TW201211082A - Copolymers for near-infrared radiation-sensitive coating compositions for positive-working thermal lithographic printing plates - Google Patents

Abstract

There is provided a copolymer having the general structure below, wherein a, b, and d are molar ratios varying between about 0.01 and about 0.90 and c is a molar ratio varying between about 0, 01 and about 0.90; A1 represents monomer units comprising a cyano-containing pendant group in which the cyano is not directly attached to the backbone of the copolymer; A2 represents monomer units comprising two or more hydrogen bonding sites; A3 represents monomer units that increase solubility in organic solvents; and A4 represents monomer units that increase solubility in aqueous alkaline solutions. There is also provided a near-infrared radiation-sensitive coating composition comprising this copolymer as well as a positive-working thermal lithographic printing plate comprising a near-infrared radiation-sensitive coating comprising this copolymer, a method of producing such a printing plate, and finally a method of printing using such a printing plate.

Description

201211082 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a thermal printing plate and a coating thereof. The invention is particularly relevant to copolymers for near-infrared radiation-sensitive coating compositions for positive and thermal printing plates. [Prior Art] In lithography, a printing plate is mounted on the drum of a printing press. The surface of the printing plate is provided with a lithographic image, the ink is applied to the image, and the ink is transferred from the printing plate to a receiving device material (usually a piece of paper) to obtain a printed copy. Typically, S, the ink is first transferred to an intermediate cover layer, which then transfers the ink to the surface of the receiving device material (offset). Traditionally known as "wet" lithography, inks and aqueous immersion liquids. (also known as dampening fluid) is provided to the lithographic image comprising the lipophilic zone (or hydrophobic zone (ie, absorbing ink or repelling moisture)) and the hydrophilic zone (or oleophobic zone (ie, absorbing moisture or repelling ink)). When the surface of the printing plate is coated with water and the ink, the hydrophilic regions retain moisture and repel the ink, and the ink containing regions receive the ink and repel the moisture. When printing, the ink is transferred to the receiving The surface of the material is such that the image is reproduced on the surface. Lithographic printing plates typically comprise an imageable layer (also known as an imaging layer or coating) which can be applied to the hydrophilic surface of a substrate, typically aluminum. The imaging layer contains more than one radiation sensitive component and is typically dispersible in a suitable adhesive. To produce the lithographic image on the printing plate, the printing plate can be imaged by directional radiation. This imaging can be performed in a variety of ways. In direct digital imaging (computer-to-print), a single print can be imaged using a variety of infrared or ultraviolet lasers, or light sources. The laser beam can be digitally controlled via a computer to activate or deactivate the laser light to cause the image exposure of the precursor to function via the digitized information stored in the computer. Therefore, when the image layers of a plurality of 4 201211082 printing plates are subjected to image exposure by image layout, the near-infrared (NIR) or ultraviolet (uv) regions ___ in the spectrum must be included. The printing plate is a printing plate that is sensitive to near-infrared radiation. The imaging device causes local variations in the imaging layer and the last name is the image on the printing plate. In fact, in these imaging system wipes, the hybrid layer usually contains a dye or secret, which absorbs the incident radiation, and is disturbed by the heterogeneous amount of the female image. Exposure to radiation will produce a physical or chemical process in the imaging layer (four) such that the imaging regions are different from the unimaged regions and the artifacts will be produced on the printing plate - the image is in the imaging layer. It may be a change of hydrophilic/lipophilic, soluble, hardened, and the like. After the exposure is completed, the exposed regions or the unexposed regions of the imaging layer can be corrected for the surface of the dragon water below the substrate using a suitable smear. The 彡 侧 side is usually tested! The raw water solution 'containing inorganic salts' includes, for example, sodium sulphate (s), sodium hydroxide, sodium hydroxide, pGtassiumhydiOxide, and various surface activities. Agent. The lithographic printing plate developed on the printing press can be directly mounted on a printing press after imaging is completed, and (iv) contact with ink and/or immersion for development during the initial printing operation. change. The exposed areas of the image layer - some unexposed parts can be removed by the ink and / or immersion liquid - without having to be more specific - a so-called on-press development system is 4 The exposed printing plate apparatus is placed on the plate cylinder of the printing machine, and when a plurality of non-image areas are removed by rotating the 5th roller, an immersion liquid and ink can be added. This technique can be mounted - a printed but undeveloped printing plate (also known as a printing plate precursor) to form a printing press and form a printing plate on a typical printing line. If the exposed areas are removed right, the precursor is a positive. In other words, if the unexposed areas are removed, the precursor is a negative. In each case, the remaining regions of the imaging layer (ie, the image regions) are acceptable for ink, and the regions of the hydrophilic surface that are exposed during the development process are acceptable for moisture and various aqueous solutions (usually An infusion), and not 201211082 will accept ink. The use of a wide variety of copolymers comprising a -cyano group (-CN) is well known in the art, wherein the base can be directly bonded to produce a single and multi-layered master key. The cyano-containing (-CN) copolymers are directly attached to the backbone of the polymer and typically provide a variety of good film forming properties, mechanical strength, and chemical resistance on the press. Acrylonitrile and methacryl nitrile are liquids having a low Buddha point (< 100 ° C). Both have recently been classified as harmful and highly toxic substances. Therefore, the two need specific transportation for transportation. In the expected processing, use, and processing conditions T, the 8-hour time weight average of the product cap shall not exceed lPPm (air navigation). This requirement is extremely difficult to achieve when acrylonitrile and methyl propylene, which are commonly used in shirts, are used in the manufacture of multiple lithographic offset plates. < SUMMARY OF THE INVENTION According to the present invention: L - a copolymer comprising the general structure: _ - _ r - - Α 1 - - A2 - - - A3 - - A4- a L · bc - _ where a , b and d 疋 vary between about 0.01 and 〇 9 的 a plurality of molar ratios between about 0 and 0.90, a molar ratio, Μ indicates that the monomer unit contains a Wei-based group , does not directly connect the main chain of the copolymer; cyanide 2 represents a multi-disassembly unit, including the listening position on both sides; A3 represents the decomposed unit, which can increase the solubility of the solvent of the township; 2 ^ 乂 and 八 4 Not much disintegration unit can increase the solubility in a variety of alkaline aqueous solutions. The copolymer of item 1, wherein the chemical formula of Α! is: 6 201211082

Wherein: R is hydrogen, methyl or ethyl.

Ri may be absent or represent one to four alkyl substituents; such alkyl substituents may optionally contain more than one ethane, ester, amine, amide , urea (urea), pyridazinyl, suif〇namide, or carbamate functional groups, the alkyl substituents may optionally be substituted by more than one cyano group; Is a guanamine or ester linker,

Vi may be absent or represent a burnt group, and may optionally contain more than one of B (10), a cool amine, an amine, a urea, a sulfinyl group, a styrene amine, or an amino phthalate functional group, which may be optionally selected. Substituted by more than one cyano group; and w is -CN or ~V-^v^cn 3. The copolymer of item 1 or 2, wherein 乂 is

S 7 201211082

Γ R a 1 plant R

Wherein R is hydrogen, methyl or ethyl, and η can vary between 1 and 10. 8 201211082

a side group of a 5,5-dialkylhydantoin group, such as a 5,5-dimethylhyd-in group, an aminosulfonamide group, or a hydroxy group base. The copolymer of any one of items 1 to 3, wherein the chemical formula of A2 is:

Wherein: R is hydrogen, sulfhydryl or ethyl.

Ri may be absent or represent one to four alkyl substituents, optionally containing more than one ether 'ester, amine, guanamine, urea, piperidinyl, sulfonamide or carbamate Functional group; U2 may be absent or represent a guanamine or ester linker; V2 may be absent or represent a burnt group, optionally containing more than one riddle, ester, amine, amine, urea, piperazinyl, sulfonamide Or a carbamate functional group; and 9 £ 201211082

Wherein r2 is present as a separate hydrogen or alkyl group, optionally containing more than one of the ether, the S, the amine, the guanamine, the exhibitin, the sulphate, the amine or the urethane functional group. 6. The copolymer of item 5, wherein Y is

Ch3 7. The copolymer of item 5, wherein A2 is:

10 201211082 R Π

〇 r

8. The copolymer of any of items i to 7 wherein e is a change between about read and minus. 9. The copolymer of item 8, wherein A3 comprises a pendant or aryl (tetra) pendant group which is in fact substituted by a fluorenyl group. 10. The copolymer of item 8, wherein A3 has the formula: Ϊ3 z wherein R is argon, methyl or ethyl, and U3 may be absent or represents a guanamine or vinegar linker:

11 S 201211082 z is an alkyl or aryl group which may be optionally substituted by more than one hydroxy group, alkyloxy group, or dentate (haUde), which may optionally be more than one Substituting a base group, an alkoxy group, or a burn group substituted with a compound. 11. The copolymer of item 9, wherein eight of three are:

Wherein R is hydrogen, methyl or ethyl. The copolymer according to any one of the preceding claims, wherein A4 comprises a pendant group comprising a cis acid group or a phosphoric acid group. The copolymer of any one of the items 1 to 11, wherein the chemical formula of A4 is:

R

Wherein R is hydrogen, methyl or ethyl, R1 may be absent, or represents one to four alkyl substituents; these alkyl substituents may optionally contain more than one ethyl, ester, amine, guanamine, urea, a pyrazinyl, a decylamine or a methacrylate functional group;

Ui may be absent or represent a guanamine or g-linker; V4 may be absent or represent a burnt group, and may optionally contain more than one ethylidene, ester, amine amide, elastin, piperazinyl, sulfonamide or amino group. Formate functional group; and 12 201211082

V _^V4—COOH or

A is -COOH, ·ΡΟ(ΟΗ)2-po(oh)2. The copolymer according to any one of items 1 to 12, wherein A4 is a monomer, a polymerizable acrylic acid, methacrylic acid, 4-carbonyl-phenyl-methyl group 4-carboxyphenylmethacrylamide, 4-carboxyphenylacrylamide, vinyl benzoic acid, vinyl phosphoric acid, mercaptoacrylic acid-alkane It is obtained by methacrylyl alkyl phosphoric acid or acrylyl alkyl phosphoric acid monomer. 15. A near-infrared light-sensitive paint composition comprising: one of the copolymers defined in any one of items 1 to 13; a binder resin; a near-infrared radiation absorbing compound; and a plurality of optional additions Things. 16. A positive thermal printing plate comprising a near infrared radiation sensitive coating which can be prepared from the coating composition of item 14. 17. A positive thermal printing plate comprising a near infrared radiation sensitive coating comprising: one of the copolymers defined in any one of items 1 to 13; a binder resin; a near infrared radiation absorbing compound ; and a number of optional additives. 18. A method of producing a positive thermal print plate comprising the steps of: 13 201211082 a) providing a piece of substrate, and b) applying the coating composition of item 14 to the substrate. 19. A printing method comprising the steps of: a) providing a positive thermal printing plate according to item 15 or item 16, b) imaging the printing plate with near infrared radiation, c) printing the printing plate Developing, and d) printing using the printing plate on a printing press. e) Printing using the printing plate on a printing press. 20. 21. 22. Monomer unit A1. A monomer of a derogatory type is equivalent to a monomer as defined in any one of items 1 to 3, which is equivalent to a unit of any one of items 1 and 4 to 7. A2. A monomer corresponding to the unit A3 of the item No. and item 9 to item 11.义义-种单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单单DETAILED DESCRIPTION OF THE INVENTION The present invention provides a copolymer comprising a plurality of monomer units VIII. The monomer units comprising a plurality of leak-containing groups, wherein the cyano group is not directly bonded to the polymer and at least one other monomer unit Main chain. The "copolymer" used in the present invention; I: a polymer composed of at least two different types of monomer units. These monomer units have relatively small molecules which are capable of linking a relatively large number of other monomer units to form a chain which forms a polymer or copolymer. The "backbone" of one of the polymers or copolymers used in the present invention means the series of covalently bonded atoms from the monomer units which together create a continuous chain of the polymer or copolymer. A "side group" means a group of atoms, and 201211082 can be attached to the backbone of the copolymer rather than to the backbone of the link. Similarly, a "cyan-containing pendant group" means a pendant group containing a cyano group (_〇ξΝ). Thus, in the above description, the cyano group is contained in one side group and is not directly bonded to the main chain of the copolymer; the cyano group instead connects the side groups, in more specific embodiments shown below, Side base

Q is attached to the backbone. More specifically, the monomer unit contains a cyano group comprising a pendant group, and the monomer monoterpenes cannot be CN, wherein R is any pendant group. Conversely, the monomeric unit of the monomer unit can be: CN wherein R and Q are any of a plurality of pendant groups. In the present invention, "integral" represents a compound which can form a single sheet according to polymerization.

Q body unit. E.g,

\, CN is the monomer' capable of producing a monomer in a polymer or copolymer. The copolymer is coated with a plurality of near-infrared radiation green paints of a plurality of layers. In a plurality of embodiments, the filament may be a high molecular weight copolymer containing a copolymer having a molecular weight of 10,000 g/mol or more. In the embodiment, the comon has the general structure: - η - Α 1 - - A2 - A3 a L b - _ C - d where a, b, and d are between about 0.01 and 0.90. a plurality of molar ratios, c is a molar ratio varying between approximately G and G.9G, and A1 represents a plurality of monomeric units comprising a pendant group containing an aryl group, wherein the cyano group is not straight 15 201211082 Connected to the main chain of the copolymer; A2 indicates that the disintegration unit ' contains more than two thief bond positions; indicates that the monomer unit can increase the solubility in various organic solvents · and A4 indicates a plurality of monomer units, Increase the solubility in a variety of aqueous solutions. It can be understood from the above generalizing that the silk material can contain two different A1 precursors, two different A2 monomer units, two different singular monomers and/or two or more. Different A4 monomer units. Medium, ^中'. Can be. ' indicates that A3 is not required. Therefore, a plurality of examples β exist in the above chemical structure. In other various embodiments, there is a variation between the 〇.9〇. In an embodiment, a, b, c, and/or _〇ι, 〇2, = 〇·4 〇.5, 〇.6, 〇.7, 〇.8 or greater, and/or 0.8, 0.7 , 0.6, 0.5, 〇, 4, 0.3, 0.2, in various embodiments, the chemical formula of Α1 is:

Wherein: R is hydrogen, methyl or ethyl, 16 201211082 R1 may be absent or represent one to four alkyl or alkoxy substituents; such alkyl substituents may optionally contain more than one ether, ester, amine , amidoxime, urea, piperazinyl, indoleamine, or carbamate functional group 'The alkylate substituents may be optionally substituted by more than one cyano group, U1 being a guanamine or ester linker, VI may be absent or represent an alkyl group, and may optionally contain more than one ether, vinegar, amine, capacamine, urea, pyrazinyl, decylamine, or carbamate functional group, optionally substituted by a Substituted by the above cyano group, and

In the present invention, although a monoalkyl group contains (or optionally contains) a functional group, this means that the functional group may be located at the end of the base or between any two carbon atoms of the indenter. More generally, when more than one functional group is contained in an alkyl group, the functional groups are not necessarily separated by a plurality of carbon atoms in the alkyl group; that is, the functional groups may be directly linked to each other. Obviously, when the functional group (containing two available linkages as shown below) is located at the end of the alkyl group, one of the used linkages will be attached to the carbon atom at the end of the radical, and the other linkage Will connect a hydrogen atom. In the present invention, although a monoalkyl group may be substituted (or alternatively substituted) with a group, this representation has the general meaning of the art that one of the hydrogen atoms of the alkyl group is composed of This group is replaced. Piperazine-based functional group

It is more certain that 'the invention #- 趟 趟 functional group is a functional group (or linker) is - (C = 0) - 0 to 0 - (C = 0) -; - an amine functional group is _ Bullying 3_; A guanamine functional group (or linker) is -(C=0)-NRr or -NR3-(〇0)·; A urea functional group is 掀3 ((>〇)3_ ; One sulfonamide functional group is -SOrNR3· or -NRrSOr; and one carbamate functional group is -NR3-(C=0)-0- or -〇-(C=〇)-NR3·. In the functional group, R3 is hydrogen or a hospital base,

S 17 201211082 The alkyl group may be optionally substituted by more than one hydroxyl group, alkoxy group or halide. In an embodiment, A1 is

18 201211082

X> V is either hydrogen, p- or ethyl

-CN - Aspect, too. Sign and n can vary between 1 and 10. The present invention is also related to a plurality of monomers (four) or a combination of -_, which is equivalent to all subgroups of the monomers. The multiple monomers are related, and related. For the sake of simplicity, the material is re-weighted. The monomers are easily provided on (4). In fact, the hair of the hair, the chemistry of some monomers

HzC R " is a compound which forms a monomer unit according to polymerization. E.g,

Q

CN is the single It's biopolymer-polymer or copolymer monomer monoterpene eN. How easy it is for those who are familiar with the technology: in addition to the two monomer units connected to the other two monomer units (connecting the left and right sides of the above chemical formula), the two-cakes are equivalent to the material of the bribe-like monomer unit. Thief monomer unit. As described above, ^2 is - the monomer unit' contains two or more hydrogen bond positions. In various embodiments, A2 contains three, four, or five hydrogen bond positions. A2 contains multiple functional groups that can form multiple hydrogen bonds. The bases are familiar to those skilled in the art, and the functional groups comprise a plurality of groups 'the base SUX-polar covalent bonds and contain __ domain atoms and contain a plurality of groups' Some of the radicals contain an electron-containing atom containing a pair of free electrons. The radicals include, but are not limited to, 201211082, which are obtained from the red group, the silk, the amine, the amine, the amine, and any one of them. In a particular embodiment, the chemical formula of Α1 is:

Wherein: R is hydrazine, methyl or ethyl, R1 may be absent, or represents one to four alkyl substituents. The alkyl substituents may optionally contain more than 3 ethers, vinegar, amines, guanamines, ureas, a sulfhydryl, sulfonamide or a sulfhydryl functional group; U2 may be absent or represent a guanamine or ester linker; V2 may be absent or represent an alkyl group, optionally containing more than one ether, ester, amine, Amidoxime, auxin, piperazinyl, sulfonamide or carbamate functional group, and Υ is -OH, -S02-NH-R2

An OH,

20 201211082

Wherein R2 is present as a single hydrogen or alkyl group each time, optionally containing more than one ether, ester, amine, guanamine, urea, piperazinyl, sulfonamide or carbamate functional group. In an embodiment, A2 comprises a pendant group comprising a 5,5 dialkylhydantoin,

I

〇γΝ Ν - Η For example, a 5,5 dimethylethylcarbazide group (i.e., ch3), an aminosulfonamide (e.g., -NH-C6H4-S02-NH2) group or a hydroxyl group. In an embodiment, A2 is

S 21 201211082

CH, on the one hand, hydrogen, T-based or ethyl. The invention is also related to the identification or combination of a plurality of monomers for the accumulation of -_, the tree_ and all subgroups corresponding to the monomers .夕2 is related to the eve of a single element, and the related person can easily be provided by the above ^ _ some single _ chemical formula. Familiar with the popularity of this technology. In fact, the chemical formula of the chest, the early body, the early Α2, the chemical formula of some monomers, in fact, the fineness of the wheel - the polymerization of

Q forms a monomer unit. For example, \(10) is the monomer which produces a monomer or unit in a polymer or copolymer 22 201211082. It will be readily understood by those skilled in the art that in addition to connecting the monomer unit to the other two monomer units (connecting the left and right sides of the above chemical formula), the two bonds can be replaced by a double bond, which is equivalent to any particular monomer unit. This monomer is equivalent to the monomer unit. As described above, A3 is a monomer unit which can increase the solubility in a plurality of organic solvents. The organic solvents comprise a plurality of solvents commonly used in the manufacture of a plurality of thermal printing plates; for example: alcohol, ketone, N,N,-dimethylformamide (N,N,-dimethylf〇) Rmamide), N-methyl-2-pyrrolidone, 1,3-dioxolane (i, 3-diox〇lane) and various other general polar solvents. In an embodiment, A3 comprises a pendant or aryl pendant group. These hospital bases and aryl groups increase the solubility in a variety of organic solvents. Therefore, the solubility of the copolymer can be adjusted by varying the molar ratio e. In the examples, the chemical formula of 'A3' is:

Wherein R is I, methyl or ethyl, U3 may be absent or represent a guanamine or ester linker, and Z is a pendant or aryl group, which may optionally consist of more than one hydroxy, alkoxy, or Substituting the complex 'The aryl group may be optionally substituted by more than one leuco group substituted with more than one hydroxyl group, alkoxy group or a toothed compound.

£ 23 201211082 In the gas regime, A3

Or wherein R is hydrogen, methyl or ethyl. The invention is also related to a plurality of monomers. It is better to throw the earth or combine it with H. All of the above-mentioned singles are the same as those of the sub-groups. A3's multiple monomers are related, and related

士可=1:: The chemical formula of these monomers will not be repeated here. Those who are familiar with _ (4) These monomer units A are provided on W. In fact, the a_ system of the present invention - ^ = push - the chemical of some monomers $ early body is - compound, according to polymerization H2%

And a monomer unit is formed. For example, gamma A π is the material 11 ’ kesheng-polymer or copolymer

, monomer single it ° °. Those skilled in the art can easily understand that in addition to connecting the monomer unit to the other two monomer units (connecting the left and right sides of the above chemical formula), two bonds can be used - the double bond is taken from the cake. The age of the same thief monomer unit. As described above, A4 can increase the solubility in an aqueous alkaline solution. Thus, m typically comprises a pendant group containing an acid functional group, such as a monoacid (_c〇〇H), or a disc acid (p〇). The acid functional groups may increase in the aqueous solution. Solubility H The copolymerization_solubility 2 can be adjusted by varying the molar ratio d. Also in a particular embodiment, the chemical formula of A4 is: 24 201211082

A or A wherein R is hydrogen, methyl or ethyl, R1 may be absent, or represents one to four alkyl substituents; such alkyl substituents may optionally contain more than one ethyl bond, ester, amine, guanamine , exhibitin, limazinyl, decylamine or carbamate functional group, U4 may be absent or represent a guanamine or ester linker; V4 may be absent or represent an alkyl group, optionally containing more than one ether, ester , amine, guanamine, urea, beta base, continued guanamine or carbamate functional groups, and

Α is -COOH, ·Ρ〇(〇η)2 v4-cooh or v4—P0(0H)2 In the examples, A4 is a monomer, polymerizable acrylic acid, methacrylic acid, 4-carbonyl-phenyl group~ Obtained as methyl propyl guanamine, a thiol-phenyl propylene amine, a vinyl benzoic acid, an ethylene acid-filled acid, a methacrylic acid-alkyl phosphate or an acrylic acid-alkyl acid monomer. In one aspect, the invention also faces a plurality of monomers. More specific, this is the equivalent of the A4_fine, and the equivalent. In fact, the singularity of the "single 7 material __ some monomeric chemical precursors" is a compound that can be polymerized.

S 25 201211082 h2c<

Q forms a monomer monomer that produces a polymer or copolymer

Monomer unit in Q. Those skilled in the art can understand that, except that the two bonds connecting the other monomer units (connecting the left and right sides of the above chemical formula) can be replaced by a double bond, it is equivalent to a bribe. Monomer, etc. Methods of Making Copolymers These cohesives of the present invention have generally reduced toxicity and are inexpensive to manufacture. These copolymers can be obtained by polymerizing a plurality of organic solvents, which are equivalent monomers. Examples of the hair styling agent include 2,2, azo (2_a = a nitrile) (2, 2'-az〇biS (2-methylbU_nitrile)), benzoquinone (benz〇yl per〇xide), And ammonium persulfate (ammonium P_lfate). The final copolymer can then be isolated, filtered, and dried by precipitation in water, or a mixture of water and alcohol, until a constant weight is obtained. Near Infrared Radiation Sensitive Coating Ingredients for Positive and Thermal Printing Plates In another aspect, the present invention relates to a plurality of near infrared radiation sensitive coating compositions for use in such single or multi-layer positive thermal printing plates. These printing plates can be directly imaged using a variety of near-infrared laser imaging devices using computer direct plate and digital offset printing techniques. Accordingly, the present invention relates to a near-infrared light-sensitive coating composition relating to a positive thermal printing plate comprising: a copolymer as defined above, preferably at a level of 15% by weight and 85 % by weight. Between: a binder resin is preferred, and its content is between 15% and 85% by weight; a near-infrared radiation absorbing compound, preferably, the content is 1.0% by weight and 15 〇/〇 26 201211082; and several optional additives, preferably, between 0.50% and 2.0% by weight. From the above, the coating composition may comprise a mixture of a plurality of copolymers, a mixture of a plurality of binder resins, a mixture of a plurality of near infrared radiation absorbing compounds, and/or a mixture of a plurality of optional additives. For example, a plurality of visible colorants, a plurality of film forming additives, and a plurality of stabilizers. These coating ingredients can be used to prepare a coating for use in a positive thermal printing plate. The coating composition is sensitive to radiation because when exposed to radiation, there is a physical or chemical process in the coating (which is produced by the coating composition), which results in 1) the imaging regions are different from the exposure after exposure to radiation. The unimaged areas, and 2) development, produce an image on the printing plate. Adhesive Resin According to the present invention, the coating composition comprises a plurality of binder resins, preferably at a level of between 15-20% and 80-85% by weight. Suitable adhesive resins for use in a plurality of positive thermal printing plates are known to those skilled in the art. Examples of various binder resins include a plurality of polymers and copolymers comprising a plurality of warp groups which can form a hydrogen bond network using the polymers of the present invention. For example, the binder resins are a plurality of phenolicresins, acetal polymers, and cellulosic polymers. In various embodiments, the binder resin is Thermomag® 7525 (a phenolic resin,

American Dye Source, Inc. (available from Baie d’Urfe, Quebec, Canada), Thermogak® 0802 (a kind of polycondensation polymer, available from American Dye Source, Inc. (Baie d, Urfe, Quebec,

Canada)), and hydroquinone acetate cellulose (cellul〇se hydr〇gen phthalate, available from Kodak (Kingsport, Tennessee, USA)). Near Infrared Radiation Absorbing Compound According to the present invention, the coating composition further comprises a near-infrared ray absorbing compound, preferably a content of between 1 fox and 15% by weight. For use in multiple positive thermal printing plates £ 27 201211082 Suitable near infrared radiation absorbing compounds are known to those skilled in the art. The near infrared radiation absorbing compounds have more than one absorption band with a wavelength between about 780 and 1,10 nm. These materials convert the inhaled near-infrared radiation into heat. For example, a variety of suitable near infrared absorbing compounds are the various cyanine molecules and merocyanine dyes described in U.S. Patent Nos. 5,397,690 and 6,326,122, which are incorporated herein by reference. Examples of other various near-infrared absorbing molecular dyes include the following (acquired by American Dye Source, Inc. (Baie d’Urfe, Quebec, Canada)

ADS780AT '

ADS830AT, and

ADS821AT. A variety of other suitable near-infrared absorbing polymers are those described in U.S. Patent Nos. 6, 4,177, 182, and 7, 473, 515, which are incorporated herein by reference. American Dye Source, Inc. (Baied 'Urfe, Quebec, Canada) obtained and has the following structure:

HSC—

Thermolak® 8010 where a, b, c, d, and e are the molar ratios 其 1〇, 0 30, 0·5〇, 0.08, and 0.02, respectively;

Thermolak® 1010 where a, b, and c are the molar ratios of 〇.73, 〇 25, and 〇 〇2, respectively. Preferably, the near infrared radiation absorbing polymer in the coating composition is present in an amount of about 7 °/ppm by weight. And 15%. A plurality of near-infrared radiation absorbing materials for use in the coating composition of the present invention may be a plurality of near-infrared radiation-absorbing gallotannic compounds as described in U.S. Patent Application Serial No. 61/255,918, incorporated herein by reference. This article. These compounds are available from Americ: Dye Source, Inc. (Baie d'Urfe, Quebec, Canada). An example of the tannin compound is:

E 29 201211082 cio;

Preferably, the near infrared radiation absorbing tannin compound is present in an amount between about 2°/〇 and 5% by weight. Multiple Optional Additives These optional additives can be used in the above coating compositions, including a variety of visible colorants, film forming agents, and shelf life stabilizers, the use of which are prior art Well-known professionals in the field. The absorption band of the various visible colorants used in various embodiments is between 450 and 780 plus 11 'better' at levels between about 1% and 5% by weight. Examples of such visible colorants include various cationic dyes such as blue 3, basic blue 7, basic blue 11, basic blue 17' basic blue 26, basic blue 66, basic red 9, basic red 29, basic violet 2, basic violet 3, basic violet 4, basic violet 6, basic violet 14, basic green 4 and 30 201211082 basic green 5 〇 The coating composition can further comprise a variety of film-forming agents, which can provide more uniform coverage and a smoother upper The surface is such that the formation of a plurality of scratches can be reduced during handling and packaging. Examples of multiple film-forming agents comprise a plurality of siloxane copolymers comprising polyethers, polyesters, and various pendant alkyl groups, such as by Βγκ usa (Wallingford, Connecticut) ,USA), commercially available under the trade names BYK 3〇6, Βγκ 3〇7, BYK 310, BYK 333, and BYK 337 ^Another suitable film-forming agent is a siloxane copolymer containing 'polyethylene oxime and various dazzles • The base group 'is available from American Dye Source, the name; Thermog® P1000S. Preferably, among the coating ingredients, the amount of the plurality of film-forming agents is between about 1% and 6% by weight. The coating composition may further comprise a plurality of stabilizers having a shelf life, such as the stabilizers described in U.S. Patent No. 6,884,568, which includes 3-sulfo-based, 2,4-tris(3-mercapto-1,2,4- Triazole); 3-mercapto-4-methyl-4H-1,2,4-triazole (3-mercapto-4-methyl-4H-l,2,4-triazole); 3-mercapto-5-(4 -° ratio bite base - 4H-1,2,4-triazole (3-mercapto-5-(4-pyridyl)-1 Η-1,2,4-triazole); 2-mercaptobenzimidazole (2 -mercaptobenzimidazole); 2-mercaptobenzoxazole; 2-mercaptobenzoxazole; 2-mercapto is stupid. 2-mercaptobenzothiazole; 6-ethoxy-2-mercaptobenzothiazole; 2-mercapto-5-methyl-1,3,4-nonylbenzene miso (2-mercapto-5-methyl-l,3,4-thiadiazole); 2-mercapto-5-phenyl-1,3,4-oxadipine (2-mercapto-5-phenyl-1,3, 4-oxadiazole) 2-mercapto-5-(4-° ratio) II,3,4-° 2-mercapto-5-(4-pyridyl-l,3,4-oxadiazole ; 5·mercapto-3-methylthio-l,2,4-thiadiazole; 2-Myl-5-methylthio -1,3,4-嗟2. 2-mercapto-5-methylthio-l, 3,4-thiadiazole; 2-mercaptoimidazole; 2-mercapto-l-methylimidazole; 5-mercapto-l-methyl-lH-tetrazole; and 5-mercapto-1-benzene

31 E 201211082 Base-m-four wonderful apt0 ring_1Η•嫩2吟 The content of various heat stabilizers is between about 丨% and 4% by weight. The coating composition also contains more than one type of coating material formed on a substrate. Any solvent familiar to those skilled in the art and suitable for the purpose can be used. The solvent includes, but is not limited to, n-propanol, isopropanol (is〇pr〇pan〇i), 2-methoxypropanol (2_m-Xyp nd), ethylene glycol (ethylglyeQl), Water or a mixture of the above. Positive Film Thermal Printing Plate and Method of Making and Using On the other hand, the present invention relates to a positive thermal printing plate comprising a near infrared light sensitive coating which can be prepared from the above coating composition. In another aspect, the present invention relates to a positive-working thermal printing plate comprising a near-infrared radiation-sensitive coating comprising: a copolymer as defined above; a binder resin as defined above; Light absorbing compound; and a plurality of optional additives as defined above. Within the printing plate, the near infrared radiation sensitive coating is deposited on a substrate. In various embodiments, the substrate is an electric ship, a variety of plastic or paper. The multi-strength substrate can be a brushed particle or an electric mineral engraving, and a multi-faceted solution can be used. The near-infrared radiation sensation coating has a coating weight of between 1.0 and 3.0 g/m2. In the embodiment, there may be more than - layers between the substrate and the near infrared radiation sensitive coating, and/or on the surface of the near infrared light sensitive coating, which is familiar to those skilled in the art. . For example, a '-layer polymeric adhesion promoting layer and/or insulating layer can be positioned between the substrate and the near infrared radiation sensitive coating. The layer may be composed of polyacrylic acid (), polyacrylic acid monovinyl phosphate copolymer (tetra) y (aci^lic acid c〇々 (four) batch 〇 sph〇ric acid)) or polyethylene sulphate (polyvinyl ph〇Sph〇 Rjc acid) obtained a variety of aqueous solutions of 32 201211082 and then dried with hot air at a temperature of about 110 。. The adhesion layer of the adhesion promoting layer and/or the heat insulating layer may be between about G.1 and i〇g/m2. A plurality of protective films may also be provided on the surface of the near-infrared light-sensitive paint. The near-infrared light-sensitive paint can usually be protected from the surrounding harmful radiation, moisture, scratches, punctures and the like. In another aspect, the invention relates to a method of making a positive thermal printing plate comprising the steps of: a) providing a sheet substrate, and applying _ layer of the coating as defined above Ingredients. In an implementation, the method further comprises ageing: prior to step b), a polymeric adhesion promoting layer and/or a thermal barrier layer is applied to the substrate. In another aspect, the invention relates to a printing method comprising the steps of: a) providing a positive thermal printing plate as defined above, and b) imaging the printing plate with near-infrared light, tearing the printing The plate is developed, and d) is brushed using the printing plate on the printing press. These printing plates can be directly imaged using a variety of laser imaging devices using computer-to-plate and digital offset printing techniques. Upon application, the imaged print can be developed outside of the printer with water or a developer. In use, the copolymer and binder in the coating can form an adhesive network by forming a plurality of nitrogen bonds. When the near-infrared light-absorbing compound is exposed to near-infrared light, the near-infrared radiation absorbing compound absorbs the inhaled near-infrared radiation and generates ..., which will interrupt the hydrogen in the imaged regions. The network of bonds will cause the exposed areas to be more soluble in water or developer (developer outside the printing press), or more soluble in the immersion liquid and various inks than the less exposed areas. This allows for the development of these printing plates (on the press or outside the press). The partial compounds described herein can exist in multiple versions of different isomers (e.g., optical, geometric, and/or positional isomers). The invention encompasses all such isomers. Unless otherwise specified, "alkyl" as used in the present invention denotes a linear or branched alkyl group containing from 丨 to 24 carbon atoms, and "aryl" means having from 1 to 3 rings and optionally containing one or

S 33 201211082 An aryl group of two heteroatoms (eg nitrogen, oxygen, and sulfur). Similarly, "alkoxy" means a linear or branched alkoxy group (R-0-) having from 1 to 24 carbon atoms. In the present invention, "halide" means F_, Cl-, Br-, or I-. Unless otherwise stated, the weight percent values of the present invention are based on the total net weight of the coating composition. As used herein, "near-infrared radiation" means electromagnetic radiation, such as electromagnetic radiation that is produced by a laser and has a wavelength between about 700 and 110 nm. Examples of such near-infrared radiation are not limited to the light emitted by a plurality of diode lasers, and the diode lasers can be equipped with a variety of plate output machines (available from Creo-Kodak, Dinippon Screen, Heidelberg, and Presstek International). . As used herein, "about" means that both 5% and 5% of the value are acceptable. Other objects, advantages and features of the invention will become apparent from the <RTIgt; DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS The present invention can be further illustrated in detail by the following non-limiting examples. These examples use the compounds listed in the following glossary. Glossary

The Basic violet 3 visible colorant&apos; can be obtained from Spectra Colors (Keamy, New Jersey USA). DMF N,N-Di"N,N-dimethylformamide Dowanol PM 2-methoxypropanol&apos; is available from Dow Chemicals (USA and Ho Chi Minh City, Vietnam). EMA Ethyl methacrylate, available from Sigma Aldrich (Canada) 34 201211082 GSP90 An alkaline aqueous developer for positive thermal lithographic offset printing plates with a conductivity of 80 mS/cm at 25 ° C. Mylan Group ( Travinh City, Travinh Province, Vietnam). HDB-01 O 3-[4-styrene] 5-[4-Vinylbenzyl]-5,5-dimethylhydantoin, available from American Dye Source, Inc. (Baie d 'Urfe, Quebec, Canada). HDB-02 3-{2-Methyl-2-[N-[(3-ethyl-5,5-dimethylhydantoinyl)ureido]ethyl}-2-m ethylvinyl benzene by American Dye Source, Inc_(Baie d'Urfe, Quebec, Canada). HDB-03 J, nh2 N-(4-aminosulfonylphenyl)methacrylamide, available from American Dye Source, Inc. (Baie d'Urfe, Quebec, Canada). HDB-04 \/NH2 UXr. O 2-[N,-(4-aminosulfonylphenyl)ureido]-ethylmethacrylate » is available from American Dye Source, Inc. (Baie d'Urfe, Quebec, Canada). s 35 201211082 HDB-05 0 2-[N'-(4-hydroxyphenyl)ureido]ethylmethacrylate, available from American Dye Source, Inc. (Baie d'Urfe, Quebec, Canada). HDB-06 i ο 2-(5,5-Dimethylhydantoinylethyl methacrylate), available from American Dye Source, Inc. (Baie d' Urfe, Quebec, Canada). MCN-01 CH3 0 h2c^Y°^n^cn o 2-(Cyanomethylamido)ethylmethacrylate, available from American Dye Source, Inc. (Baie d’Urfe, Quebec, Canada). MCN-02 0 2-[N'-(4-Cyanophenyl)ureido]ethylmethacrylate, available from American Dye Source, Inc. (Baie d'Urfe, Quebec, Canada). MCN-03 O CN 2-[N'-(2-Cyanophenyl)ureido]ethylmethacrylate, available from American Dye Source, Inc. (Baie d'Urfe, Quebec, Canada). 36 201211082 MCN-04 CH3 · 4-Cyanophenyl methacrylamide, available from American Dye Source, Inc. (Baie d'Urfe, Quebec, Canada) MEK Mercaptoethyl Ketone (Methyl) Ethyl ketone), available from Sapa Chemicals (Ho Chi Minh City, Vietnam). MMA Methyl acrylate (Methylmethacrylate) available from Sigma Aldrichfanada). NMP N-methyl-2-pyrroIidone, available from Sapa Chemicals (Ho Chi Minh City, Vietnam). An aqueous solution of PG aqueous solution containing 60% by weight of propylene glycol was obtained by (Mylan Group, LongDuc Industrial Park, Travinh City, Travinh Province, Vietnam). The aqueous solution of PM aqueous solution 'water contains 60% by weight of propylene glycol methyl ether, which can be obtained by (Mylan Group, LongDuc Industrial Park, Travinh City, Travinh Province, Vietnam). Stabilat-20 aqueous solution containing 20% by weight of Stabilat D2010 (a concentrated infusion for sheetfed printing, available from FUJIFILM Hunt Chemicals Singapore Pte. Ltd. (Singapore)). Thermolak® Oxygenated Copolymer, comprising polyethyl ketone and multiple alkyl groups, available from American Dye P1000S Source, Inc. (Baie d’Urfe, Quebec, Canada). The Thermolak® 1010 Near Infrared Absorbing Polymer has a maximum absorption peak of 800 nm in a methanol solution and is available from American Dye Source, Inc. (Baie d’Urfe, Quebec, Canada). s 37 201211082

Thermolak® 7525 Novolak resin, available from American Dye Source, Inc. (Baie d, Urfe, quebec, Canada). V59 Azobisisovaleronitrile (2,2,-azobis(2-methylbutyronitrile), available from Wako (USA). Synthesis of 9h3 ch3 H3CH2C-]-N=N--CH-CH, ch3 ch3 copolymers. The copolymers are synthesized by installing a water condenser, a mechanical stirrer, a dropping funnel, and A nitrogen inlet is implemented in a four-neck glass reactor. The molecular structure of the copolymers obtained can be determined by NMR and FTIR microscopy. The average molecular weight of the copolymers prepared can be determined by size exclusion chromatography (SEC) using N,N-dimethylformamide (N, N-dimethylf_amide) solution, and recorded by the red woman _ Qing· (4) Fresh calculations. The 驴 value is determined by titration using a potassium hydroxide solution in ethanol. Example 1 The general structure of the copolymer PCN-01A is as follows:

Where a=0.20, b=0.37, C=0.35, and d=0.08 are added to a 120 ml DMF solution (where 〇2 is dissolved) at a temperature of 75 〇c, a value of a stirrer, and a nitrogen atmosphere. 〇Mole's MC off, 0.37 moles of foot, 〇35 mol of methyl acetoacetate (but 38 201211082 methacrylate), and 0 08 mol of methacrylic acid were synthesized. After 1 hour of polymerization, '2 gram of V59 was added to the reaction mixture and the polymerization was continued for another 14 hours. At a temperature of 105. (The polymerization was terminated by introducing air and stirring the reaction mixture for 2 hours. The copolymer was precipitated in 2 L of deionized water, thoroughly filtered and washed with deionized water. Under a vacuum of 40: (:: A white powder was obtained after drying. The average molecular weight and acid value were determined to be 43,400 g/mole and 26.2 mg KOH/g, respectively. Example 2 The general structure of the copolymer PCN-02A is as follows:

Where a=0.20, b=0.37, c=0.35, and d=〇.〇8 is to add 0.30 g of V59 to 120 ml of DMF solution at a temperature of 75 ° C, constant stirring, and nitrogen rolling environment (wherein dissolved)合成. 2 〇 M M-01, 0_37 Moh HDB-02, 〇.35 mol ethyl methacrylate, and 0.08 mol methacrylic acid were synthesized. After 1 hour of polymerization, 2 Torr of V59 was added to the reaction mixture and the polymerization was continued for another 14 hours. The polymerization side was terminated by mixing the air with jyf at a temperature of 105 c for 2 hours. The copolymer was thoroughly filtered and washed with deionized water in a 2 L of deionized water. After the machine is under vacuum of 4 〇〇c, it can be _-self-color powder. The average molecular weight and hearing were determined to be 74,000 g/mole and 26.4 mg KOH/g, respectively.

S 39 201211082 Example 3

The general structure of the copolymer PCN-03A is shown below as CH-, . .CH^ , -CH, CH

o=s=o I nh2 where 'except for HDB-03 with 0.37 mole instead of HDB-01, the synthesis of a=0.20, b=0.37, c=0.35, and d=0.08 is similar to the example to complete the polymerization. Thereafter, the copolymer was precipitated in 2 L of deionized water and thoroughly filtered and washed with deionized water. A white powder was obtained after drying under a vacuum of 卯%. The average molecular weight and acid value were determined to be 85 〇〇〇 m〇le/g and 24_4 g/mole respectively. The general structure of the sample 4 copolymer PCN-04A is as follows:

o = s = o I nh2 where 'in addition to HDB-04 with 0.37 mole instead of HDB-01, the synthesis of a = 0.20, b = 0.37, e = 0.35, and d = 0.08 is similar to that of Example 1. Upon completion of the polymerization, the copolymer was precipitated in 2 L of deionized water and thoroughly filtered and washed with deionized water. At 4 〇. A white powder was obtained after drying under vacuum: 201211082. The average molecular weight and acid value were determined to be 97,000 mole/g and 24.0 g/mole, respectively. Example 5 The general structure of the copolymer PCN-05A is as follows:

0^0 0^0 0^0 O^OH

Among them, except for the use of 0.37 mole HDB-05 instead of HDB-01, the synthesis of a=0.20, b=0.37, c=0.35, and d=0.08 is similar to the example. After the polymerization is completed, the copolymer precipitates. In 2 L of deionized water, it was thoroughly filtered and washed with deionized water. After drying under vacuum at 40 ° C, a white powder was obtained. The average molecular weight and acid value were determined to be 89,000 mole/g and 23.7 g/mole, respectively. Example 6 The general structure of the copolymer PCN-06A is as follows:

,丫丨 W丫 1

41 201211082 where a=0.20, b=0.37, c=0.35, and (1=0.08 is to add 0.30g of V59 to 120ml of DMF solution at a temperature of 750C, constant agitation, and nitrogen atmosphere (wherein 〇2〇 is dissolved) Synthesized from MCN-02 of Moer, 0.37 mole of HDB-02, 0.35 mole of ethyl methacrylate, and 〇·〇8 mole of methacrylic acid. After 1 hour of polymerization 2 gram of V59 was added to the reaction mixture and the polymerization was continued for another 14 hours. The polymerization was terminated by introducing air at a temperature of 105 ° C and stirring the reaction mixture for another 2 hours. It will be precipitated in 2 L of deionized water, thoroughly filtered and washed with deionized water. After drying under a vacuum of 4 〇 0 (:: a white powder is obtained. The average molecular weight and acid value are determined to be 67,000 g/m, respectively.一般le and 23.6 mg KOH/g 〇 Example 7 The general structure of the copolymer PCN-07A is as follows:

The synthesis of a=0.20, b=〇.37, c0.35' and d=:〇.〇8 is similar to Example 6 except that MCN-04 of 0.20 mole is used instead of MCN-02. Upon completion of the polymerization, the copolymer will sink in 2 L of water in the face &lt; After finishing the drying under the vacuum of 4 generations, a self-coloring powder can be obtained. The average molecular weight and acid value were determined to be 77,000 m〇le/g and 24.2 g/mQle, respectively. 42 201211082 Example 8 The general structure of the copolymer PCN-08A is as follows:

o=s=o nh2 where a=0.20, b=0.37, c=0.35, and d=〇.〇8 is at a temperature of 75〇c, the value is assigned, and the gas atmosphere will be 0·30 grams. V59 was added to 12 〇ml of DMF solution (wherein 〇 2 〇 Mo MCN-02, 0.37 莫 HDB-04, ο. % 莫 methyl acetoacetate and 0.08 mM methyl propyl) It is synthesized by citric acid. After 1 hour of polymerization, (iv) grams of V59 was added to the reaction mixture and the polymerization side was continued for another M hours. The polymerization was terminated by introducing air at a temperature of 105 ° C and then scramble the reaction filament for 2 hours. The copolymer was precipitated in 2 L of deionized water and thoroughly filtered and washed with deionized water. A white powder was obtained after drying under a vacuum of 4 〇〇c. The average molecular weight and acid value were determined to be 105,000 g/mole and 23.9 mg KOH/g, respectively. Example 9 The general structure of the copolymer PCN-09A is as follows: 43 £ 201211082

Among them, the synthesis of a=0.20, b=0.37, c=0.35, and d=0.08 is similar to the example 8 except that 0.37 mole of HDB-06 is used instead of i^jqb-04. Upon completion of the synthesis, the copolymer was precipitated in 2 L of deionized water and thoroughly transitioned and washed with deionized water. After drying under a vacuum of 4 ° C, a white powder was obtained. The average molecular weight and acid value were determined to be 92, 〇〇〇 g / m〇ie * 24.0 mg KOH / g ° Example 10 The general structure of the copolymer PCN-10A is as follows:

Among them, the synthesis of a = 〇.2〇, b=〇 37, c=0.35, and d=〇.〇8 is similar to the example 9 except that MCN-03 of 〇·2〇 莫 is used instead of MCN-02. After completion of the synthesis, the copolymer was precipitated in 2 L of deionized water and thoroughly filtered and washed with deionized water. After drying under vacuum, a white powder was obtained. The average molecular weight and acid value were determined to be 82, 〇〇〇 and 44 201211082 24.0 mg KOH / g 〇 positive film thermal lithographic offset printing examples 11 to 21 coating solutions containing the following various ingredients (the surface can be coated with a spin coating Covered on an aluminum substrate, where the substrate is formed into a bond particle shape using a mixed acidic solution (ie, hydrochloric acid and acetic acid) and electroplated in an aqueous sulfuric acid solution, followed by NaF/ at 8 〇 QC. The NaH2p〇4 aqueous solution was post-treated. The covered films were dried using 1 Torr (5: hot air. The weight of the coating was about 1.7 g/m2. The printing plates were stored at 35 ° C. A week later, the plates could be imaged using a PlateRite 8600S plate output machine (available from Screen (Japan)) with different laser powers at a drum speed of 9 〇〇 RPM. The imaged printing plate can be developed with a TungSung88 processor using Gsp9(R) developer at 23 ° C. The optical density of these printing plates can be ffishamr〇ckDensit〇meter (model: c〇1〇rPrim 415 can be obtained by Muller BV (PO Box 44 , 7913 ZG Hollandscheveld, Netherlands) Take measurements. The percentage of dots on these developed printing plates can be obtained using a Techk〇n

The SpeCtr〇Plate measuring device (model Expert, available from Techkon USALLC (Dan Sideback 01923, USA)) was measured. These printing tests can use a Heiddberg Lang (four) Shika 74 printing press (four), Germany), which uses a single sheet of black ink (available from ¥ Ink (USA)), on these developed printing plates. carry out testing. The chemical resistance test is performed at 25 〇c τ, and the developed _ plate is immersed in the alcohol-water solution (9). The optical density of the woman's version before and after the solution and the immersion liquid was recorded to calculate the chemical resistance (indicated by CR). , £ 45 201211082 Definition Correct Exposure (CE, mW): The imaging energy density required to form 5 % of the dots on the developed printing plate (according to 50% of the dots on the target). Clear point (CP, mJ/cm2): The energy density required to multiply the optical density at 0% of the dot by 1% by the dot density multiplied by 0.05. The loss of development of the coating (CDL, %) can be calculated by the following formula: CDL - [ODadl - 〇Dsub] / [ODbdl - ODsub] xl〇〇 where: For example, the optical density value at 100% dot after development; 〇 Dsub is the optical density value of the aluminum substrate of the uncovered paint; and ODbdi is the optical density value at 1% solid state before development. Smaller CE, CP, and CDL values indicate better performance of the printing plate. The chemical resistance (CR, %) can be calculated using the change in optical density and the following formula: CR = [〇Dad2 - 〇Dsub] / [ODbd2 - ODsub] x 100 where: 〇Dad2 means immersion at 25 °C after development An optical density value of an alcohol solution for 3 minutes to reach 1% of the dot; 〇Dsub is the optical density value of the aluminum substrate of the uncovered coating; and 〇Dbd2 is developed, and immersed in a The optical density value at 100% solid state before the alcohol solution. 46 201211082

Example 21 5.50 1.00 0.25 0.25 Example 20 2.00 3.50 1.00 0.25 0.25 Example 19 2.00 3.50 1.00 0.25 0.40 Example 18 2.00 3.50 1.00 0.25 0.40 Example 17 2.00 3.50 1.00 0.25 0.40 Weight (g) Example 16 2.00 3.50 1.00 0.25 0.40 Example 15 2.00 3.50 1 1.00 0.25 0.40 Example __14 2.00 3.50 1.00 0.25 0.40 杳m 瑞一1 2.00 3.50 1.00 0.25 0.40 范例 Example 12 , 2.00 3.50 1.00 0.25 0.40 Example 11 2.00 3.50 1.00 0.25 0.40 Component PCN01A PCN02A PCN03A PCN04A PCN05A PNC06A PCN07A PCN08A PCN09A PCN10A ThermolakTM 7525 Thermo lakTM 1010 Basic violet 3 ThermolakTM P1000S s 47 201211082 Weight (g) 80.0 15.0 1 5.00 Energy density (mJ/cm2) &lt;N CN η ν£&gt; Loss of coating development, CDL(%) 7.50 11.0 2.20 4.20 80.0 15.0 5.00 oo inch CN 3.20 5.40 80.0 15.0 5.00 00 § Art 00 1.50 2.80 80.0 15.0 5.00 ss (N m H VO (N 2.40 4.60 80.0 15.0 5.00 s VO 1.40 2.80 80.0 15.0 5.00 冢oo CN OO 3.70 5.60 80.0 15.0 1 5.00 00 〇CN (N 1.50 3.00 80.0 15.0 5.00 o 00 oo VO v〇CN 宕80.0 15.0 5.00 v〇宕o 1.80 3.85 80.0 15.0 5.00 z (N m 00 1.60 3.90 80.0 15.0 5.00 宕 4.20 6.80 Solvent Dowanol PM MEK NMP Laser imaging clear point, CP 20 seconds dwell time 30 seconds dwell time correct exposure, CE 20 seconds dwell time 30 seconds dwell time 23 ° C development 20 seconds 30 seconds alcohol resistance Value, CR (%) CN m CN G\ Z On 〇\ (NC\ 〇\ 00 oo 00 osr»H o Os Q\ ss r-· 〇cs 00 〇\ 〇00 om oo 〇\ CN 00 1—H Bu oo σ PG aqueous solution PM aqueous solution Stabilat-20 48 201211082 It can be observed from the table that the printing plates containing the copolymers of the invention show several advantages over the printing plates without any of the copolymers (Example 21 ). These printing plates require less energy in laser imaging and show lower coating development losses. These printing plates also show better chemical resistance against immersion liquids substituted with alcohols, such as Stabilat D2010 and aqueous solutions containing 60% Dowanol PM and propylene glycol. In contrast, it was observed that the printing plate of Example 21 was completely dissolved after being immersed in an aqueous solution containing 5 % Dowanol PM for 8 hours. Further, the printing plates containing the copolymers of the present invention can produce 18 〇〇〇 high-quality copy paper. In contrast, the print version of Example 21 produced approximately 11 inches of high quality copy paper. Finally, it can be observed that the printing plates are stored under normal indoor conditions for at least 12 months while remaining stable. ^II/IJ test shows that these copolymers for positive printing plates generally provide fast laser imaging rate, high resolution images, wide development tolerance, stable shelf life, good chemical resistance, Longer printing runs with the press. The present invention is not limited to the specific implementations described above, but modifications to the present invention are not limited to the spirit and characteristics of the present invention as defined by the patent application.

S 49 201211082 [Simple description of the diagram] None [Explanation of main component symbols] None [References] Several documents mentioned in this manual are hereby incorporated by reference in their entirety. US Patent US Provisional Patent Application 5,397,690 61/255,918 6,124,425 6,132,929 6,177,182 6,326,122 6,355,396 6,410,203 6,884,568 7,060,415 7,060,416 7,258,961 7,371,504 7,473,515 50

Claims (1)

201211082 VII. Scope of application: 1. A copolymer containing the general structure: -Α1 a Α2· b A4 —- .d where a, b and d are between approximately 〇·01 and 〇·9〇 a plurality of molar ratios, c is a molar ratio varying between about 0 and 0.90, and A1 represents a plurality of monomer units comprising a pendant group containing a cyano group, wherein the cyano group is not directly bonded to the copolymer The primary key; A2 means multi-solution fresh element, containing two hydrogen bond positions; A3 table is a single cell single 1, can increase the conversion of multi-finance machine 丨 and A4 table is not painful single fresh % can increase multi-homing The solubility of the water towel. 2. According to the special shot, please refer to the item described in item ,, where αι _ 丄 Τ1 Or ο 丫1 w where R is hydrogen, methyl or ethyl, S 51 201211082 R1 may be absent or represent one to four alkyl substituents; the alkyl substituents may optionally be more than 3 a sulphuric acid, an amine, an amine, a urea, a sulfhydryl group, a urethane or a carbamate functional group, which may be optionally substituted by more than one cyano group; U1 is a guanamine or An ester linker, V1 may be absent or represent an alkyl group, and may optionally contain more than one ether, ester, amine, guanamine, urea, piperazinyl or amino phthalate functional group, optionally having more than one alkyl group. Substituted by cyano, and W is -CN or ~cn 〇 52 201211082 Or CN wherein R is hydrogen, methyl or ethyl, and η can vary between 1 and 10. 4. The copolymer of any one of clauses 1 to 3, wherein the oxime 2 comprises a pendant group containing a 5,5-dialkylhydantoin group, such as a 5,5- Dimethylethalurolide, an aminosulfonamide or a hydroxyl group. 5. The copolymer of any one of clauses 1 to 3 of the patent application, wherein the chemical formula of Α2 is: Or £ 53 201211082 R is hydrogen, methyl, or ethyl, R1 may be absent, or represents one to four alkyl substituents. The alkyl substituents optionally contain more than one ether, ester, amine, guanamine, urea, and piperazine. a sulfinyl, sulfonamide or amino phthalate functional group; U2 may be absent or represent a guanamine or ester linker; V2 may be absent or represent a burnt group, optionally containing more than one ether, ester, amine, guanamine , urea, piperazinyl, sulfonamide or amino phthalate functional groups, and Y is -OH, - S02-NH-R2 Each of R2, which is presented as a single hydrogen or a burner, can optionally contain more than one ether, ester, amine, guanamine, urea 'piperazinyl, sulfonamide or carbamate functional group. 54 201211082 6. Copolymer according to item 5 of the patent application, wherein Y is 7. The copolymer according to item 5 of the patent application, wherein Α2 is: £ 55 201211082 8. The copolymer according to any one of clauses 1 to 7 of the patent application, wherein c is between about 〇·〇1 and 0.90. 9. The copolymer of claim 8 wherein A3 comprises a monoalkyl or aryl pendant group which is actually substituted by an alkyl group. 10. The copolymer according to item 8 of the patent application, wherein the chemical formula of A3 is: Γ~ R -I Z wherein R is hydrogen, methyl or ethyl, U3 may be absent or represents a chiral amine or vinegar linker; and z is alkyl or aryl 'the alkyl group may optionally consist of more than one hydroxy, alkoxy, Alternatively, the aryl group may be replaced by more than one alkyl group substituted with more than one mesogen, alkoxy group or an image. 11. The copolymer according to item 9 of the patent application, wherein A3 is: Wherein R is hydrogen, decyl or ethyl. 12. The copolymer of any one of clauses 1 to 1 wherein the pendant group&apos; contains a monocarboxylic acid group or a monophosphate group. 13. The copolymer according to any one of the preceding claims, wherein the chemical formula of a4 is: 56 201211082 R is hydrazine, methyl or ethyl ' wherein &amp; may be absent, or represents - to four filament substitutions; some alkyl substituents (iv) optionally contain more than one acetamidine, s, amine, guanamine, urea , a slightly sulfhydryl, a hydrazine or carbamate functional group, only a may be absent or represent a guanamine or ester linker; V4 may be absent or represent an alkyl group, optionally containing more than one ether, ester, amine , amidoxime, urea, piperazinyl, sulfonamide or carbamate functional groups, and The copolymer of any one of clauses 1 to 12 wherein the ruthenium 4 is a monomer capable of polymerizing a plurality of acrylic acid, methacrylic acid, 4-rebel-phenyl-methacrylamide It is obtained by 4-carbonyl-phenyl-acrylamide, vinyl benzoic acid, vinyl phosphoric acid, methacrylic acid-alkyl phosphite or acrylic acid-alkyl phosphate monomer. 15. A near-infrared radiation-sensitive coating composition comprising: a copolymer as defined in any one of claims 1 to 13; a binder resin; S 57 201211082 a near-infrared radiation absorbing compound; Multiple optional additives. 16. - Positive film thermal printing plate, &amp; containing - near infrared radiation sensitive coating, which can be prepared from the coating composition of claim 14 of the patent application. 17. a positive < </ RTI> < </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> a resin; a near infrared radiation absorbing compound; and a plurality of optional additives. 18. A method of producing a positive thermal print plate, the method comprising the steps of: c) providing a piece of substrate, and d) applying the coating composition of claim 14 of the patent application to the substrate . 19. A printing method comprising the steps of: 提供 providing a positive thermal print plate according to item 15 or item 16 of the patent application, g) imaging the printing plate with near infrared radiation, h) printing the same Printing, and i) printing using the printing plate on a printing press. 20. A monomer' is equivalent to a monomer unit A1 as defined in any one of the patent application scopes i to 3. 21. A monomer unit' corresponds to a monomer unit A2 as defined in any one of claims 1 and 4 to 7. 22. A monomer which is equivalent to a monomer unit A3 as defined in any one of claims 1 and 9 to 5 of the patent application. 58 201211082 23. A monomer corresponding to a monomer unit A4 as defined in the first and third paragraphs of the patent application. 12. Any of the 13th items £ 59 201211082 IV. Designated representative map: (1) The representative representative of the case is: (). (2) A brief description of the symbol of the representative figure: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: