 6-membered non-aromatic carbocycbc ring; 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).

This invention also provides a method for providing a lithographic printing plate, comprising:

A) imagewise exposing the lithographic printing plate precursor according to any embodiment of the present invention described herein 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.

The present invention provides a printout image generated in the infrared radiation-sensitive image-recording layer in the regions exposed to relatively low energy imaging infrared radiation. Such a printout image is not only stable during dark storage, but it also has a suitable color hue as indicated by a good cyan ΔOD value and thus is more readable by cameras and other reading devices used in press automation and equipped with a light source having a peak emission around 617 nm. Moreover, in many embodiments, the imaging chemistry used to provide the desirable printout image does not adversely affect imaging speed, on-press developability, or lithographic printing image durability. Further details of the present invention and the results obtained thereby are provided as follows.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

As used herein, the term “infrared radiation absorber” refers to a compound or material that absorbs electromagnetic radiation in the near-infrared (near-IR) and infrared (IR) regions of the electromagnetic spectrum, and it typically refers to compounds or materials that have an absorption maximum in the near-IR and IR regions.

As used herein, the terms “near-infrared region” and “infrared region” refer to radiation having a wavelength of at least 750 nm and higher. In most instances, the terms are used to refer to the region of the electromagnetic spectrum of at least 800 nm and up to and including 1400 nm.

For the purposes of this invention, the strength of printout images is generally indicated by the DE parameter or value, which is the Euclidean distance in CIE 1976 L*a*b* color space between the colors of radiation-exposed region and radiation non-exposed region measured from reflection measurement in 45/0 geometry (non-polarized), using CIE 2° observer and D50 as illuminant according to EN ISO 11664-4 “Colorimetry — Part 4: CIE 1976 L*a*b* Colour space.” and other known references. Color measurements can be done using commercial instruments such as Techkon SpectroDens. In CIE 1976 L*a*b color space, a color is expressed as three numerical color values: L* for the lightness (or brightness) of the color, a* for the green-red component of the color, and b* for the blue-yellow component of the color values.

For the purpose of this invention, visible spectral region refers to a spectral region for electromagnetic radiation having a wavelength from 400 nm to 700 nm.

Unless otherwise indicated, the term “weight %” refers to the amount of a component or material based on the total solids of a composition, formulation, or layer. Unless otherwise indicated, the percentages can be the same for either a dry layer or the total solids of the formulation or composition.

As used herein, the terms “on-press developable” and “on-press developability” refer to the capability of developing a precursor according to the present invention after infrared radiation exposing (imaging), by mounting the imaged precursor on a suitable printing press, and carrying out development during the first few printed impressions using a fountain solution, a lithographic printing ink, or a combination of a fountain solution and a lithographic printing ink.

Uses

The lithographic printing plate precursors according to the present invention are useful for providing lithographic printing plates that exhibit desirable printout images after imagewise exposure. These lithographic printing plates are useful for lithographic printing during press operations. Lithographic printing plates can be prepared using on-press or off-press processing according to this invention. The lithographic printing plate precursors are prepared with the structure and components described as follows.

Lithographic Printing Plate Precursors

The precursors according to the present invention can be formed by suitable application of an infrared radiation-sensitive image-recording composition (as described below) to a suitable substrate (as described below) to form an infrared radiation-sensitive image recording layer that is negative- working. In general, the infrared radiation-sensitive image-recording composition (and resulting infrared radiation-sensitive image-recording layer) comprises: component (1) a free radical initiator composition that is capable of generating free radicals upon exposure to infrared radiation, and which also comprises an electron-donating agent; component (2) a free radically polymerizable composition; and component (3) a color-changing compound that is represented by the Structure (I) described below. All of these components (1), (2), and (3) are defined in detail below, and these components are the only essential components necessary to achieve the advantages of the present invention.

In some embodiments, the infrared radiation-sensitive image- recording composition (and resulting infrared radiation-sensitive image-recording layer) can further comprise a component (4) infrared absorbing material (or a mixture of two or more thereol) that is different from the (3) color-changing compound; and component (5) acid-sensitive dye precursor (or mixture of two or more thereol) that is different from all of the components (1), (2), (3), and (4); and a component (6) non-free radically polymerizable polymeric material (or mixture of two or more thereol) that is different from all of the components (1), (2), (3), and (4); or all of these components (4) through (6), all of which are described below. In some highly useful embodiments, the infrared radiation-sensitive image recording layer consists essentially of all of the noted components (1) through (6) to provide a desired lithographic printing plate precursor with desirable printout image and the best overall imaging and printing properties.

There is generally only one infrared radiation-sensitive image- recording layer in each precursor. This layer is generally the outermost layer in the precursor, but in some embodiments, there can be an outermost water-soluble hydrophilic protective layer (also known as a topcoat or oxygen barrier layer), as described below, disposed over (or directly on and in contact with) the infrared radiation-sensitive image-recording layer.

Substrate:

The substrate that is used to prepare the precursors according to this invention generally has a hydrophilic imaging-side surface, or at least a surface that is more hydrophilic than the applied infrared radiation-sensitive image-recoding layer. The substrate generally comprises an aluminum-containing support that can be composed of raw aluminum or a suitable aluminum alloy that is conventionally used to prepare lithographic printing plate precursors.

The aluminum-containing substrate can be treated using techniques known in the art, including roughening of some type by physical (mechanical) graining, electrochemical graining, or chemical graining, which is followed by one or more anodizing treatments. Each anodizing treatment is typically carried out using either phosphoric or sulfuric acid and conventional conditions to form a desired hydrophilic aluminum oxide (or anodic oxide) layer on the aluminum- containing support. A single aluminum oxide (anodic oxide) layer can be present or multiple aluminum oxide layers (for example an inner aluminum oxide layer and an outer aluminum oxide layer disposed on the inner aluminum oxide layer), each having multiple pores with varying depths and shapes of pore openings, can be present. Such processes thus provide an anodic oxide layer(s) or aluminum oxide layer(s) underneath an infrared radiation-sensitive image-recording layer. Teaching about providing two sequential anodizing treatments to provide different aluminum oxide layers (such as an outer aluminum oxide layer disposed on an inner aluminum oxide layer) in a substrate are described for example, in U.S. Patent Application Publication 2018/0250925.

Sulfuric acid anodization of the aluminum support generally provides an aluminum (anodic) oxide weight (coverage) on the surface of at least 1 g/m ² and up to and including 5 g/m ² and more typically of at least 1.5 g/m ² and up to and including 4 g/m ² . Phosphoric acid anodization generally provides an aluminum (anodic) oxide weight on the surface of from at least 0.5 g/m ² and up to and including 5 g/m ² and more typically of at least 1 g/m ² and up to and including 3 g/m ² .

An anodized aluminum-containing substrate can be treated with an alkaline or acidic pore-widening solution to provide an anodic oxide layer containing columnar pores. In some embodiments, the treated aluminum- containing substrate can comprise a hydrophilic layer disposed directly on a grained, anodized, and post-treated aluminum-containing support, and such hydrophilic layer can comprise a non-crosslinked hydrophilic polymer having carboxylic acid side chains.

Alternatively, an anodized aluminum-containing support can be further treated to seal the anodic oxide pores or to hydrophilize its surface, or both, using known post-anodic treatment processes, such as post-treatments using aqueous solutions of hydrophilic materials. Representative hydrophilic materials of this type to provide a hydrophilic layer (such as a hydrophilic polymer coating) include but are not limited to poly(vinyl phosphonic acid) (PVPA), vinyl phosphonic acid copolymers, poly [(meth)acry lie acid] or its alkali metal salts, or (meth)acrylic acid copolymers or their alkali metal salts, mixtures of phosphate and fluoride salts, or sodium silicate. Such hydrophilic coating can be disposed on the outermost aluminum oxide layer (such as an outer aluminum oxide layer if multiple aluminum oxide layers are present). The post-treatment process materials can also comprise unsaturated double bonds to enhance adhesion between the treated surface and the overlying infrared radiation exposed regions. Such unsaturated double bonds can be provided in low molecular weight materials or they can be present within side chains of polymers.

Particularly useful hydrophilic layer or coating materials for this purpose comprise: a compound having one or more ethylenically unsaturated polymerizable groups, one or more -OM groups at least one of which is connected directly to a phosphorus atom, and a molecular weight of less than 2000 g/mol, wherein M represents a hydrogen, sodium, potassium, or aluminum atom; and one or more hydrophilic polymers at least one of which hydrophilic polymers is a hydrophilic copolymer that comprises at least (a) recurring units comprising an amide unit, and (b) recurring units comprising an -OM’ group that is directly connected to a phosphorus atom, wherein M’ represents a hydrogen, sodium, potassium, or aluminum atom. This hydrophilic layer can be disposed over the outermost aluminum oxide layer at a dry coverage of at least 0.0002 g/m ² and up to and including 0.1 g/m ² .

The substrate can be formed as a continuous roll (or continuous web) of sheet material that is suitably coated with an infrared radiation-sensitive image-recording layer formulation and optionally a hydrophilic protective layer formulation, followed by slitting or cutting (or both) to size to provide individual lithographic printing plate precursors having a shape or form having four right- angled comers (thus, typically in a square or rectangular shape or form).

Infrared Radiation-sensitive Image-recording Laver:

The infrared radiation-sensitive recording layer composition (and infrared radiation-sensitive image-recording layer prepared therefrom) according to the present invention is designed to be “negative-working” as that term is known in the lithographic art. In addition, the infrared radiation-sensitive image- recording layer can be designed with a certain combination of components to provide on-press developability to the lithographic printing plate precursor after exposure, for example to enable on-press development using a fountain solution, a lithographic printing ink, or a combination of the two. The present invention utilizes component (1) a free radical initiator composition that is capable of generating free radicals upon exposure to infrared radiation. Such component (1) initiator composition can comprise one or more organohalogen compounds (for example trihaloalkyl compounds); halomethyl triazines; bis(trihalomethyl) triazines; or one or more onium salts such as iodonium salts, sulfonium salts, diazonium salts, phosphonium salts, and ammonium salts, many of which are known in the art. Representative compounds other than onium salts are described for example in [0087] to [0102] of U.S. Patent Application Publication 2005/0170282 (Inno et al., US ‘282) and U.S. Patent 6,309,792 (Hauck et al, and also in Japanese Patent Publication 2002/107916 and WO 2019/179995. The component (1) free radical initiator composition can include an iodonium cation or sulfonium cation, or both. Useful onium salts are described in [0103] to [0109] of the cited US publication ‘282. Useful onium salts comprise at least one onium cation in the molecule and a suitable anion. Examples of the onium salts include diaryliodonium salts, triphenylsulfonium, diphenyliodonium, diphenyldiazonium compounds, and derivatives thereof that are obtained by introducing one or more substituents into the benzene ring of these compounds. Suitable substituents include but are not limited to, alkyl, alkoxy, alkoxycarbonyl, acyl, acyloxy, chloro, bromo, fluoro and nitro groups. Useful onium cations for the onium salts include iodonium cations such as diaryliodonium cations, for example having two substituted or unsubstituted phenyl groups. Examples of anions in onium salts include but are not limited to, halogen anions, ClO ₄ -, PF ₆ -, BF ₄ -, SbF ₆ -, CH ₃ SO ₃ -, CF ₃ SO ₃ -, C ₆ H ₅ SO ₃ -, CH ₃ C ₆ H ₄ SO ₃ -, HOC ₆ H ₄ SO _3- , ClC ₆ H ₄ SO ₃ -, and boron anions as described in U.S. Patent 7,524,614 (Tao et al.). Representative useful iodonium salts are described in U.S. Patent 7,524,614 (noted above) in Cols. 6-7 wherein the iodonium cation can contain various listed monovalent substituents “X” and “Y,” or fused carbocyclic or heterocyclic rings with the respective phenyl groups.

Useful onium salts can be polyvalent onium salts having at least two onium ions in the molecule that are bonded through a covalent bond. Among polyvalent onium salts, those having at least two onium ions in the molecule are useful and those having a sulfonium or iodonium cation in the molecule are useful.

Furthermore, the onium salts described in paragraphs [0033] to [0038] of the specification of Japanese Patent Publication 2002-082429 [or U.S. Patent Application Publication 2002-0051934 (Ippei et al.)], or the iodonium borate complexes described in U.S. Patent 7,524,614 (noted above), in Cols. 6 and 7 can also be used. Representative iodonium borate salts are listed in Col. 8 of U.S. Patent 7,524,614 (noted above).

In some embodiments, a combination of onium salts can be used as part of the component (1) free radical initiator composition, for example a combination of compounds described as Compounds A and Compounds B in U.S. Patent Application Publication 2017/0217149 (Hayashi et al.).

The component (1) free radical initiator composition used in the practice of the present invention should include one or more electron-donating agents that not only participate in generation of free radicals for polymerization of the (2) free radically polymerizable compounds described below, but also facilitate the color changing reaction of the (3) color-changing compound described below. For example, electron donating compounds that are particularly useful include borate compounds and other organic compounds that have an oxidation potential (Vox) of less than 1.1 vs. an Ag/AgCl electrode.

Representative compounds that can act as electron-donating agents in the practice of this invention include compounds having a partial structure in which a nitrogen atom, an oxygen atom, or a sulfur atom is directly bonded to an aromatic or heteroaromatic group. Some potentially useful electron-donating compounds are described in [0013] to [0015] of Japanese Patent Application Publication 2005-062482A, including A-l through A-25 in [0017] to [0020], A skilled worker using the teaching provided herein would be able to utilize routine experimentation to determine which compounds would be acceptable electron- donating compounds according to the present invention.

Useful compounds that can be used as electron-donating agents include organic borate salts that are organic borate salts represented by the following Structure (III). wherein R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are independently substituted or unsubstituted alkyl groups, for example having 1 to 12 carbon atoms that can be substituted with one or more fluoro, chloro and bromo groups; or substituted or unsubstituted aryl groups having 6 to 10 carbon atoms in the aromatic rings and which can be substituted with one or more fluoro, chloro, bromo, alkyl, alkoxy, alkoxy carbonyl, and acyloxygroups, with the substituted or unsubstituted 6-membered aromatic (phenyl) groups being most useful. In most embodiments, at least three of R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are the same or different substituted or unsubstituted aryl groups as defined above, and in the best embodiments, all of R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are the same substituted or unsubstituted phenyl groups, and for example, with all of these groups being the same substituted phenyl group.

In Structure (III), n is an integer equal to or greater than 1 ; and M ⁿ⁺ is an n-valent cation, such as but not limited to, monovalent alkali metal cations, ammonium cations, monomeric and polymeric onium cations, such as iodonium, sulfonium or diazonium cations, or any other inorganic or organic molecule with cationic charge including cyanine dyes with cationic charge. In some embodiments, M ⁿ⁺ can represent one or more molecules of an iodonium anion such one or more molecules or a diaryliodonium anion, as described above.

The one or more electron-donating agents useful in the present invention can be present in the infrared radiation-sensitive image-recording layer in an amount of at least 0.5 weight % or at least 1 weight % and up to and including 10 weight %, or up to and including 20 weight %, based on the total coverage (solids) of the infrared radiation-sensitive image-recording layer.

The component (1) free radical initiator composition can be present in the infrared radiation-sensitive image-recording layer in amounts (molar or weight ratios) that would be readily apparent to a skilled worker in the art of preparing on-press developable lithographic printing plate precursors, and the minimum and maximum total amounts are generally at least 1 weight % and up to and including 20 weight % of all components including the electron-donating agent, based on the total coverage (solids) of the infrared radiation-sensitive image-recording layer.

Since the component (1) free radical initiator composition can have multiple components it would be readily apparent to one skilled in the art as to the useful amount(s) or dry coverage of the various components of the component (1) free radical initiator composition in the infrared radiation-sensitive image- recording layer, based on the knowledge of a skilled artisan and the representative teaching provided herein including the working examples shown below. Useful component (1) free radical initiator composition materials can be readily obtained and mixed in appropriate molar or weight ratios for use in the present invention.

Another essential feature of the infrared radiation-sensitive image- recording layer is a component (2) free radically polymerizable composition that comprises one or more free radically polymerizable components, each of which contains one or more free radically polymerizable groups that can be polymerized using free radical initiation during infrared radiation exposure. In some embodiments, at least two free radically polymerizable components, having the same or different numbers of free radically polymerizable groups in each molecule, are present. Thus, useful free radically polymerizable components can contain one or more free radical polymerizable monomers or oligomers having one or more polymerizable ethylenically unsaturated groups (for example, two or more of such groups). Similarly, crosslinkable polymers having such free radically polymerizable groups can also be used. Oligomers or prepolymers, such as urethane acrylates and methacrylates, epoxide acrylates and methacrylates, polyester acrylates and methacrylates, poly ether acrylates and methacrylates, and unsaturated polyester resins can be used. Some free radically polymerizable components comprise carboxyl groups.

It is possible for one or more free radically polymerizable components to have large enough molecular weight or to have sufficient polymerizable groups to provide a crosslinkable polymer matrix that functions as a “polymeric binder” for other components in the infrared radiation-sensitive image-recording layer. In such embodiments, a distinct (6) non-free radically polymerizable polymer material (described below) can be replaced.

Useful free radically polymerizable components include urea urethane (meth)acrylates or urethane (meth)acrylates having multiple (two or more) polymerizable groups. Urethane acrylates having two up to fifteen acrylate groups can be prepared by reacting a triisocyanate such as DESMODUR ^® N100 (Bayer Corp., Milford, Conn.) or a diisocyanate such as hexane- 1,6-diisocyanate with hydroxyethyl acrylate, pentaerythritol triacrylate or dipentaerythritol pentaacrylate. Such urethane or urea (meth)acrylate compounds have the number of (meth)acrylate groups per molecule as high as fifteen or more. Commercially available urethane acrylates having fifteen acrylate groups include U-15HA and UA-53H available from Shin-Nakamura Chemical Co. Ltd.

Useful free radically polymerizable compounds include non- urethane and non-urea (meth)acrylates derived from polyfunctional alcohols such as NK Ester A-DPH (dipentaerythritol hexaacrylate) that is available from Kowa American, and Sartomer SR399 (dipentaerythritol pentaacrylate), Sartomer 355 (di-trimethylolpropane tetraacrylate), Sartomer SR295 (pentaerythritol tetraacrylate), Sartomer SR415 [ethoxylated (20)trimethylol propane triacrylate], Sartomer SR494 (ethoxylated pentaerythritol tetraacrylate) that are available from Sartomer Company, Inc. These non-urethane and non-urea (meth)acrylates can also have a large number of (meth)acrylate groups per molecule.

Numerous other free radically polymerizable components are known in the art. For example, useful free radically polymerizable components are also described in EP 1,182,033A1 (Fujimaki et al), beginning with paragraph [0170] and in U.S Patents 6,309,792 (Hauck et al.), 6,569,603 (Furukawa), and 6,893,797 (Munnelly et al). Other useful free radically polymerizable components include those described in U.S. Patent Application Publication 2009/0142695 (Baumann et al.).

The one or more components of the component (2) free radically polymerizable composition can be generally present in a total amount of at least 10 weight % or of at least 20 weight % and up to and including 50 weight %, or up to and including 70 weight %, all based on the total coverage (solids) of the infrared radiation-sensitive image-recording layer.

A third essential component of the infrared radiation-sensitive image-recording composition and image-recording layer is a component (3) color- changing compound, or a mixture of two or more thereof, each of which is represented by the following Structure (I):

Structure (I) wherein Art and Ar2 independently represent the atoms necessary to complete substituted or unsubstituted aromatic rings or to complete substituted or unsubstituted heteroaromatic rings. An appropriate number of carbon atoms is required to complete a substituted or unsubstituted aromatic ring for one or both of Arl and Ar2, such as for the completion of benzene (benzo) or naphthalene (naphtho) rings. Moreover, an appropriate number of carbon and one or more heteroatoms are required to complete a substituted or unsubstituted heteroaromatic ring for one or both of Arl and Ar2, such as for completion of pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazinyl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin- 5-yl, or pyrimidin-6-yl, pyrazine, triazine, pyrrol, furan, thiophene, pyrazole, oxazole, imidazole, thiazole, or triazole rings. In many useful embodiments of this invention, Arl and Ar2 are the same atoms necessary to complete substituted or unsubstituted aromatic rings, such as substituted or unsubstituted benzene (benzo) rings. Moreover, one or both of the aromatic rings of Arl and Ar2 can be substituted, for example, with one or more optionally substituted alkyl groups, alkoxy groups, halo groups, cyano groups, -COOR’ group, -SO3R’ group, or -SO2R’ group, wherein R’ represents a substituted or unsubstituted alkyl group, that can be the same or different for each of the noted groups. It is particularly useful when one or both of Arl and Ar2 are substituted with one or two of the same or different halo groups, such as fluoro atoms.

Further, in Structure (I), 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. In many useful embodiments of the present invention, each representation of Y is the same or different dialkylmethylene group, or even the same dialkylmethylene group wherein R ⁴ and R ⁵ are the same unsubstituted alkyl group having 1 or 2 carbon atoms. A skilled chemist would be able to make numerous compounds wherein Y is varied among the possible groups, including the many possible dialkylmethylene groups.

Also in Structure (I), R is hydrogen, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. In particular embodiments, R is hydrogen or an unsubstituted alkyl group having 1 or 8 carbon atoms.

In Structure (I), R'and R ² are independently substituted or unsubstituted alkyl groups, each of which has from 1 to 12 carbon atoms, and in many embodiments, one or both of such alkyl groups comprise ether or ester linkages that interrupt the carbon chain or also in the case of ester groups, terminate the alkyl chain.

R ³ is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 or 10 carbon atoms in the aromatic ring having 6 or 10 carbon atoms in the carbocyclic ring, or a substituted or unsubstituted heteroaryl group having 5 to 10 carbon and heteroatoms in the aromatic ring. For example, R ³ can be a haloalkyl group having 1 to 12 carbon atoms, wherein one or more of the hydrogen atoms are replaced with halogen atoms such as fluoro or chloro atoms.

A ¹ and A ² independently represent substituted or unsubstituted alkyl groups, or together they represent the two or three carbon atoms necessary to form a substituted or unsubstituted 5- or 6-membered non-aromatic carbocyclic ring, such as a cyclohexylene moiety or a cyclopentylene moiety.

Lastly, in Structure (I), Za represents one or more counter ions to balance the electric charge in the rest of the color-changing compound according to Structure (I). When the rest of the color-changing compound according to Structure (I) is positively charged, Za represent an anion. Many useful anions are known such as halogen anions, , and boron-containing anions as described for example in U.S. Patent 7,524,614 (noted above). Useful boron- containing anions include tetraaryl borate anions (such as tetraphenyl borate) as described above for the electron-donating agent. In some embodiments, Za can be supplied by the electron-donating agent in the (1) free radical initiator composition. When the rest of the color-changing compound according to Structure (I) is negatively charged, Za represents a cation. Useful cations are known in the art, for example, alkali metal ions, alkali earth metal ions, tertiary and quaternary ammonium ions, and onium ions such as an iodonium ion, sulphonium ion, or phosphonium ion. Za can be also supplied by the onium compounds in component (1) free radical initiator composition described above.

The component (3) color-changing compound, singly or mixture of two or more thereof, can be generally present in the infrared radiation-sensitive image-recording layer in an amount of at least 0.5 weight %, or at least 1 weight % and up to and including 10 weight % or up to and including 15 weight %, based on the total weight of that infrared radiation-sensitive image-recording layer.

While not essential, the infrared radiation-sensitive image- recording layer can also include a component (4) infrared absorbing material (one or a mixture of two or more thereol) that is different from the component (3) color-changing compounds described above. The (4) infrared radiation absorber provides desired infrared radiation sensitivity or converts radiation to heat, or both. Useful infrared radiation absorbers can be pigments or infrared radiation absorbing dyes. Suitable dyes are those described in U.S. Patents 5,208,135 (Patel et al.), 6,153,356 (Urano et al.), 6,309,792 (Hauck et al.), 6,569,603 (Furukawa), 6,797,449 (Nakamura et al.), 7,018,775 (Tao), 7,368,215 (Munnelly et al.), 8,632,941 (Balbinot et al.), and U.S. Patent Application Publication 2007/056457 (Iwai et al.). At least one (4) infrared radiation absorber in the infrared radiation- sensitive image-recording layer can be a cyanine dye comprising a suitable cationic cyanine chromophore and a tetraarylborate anion such as a tetraphenylborate anion as described in United States Patent Application Publication 2011/003123 (Simpson et al.).

The total amount of the component (4) infrared radiation absorber can be at least 0.5 weight % or at least 1 weight % and up to and including 15 weight %, or up to and including 30 weight %, based on the total weight of the infrared radiation-sensitive image-recording layer.

Another optional component of the infrared radiation-sensitive image-recording layer is a component (5) acid-sensitive dye precursor (singly or a combination of two or more thereol). Useful component (5) acid-sensitive dye precursors are compounds that are colorless or nearly colorless in the neutral form and that switch to a colored form when protonated. Many leuco dyes are known for this purpose including those described in [0209] to [0222] of EP 3,418,332A2 (Inasaki et al., corresponding to U.S. Patent Application Publication 2018/0356730) and in [0044] to [0046] of EP 2,018,365B1 (Nguyen et al., corresponding to U.S. Patent 7,910,768). These component (5) acid-sensitive dye precursors are different from all of the components (1), (2), (3), and (4) defined above.

In some embodiments, at least one of the component (5) acid- sensitive dye precursors comprises a lactone substructure. Useful component (5) acid-sensitive dye precursors can be represented by one or more of the following Structure (Cl) and Structure (C2):

wherein R ¹¹ through R ¹⁹ are independently hydrogen, unsubstituted or substituted alkyl groups, or unsubstituted or substituted aryl groups. Such substituted or unsubstituted alkyl groups can have 1 to 20 carbon atoms, and one or more substituents can include but are not limited to halogen, alkyl, aryl, alkoxy, and phenoxy groups. Useful substituted or unsubstituted aryl groups can be carbocyclic aromatic rings or heterocyclic aromatic rings, and such groups can have two or more fused rings. Useful substituents for the aryl rings can include those described above for the alkyl groups. However, skilled chemists could design other useful component (5) acid-sensitive dye precursors using this teaching about Structures (Cl) and (C2) as guidance.

As noted above, such component (5) acid-sensitive dye precursors can be present in an amount of at least 0.5 weight % and up to and including 10 weight %, based on the total coverage (solids) of the infrared radiation-sensitive image-recording layer.

It is also optional that the infrared radiation-sensitive image- recording layer further comprises a component (6) non-free radically polymerizable polymeric material (or polymeric binder), or a mixture of two or more, each of which does not have any functional groups that, if present, would make the polymeric material capable of free radical polymerization. Thus, such component (6) non-free radically polymerizable polymeric material is different from all of components (1), (2), (3), and (4) described above.

A useful component (6) non-free radically polymerizable polymeric material generally can have a weight average molecular weight ) of at least 2,000, or at least 20,000, and up to and including 300,000 or up to and including 500,000, as determined by Gel Permeation Chromatography (polystyrene standard).

Such component (6) non-free radically polymerizable polymeric material can be selected from polymeric binder materials including polymers comprising recurring units having side chains comprising polyalkylene oxide segments such as described in U.S. Patent 6,899,994 (Huang et al.). Other useful polymeric binders comprise two or more types of recurring units having different side chains comprising polyalkylene oxide segments as described in WO Publication 2015-156065 (Kamiya et al.). Some of such polymeric binders can further comprise recurring units having pendant cyano groups as described in U.S. Patent 7,261,998 (Hayashi et al.).

Such component (6) polymeric non-free radically polymerizable material also can have a backbone comprising multiple (at least two) urethane moieties as well as pendant groups comprising the polyalkylene oxide segments.

Some useful component (6) non-free radically polymerizable polymeric materials can be present in particulate form, that is, in the form of discrete particles (non-agglomerated particles). Such discrete particles can have an average particle size of at least 10 nm and up to and including 1500 nm and are generally distributed uniformly within the infrared radiation-sensitive image- recording layer. Average particle size can be determined using various known methods and nanoparticle measuring equipment, including measuring the particles in electron scanning microscope images and averaging a set number of measurements.

The component (6) non-free radically polymerizable polymeric material(s) can be present in an amount of at least 10 weight %, or at least 20 weight % and up to and including 50 weight %, or up to and including 70 weight %, based on the total coverage (solids) of the infrared radiation-sensitive image- recording layer.

The infrared radiation-sensitive image-recording layer can also optionally include crosslinked polymer particles having an average particle size of at least 2 pm or of at least 4 pm, and up to and including 20 pm as described in U.S. Patents 9,366,962 (Hayakawa et al), 8,383,319 (Huang et al), and 8,105,751 (Endo et al). Such crosslinked polymeric particles can be present in only one or both of the infrared radiation-sensitive image-recording layer and the hydrophilic protective layer when present (described below).

The infrared radiation-sensitive image-recording layer can also include a variety of other optional addenda such as dispersing agents, humectants, biocides, plasticizers, surfactants for coatability or other properties, viscosity builders, pH adjusters, drying agents, defoamers, development aids, rheology modifiers, or any other addenda commonly used in the lithographic coating art, in conventional amounts. The infrared radiation-sensitive image-recording layer can also include a phosphate (meth)acrylate having a molecular weight generally greater than 250 as described in U.S. Patent 7,429,445 (Munnelly et al).

The useful dry coverage (typically total solids with minimal water and organic solvents) of the infrared radiation-sensitive image-recording layer is described below.

Hydrophilic Protective Laver:

In some embodiments of the present invention, the infrared radiation-sensitive image-recording layer is the outermost layer with no layers disposed thereon. It is possible that the precursors can be designed with a hydrophilic protective layer (also known as a hydrophilic overcoat, oxygen-barrier layer, or topcoat) disposed directly on a single infrared radiation-sensitive image- recording layer (no intermediate layers between these two layers).

Such hydrophilic protective layers can comprise one or more film- forming water-soluble polymeric binders in an amount of at least 60 weight % and up to and including 100 weight %, based on the total dry weight of the hydrophilic protective layer. Such film-forming water-soluble (or hydrophilic) polymeric binders can include a modified or unmodified poly(vinyl alcohol) having a saponification degree of at least 30% or a degree of at least 90%, or a degree of up to and including 99.9%.

One or more acid-modified poly(vinyl alcohol)s can be used as film-forming water-soluble (or hydrophilic) polymeric binders. For example, at least one poly(vinyl alcohol) can be modified with an acid or ester group such as a carboxylic acid, sulfonic acid, sulfuric acid ester, phosphonic acid, or phosphoric acid ester group. Useful modified poly(vinyl alcohol) materials include sulfonic acid-modified poly(vinyl alcohol), carboxylic acid-modified poly(vinyl alcohol), and quaternary ammonium salt-modified poly(vinyl alcohol), glycol-modified poly(vinyl alcohol), or combinations thereof.

When present, the hydrophilic protective layer is provided as a hydrophilic protective layer formulation and dried to have a dry coverage of at least 0.1 g/m ² and up to but less than 4 g/m ² . In some embodiments, the dry coating coverage is as low as 0.1 g/m ² and up to and including 1.5 g/m ² or at least 0.1 g/m ² and up to and including 0.9 g/m ² .

The hydrophilic protective layer can optionally comprise organic wax particles dispersed generally uniformly within the one or more film-forming water-soluble (or hydrophilic) polymeric binders as described in U.S. Patent Application Publication 2013/0323643 (Balbinot et al.).

Preparing Lithographic Printing Plate Precursors:

The lithographic printing plate precursors according to the present invention can be provided as follows. An infrared radiation-sensitive image- recording layer formulation comprising essential components (1), (2), and (3), and optional components (4), (5), (6) and other optional addenda, can be applied to a hydrophilic surface of a suitable aluminum-containing substrate, usually in the form of a continuous web, using any suitable equipment and procedure, such as spin coating, knife coating, gravure coating, die coating, slot coating, bar coating, wire rod coating, roller coating, spray coating, or extrusion hopper coating. Once the infrared radiation-sensitive image-recording layer formulation is applied at a suitable wet coverage, it is dried in a suitable manner to provide a dry coverage, thereby providing an infrared radiation-sensitive continuous web or an infrared radiation-sensitive continuous article. The components and addenda of the infrared radiation-sensitive image-recording layer can be designed such that upon, imaging, this layer is readily removed on-press using either or a combination of a lithographic printing ink and a fountain solution.

Before the infrared radiation-sensitive image-recording layer formulation is applied, the substrate can be electrochemically grained and anodized to provide a suitable hydrophilic anodic (aluminum oxide) layer(s) on the outer surface of the aluminum-containing support, and the anodized surface usually can be post-treated with a hydrophilic polymer solution.

The manufacturing methods typically include mixing the various components needed for the infrared radiation-sensitive image-recording layer in a suitable organic solvent or mixtures thereof with or without water [such as methyl ethyl ketone (2-butanone), methanol, ethanol, l-methoxy-2-propanol, 2- methoxypropanol, isopropyl alcohol, acetone, g-butyrolactone, «-propanol, tetrahydrofuran, as well as mixtures thereof], applying the resulting infrared radiation-sensitive image-recording layer formulation to a continuous substrate web, and removing the solvent(s) by evaporation under suitable drying conditions.

After proper drying, the dry coverage of the infrared radiation- sensitive image-recording layer on the substrate can be at least 0.1 g/m ² , or at least 0.4 g/m ² and up to and including 2 g/m ² or up to and including 4 g/m ² but other dry coverage amounts can be used if desired.

In some embodiments, a suitable aqueous-based hydrophilic protective layer formulation (described above) can be applied to the dried infrared radiation-sensitive image-recording layer using known coating and drying conditions, equipment, and procedures.

Imaging (Exposing) Conditions

During use, an infrared radiation-sensitive lithographic printing plate precursor of this invention can be exposed to a source of infrared radiation depending upon the infrared radiation absorber(s) present in the infrared radiation- sensitive image-recording layer. The lithographic printing plate precursors can be imaged with one or more infrared radiation-emitting lasers that emit significant infrared radiation within the range of at least 750 nm and up to and including 1400 nm, or of at least 800 nm and up to and including 1250 nm to create exposed regions and non-exposed regions in the infrared radiation-sensitive image- recording layer. Imaging can be carried out using imaging or exposing infrared radiation from an infrared radiation-generating laser (or array of such lasers). Imaging also can be carried out using imaging radiation at multiple infrared (or near-IR) wavelengths at the same time if desired.

It can be desirable to include a means for reducing or removing ozone in the environment of the laser imaging as described in U.S. Patent Application Publication 2019/0022995 (Igarashi et al.).

When an infrared radiation imaging source is used, imaging intensities can be at least 30 mJ/cm ² and up to and including 500 mJ/cm ² and typically at least 50 mJ/cm ² and up to and including 300 mJ/cm ² depending upon the sensitivity of the infrared radiation-sensitive image-recording layer.

Processing (Development) and Printing

After imagewise exposing as described above, the exposed infrared radiation-sensitive lithographic printing plate precursors having exposed regions and non-exposed regions in the infrared radiation-sensitive image-recording layer can be processed off-press or on-press to remove the non-exposed regions (and any hydrophilic protective layer over such regions). After this processing, and during lithographic printing, the revealed hydrophilic substrate surface repels inks while the remaining exposed regions accept lithographic printing ink.

Off-Press Development and Printing:

Processing can be carried out off-press using any suitable developer in one or more successive applications (treatments or developing steps) of the same or different processing solution (developer). Such one or more successive processing treatments can be carried out for a time sufficient to remove the non-exposed regions of the infrared radiation-sensitive image-recording layer to reveal the outermost hydrophilic surface of the substrate, but not long enough to remove significant amounts of the exposed regions that have been hardened.

Following any optional pre-heating, or in place of the pre-heating, the exposed precursor can be washed (rinsed) to remove any hydrophilic overcoat that is present.

Useful developers can be ordinary water or formulated aqueous solutions and can comprise one or more surfactants, organic solvents, alkali agents, and surface protective agents. Useful organic solvents include the reaction products of phenol with ethylene oxide and propylene oxide [such as ethylene glycol phenyl ether (phenoxy ethanol)], benzyl alcohol, esters of ethylene glycol and of propylene glycol with acids having 6 or less carbon atoms, and ethers of ethylene glycol, diethylene glycol, and of propylene glycol with alkyl groups having 6 or less carbon atoms.

In some instances, an aqueous processing solution can be used off- press to both develop the imaged precursor by removing the non-exposed regions and also to provide a protective layer or coating over the entire imaged and developed (processed) precursor printing surface. The aqueous solution behaves somewhat like a gum that is capable of protecting (or “gumming”) the lithographic image on the lithographic printing plate.

After off-press processing and optional drying, the lithographic printing plate can be mounted onto a printing press without any contact with additional solutions or liquids.

Printing can be carried out by applying a lithographic printing ink and fountain solution to the printing surface of the lithographic printing plate in a suitable manner. The lithographic ink is taken up by the remaining (exposed) regions of the infrared radiation-sensitive image-recording layer and transferred to a suitable receiving material (such as cloth, paper, metal, glass, or plastic) to provide a desired impression of the image thereon. If desired, an intermediate “blanket” roller can be used to transfer the lithographic ink from the lithographic printing plate to the receiving material (for example, sheets of paper).

On-Press Development and Printing:

Alternatively, the negative-working lithographic printing plate precursors of the present invention are on-press developable using a lithographic printing ink, a fountain solution, or a combination of a lithographic printing ink and a fountain solution. In such embodiments, an imaged (exposed) infrared radiation-sensitive lithographic printing plate precursor is mounted onto a printing press and the printing operation is begun. The non-exposed regions in the infrared radiation-sensitive image-recording layer are removed by a suitable fountain solution, lithographic printing ink, or a combination of both, when the initial printed impressions are made. Typical ingredients of aqueous fountain solutions include pH buffers, desensitizing agents, surfactants and wetting agents, humectants, low boiling solvents, biocides, antifoaming agents, and sequestering agents. A representative example of a fountain solution is Vam Litho Etch 142W + Vam PAR (alcohol sub) (available from Vam International, Addison, IL).

In a typical printing press startup with a sheet-fed printing machine, the dampening roller is engaged first and supplies fountain solution to the mounted imaged precursor to swell the exposed infrared radiation-sensitive image-recording layer at least in the non-exposed regions. After a few revolutions the inking rollers are engaged and they supply lithographic printing ink(s) to cover the entire printing surface of the lithographic printing plates. Typically, within 5 to 20 revolutions after the inking roller engagement, printing sheets are supplied to remove the non-exposed regions of the infrared radiation-sensitive image- recording layer from the lithographic printing plate as well as materials on a blanket cylinder if present, using the formed ink-fountain solution emulsion.

The present invention provides at least the following embodiments and combinations thereof:

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;

(2) a free radically polymerizable composition; and

(3) a color-changing compound that is represented by the following Structure (I) wherein:

Arl and Ar2 independently represent the atoms necessary to complete substituted or unsubstituted aromatic rings or to complete substituted or unsubstituted heteroaromatic rings;

R is hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl groups; R'and R ² are independently substituted or unsubstituted alkyl groups;

R ³ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group;

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; A ¹ and A ² independently represent substituted or unsubstituted alkyl groups, or together they represent the two or three carbon atoms necessary to form a substituted or unsubstituted 5-or 6-membered non-aromatic carbocycbc ring; 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).

2. The lithographic printing plate precursor of embodiment 1, wherein R ³ is a trifluoromethyl group.

3. The lithographic printing plate precursor of embodiment 1 or 2, wherein Arl and Ar2 are the same number of carbon atoms necessary to complete substituted or unsubstituted aromatic rings.

4. The lithographic printing plate precursor of any of embodiments 1 to 3, wherein one or both of the aromatic rings completed by the atoms of Arl and Ar2 are substituted with one or two halo groups that can be the same or different.

5. The lithographic printing plate precursor of any of embodiments 1 to 4, wherein A ¹ and A ² together represent the two carbon atoms needed to complete an unsubstituted 5-membered non-aromatic carbocycbc ring.

6. The lithographic printing plate precursor of any of embodiments 1 to 5, wherein Za comprises a tetraaryl borate anion.

7. The lithographic printing plate precursor of any of embodiments 1 to 6, wherein the electron donating agent is an organic borate salt represented by the following Structure (II). wherein R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are independently substituted or unsubstituted alkyl groups or substituted or unsubstituted aryl groups, and at least three of R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are the same or different substituted or unsubstituted aryl groups, n is an integer equal to or larger than 1, and M ⁿ⁺ is an n-valent cation. 8. The lithographic printing plate precursor of embodiment 7, wherein all of R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are the same or different substituted or unsubstituted aryl groups.

9. The lithographic printing plate precursor of embodiment 7 or 8, wherein all of R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are the same substituted or unsubstituted phenyl groups.

10. The lithographic printing plate precursor of any of embodiments 1 to 9, wherein R ¹ and R ² independently comprises a chain of carbon atoms interrupted by one or more ether or ester linkages.

11. The lithographic printing plate precursor of any of embodiments 1 to 10, wherein the infrared radiation-sensitive image-recording layer further comprises a component (4) infrared absorbing material that is different from the (3) color-changing compound.

12. The lithographic printing plate precursor of any of embodiments 1 to 11, wherein the (1) free radical initiator composition comprises an onium salt.

13. The lithographic printing plate precursor of any of embodiments 1 to 12, wherein the (1) free radical initiator composition comprises an iodonium cation.

14. The lithographic printing plate precursor of embodiment 12 or 13, wherein the iodonium cation is a diaryliodonium cation.

15. The lithographic printing plate precursor of any of embodiments 1 to 14, wherein the infrared radiation-sensitive image-recording layer further comprises a component (5) acid-sensitive dye precursor that is different from all of the (1), (2), (3), and (4) components defined above.

16. The lithographic printing plate precursor of any of embodiments 1 to 15, 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 (1), (2), (3), and (4) components defined above. 17. The lithographic printing plate precursor of embodiment 16, wherein the (6) non-free radically polymerizable polymeric material is present in particulate form.

18. The lithographic printing plate precursor of any of embodiments 1 to 17, wherein, after infrared radiation exposure, the infrared radiation sensitive image-recording layer is developable on-press using a lithographic ink, a fountain solution, or a combination of a lithographic ink and a fountain solution.

19. The lithographic printing plate precursor of any of embodiments 1 to 18, wherein the (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.

20. The lithographic printing plate precursor of any of embodiments 1 to 19, wherein the infrared radiation-sensitive image-recording layer is the outermost layer.

21. The lithographic printing plate precursor of any of embodiments 1 to 20, wherein the (2) free radically polymerizable composition comprises least two free radically polymerizable components.

22. The lithographic printing plate precursor of any of embodiments 1 to 21, wherein the substrate comprises an aluminum-containing substrate comprising at least one aluminum oxide layer, and a hydrophilic polymer coating that is disposed on the least one aluminum oxide layer.

23. The lithographic printing plate precursor of any of embodiments 1 to 22, wherein the substrate comprises an aluminum-containing substrate comprising at least an inner aluminum oxide layer, an outer aluminum oxide layer disposed on the inner aluminum oxide layer, and a hydrophilic polymer coating that is disposed on the outer aluminum oxide layer.

24. A method for providing a lithographic printing plate, comprising:

A) imagewise exposing the lithographic printing plate precursor according to any of embodiments 1 to 23 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.

25. The method of embodiment 24, comprising 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.

26. The method of embodiment 24 or 25, wherein the imagewise exposing is carried out using one or more infrared radiation-emitting lasers.

The following examples are provided to further illustrate the practice of the present invention and are not meant to be limiting in any manner.

An aluminum-containing substrate was prepared for the lithographic printing plate precursors in the following manner:

Hydro 1052 aluminum alloy strip or web (available from Norsk Hydro ASA, Norway) having a thickness of 0.28 mm was used as the aluminum- containing “plate” stock or support. Both pre-etch and post-etch steps were carried out in alkaline solutions under known conditions. Roughening (or graining) of the etched aluminum support was carried out by electrochemical means in a hydrochloric acid solution at 23°C to obtain an arithmetic average roughness (Ra) of 0.5 pm on a surface of the aluminum-containing support. Thereafter, the aluminum-containing supports were subjected to two individual anodizing treatments. The first anodizing process was carried out using phosphoric acid as the electrolyte to form an outer aluminum oxide layer with an average micropore diameter (D ₀ ) of 19 nm and an average dry thickness (To) of 60 nm. The second anodizing process was then carried out using phosphoric acid as the electrolyte to form an inner aluminum oxide layer with an average micropore diameter (Di) of 70 nm and an average dry thickness (Ti) of 500 nm. These two anodizing steps were carried out in a continuous process on a typical manufacturing line used to manufacture lithographic printing plate precursors. The aluminum-containing support thus prepared was coated with an aqueous solution of polyacrylic acid to give a dry thickness of 0.03 g/m ² for a substrate useful in the present invention.

A negative-working, infrared radiation-sensitive image-recording layer was then formed on the aluminum-containing substrate as described by individually coating infrared radiation-sensitive composition formulations having the components and amounts shown in the following TABLES I, II, and III using a bar coater, to provide a dry coating weight of 0.9 g/m ² after drying at 50°C for 60 seconds for each of the inventive and comparative precursors described below. The raw materials noted in TABLE I are identified in the following TABLE II, and the amounts of various components are shown in TABLE III. These materials can be obtained from one or more commercial sources of chemicals or prepared using known synthetic methods and starting materials. TABLE I

Each of the inventive and comparative lithographic printing plate precursors was evaluated using four tests: “on-press developability” (DOP), “imaging speed”, “print-out image” (PO), and “dark fading”. The results are summarized below in TABLE IV.

On-press Developability:

On-press developability was evaluated by imagewise exposing each lithographic printing plate precursor at 15-150 mJ/cm ² using a Trendsetter 3244x. Each imagewise exposed lithographic printing plate precursor was then mounted onto a MAN Roland Favorite 04 press machine without developing (processing). Fountain solution (Vam Supreme 6038) and lithographic printing ink (Gans Cyan) were supplied, and lithographic printing was performed. On- press development occurred during printing and was evaluated by counting the number of printed paper sheets needed to receive a clean background and was given one of the following qualitative values based on the number of printed paper sheets to achieve a clean background. The + and 0 evaluations are acceptable for this test parameter.

+ < 5 printing paper sheets

0 15-35 printed paper sheets

> 35 printed paper sheets

Imaging Speed:

Each of the lithographic printing plate precursors was exposed and developed as described above. Imaging speed was measured on paper after 1000 impressions by a determination of ink density for solids exposed to different energies. The inflection point of ink density vs. exposure energy is regarded as a measure for imaging speed. The following qualitative values were given as the results of the individual experiments, with lower imaging energy desirable. The + and 0 evaluations are acceptable for this parameter.

+ imaging speed < 30 mJ/cm ²

0 imaging speed = 30 - 60 mJ/cm ² imaging speed > 60 mJ/cm ² Printout Image:

Each of the lithographic printing plate precursors was imagewise exposed using a Trendsetter 800 III Quantum TH 1.7 (available from Eastman Kodak Company) at 90 mJ/cm ² to provide exposed regions and non-exposed regions in the negative-working, IR-sensitive image-recording layer. For each imagewise exposed lithographic printing plate precursor, the color difference between exposed regions and non-exposed regions was measured, within 10 minutes from the completion of the imagewise exposing, by determining the cyan ΔOD value, using a Techkon Spectro Dens spectral densitometer. The cyan ΔOD represents the difference in reflective optical density observed through a cyan filter between the exposed and non-exposed regions. The visual images on a lithographic printing plate precursor with a high cyan ΔOD absolute value are expected to be more readable by cameras and other reading devices that are built with a diode light source emitting around 617 nm light. The measured values were scored as follows.

+ 0.10 < cyan ΔOD

0 0.05 < cyan ΔOD < 0.10 cyan ΔOD < 0.05

Dark Fading:

Each lithographic printing plate was imagewise exposed as described above, and then stored in the dark for 24 hours. The cyan ΔOD measurements were then taken as described above, and given the following qualitative scores.

+ 0.10 < cyan ΔOD

0 0.05 < cyan ΔOD < 0.10 cyan ΔOD < 0.05

The results shown in TABLE IV show that the inventive infrared radiation-sensitive imaging composition containing the inventive (3) color- changing compound provided acceptable results in all four tests, and particularly improved the printout image after the dark fading test.