CN101192004A - Chemical-free negative-working photosensitive composition suitable for UV-CTP, lithographic plate made therefrom, and lithographic plate manufacturing method - Google Patents

Abstract

The invention discloses a chemical-free negative photosensitive composition suitable for UV-CTP, a lithographic plate made by using it and a lithographic plate production method, which mainly include: (1) a -(X)-( Y)-(Z)-structure unsaturated water-soluble polymer, characterized in that X represents a copolymerization unit containing a sulfonic acid group, Y represents a branched carboxylic acid copolymerization unit containing two unsaturated double bonds, and Z Represents an acrylate copolymerized unit containing an unsaturated double bond branch, and (2) a photopolymerizable prepolymer, and (3) a multifunctional monomer, and (4) one or more A photopolymerization initiator, and (5) one or more dyes or pigments. The present invention is suitable for the lithographic printing plate of UV-CTP plate making machine. The lithographic printing plate of the present invention has high sensitivity and good dot resolution, and can be directly washed with tap water or printed on the machine without any washing processing steps after exposure to ultraviolet light source. , and can get high printing resistance, especially suitable for UV-CTP plate-making machines.

Description

Chemical-free negative-working photosensitive composition suitable for UV-CTP, lithographic plate made therefrom, and lithographic plate manufacturing method

technical field

The invention relates to a chemical-free negative photosensitive composition suitable for UV-CTP, a lithographic plate made by using it, and a method for making the lithographic plate.

Background technique

The preparation of lithographic printing plates is well known in the printing industry. The plate-making process of the lithographic plate requires at least two steps to complete. One is to expose the plate coated with the photosensitive composition to a specific light source through a mask (such as a positive film type and a negative film type mask), thereby forming One is the latent image of the light image; the other is to carry out a so-called subsequent development step on the exposed printing plate, through which the excess coating is removed. Pre-coated photosensitive lithography is a sheet-like material supported by aluminum or polyester, and can be prepared through the above two steps to have both lipophilic and hydrophilic surfaces, suitable for lithographic printing. Typically, in a negative-type system, the exposed areas become insoluble or insoluble in the developer as a result of polymerization or cross-linking of the coating, so that the coating on the unexposed areas of the plate can be removed during the development step. Conversely, in a positive-film system, the development step removes material from the exposed areas of the printing plate. The developing step usually involves rinsing and washing with a developer, usually in a processing unit containing the developer. The developer used in positive-working lithographic plates is usually a strong base, and the negative-working developer usually contains an organic solvent, such as benzyl alcohol, in addition to a strong base. Of course, the development of the light image can also be accomplished by heating or other means.

The disadvantages of the above two (ie wet and thermal) development processes are that they are time-consuming and expensive. Moreover, when volatile organic compounds or strong alkalis are used as developers, the disposal of these waste liquids will bring environmental problems.

With the development of the printing industry and the improvement of people's living standards, countries all over the world have higher and higher requirements for environmental protection, so there is a need for a printing plate that does not require chemical treatment or any treatment before printing, which will not only benefit It is environmentally friendly, and it will also help reduce printing costs, reduce the space in the printing room and reduce the makeready time of printing jobs.

Constructions of positive-working printing plates that require no processing after imaging and prior to printing have been disclosed (eg, see US Patent Nos. 5,102,771; 5,225,316 and 5,314,785). These patents disclose printing plates and photoacid generating systems based on photosensitive coatings containing acrylate or methacrylate polymers. When the image is exposed to light radiation, the polymer in the light-irradiated areas decomposes to become hydrophilic, while the polymer in the non-light-irradiated areas remains ink-loving.

Precoated photonegative-type lithographic plates that do not require processing after imaging prior to printing are also known in the art. Classes of printing plates that do not require a processing step between imaging and printing are disclosed in US Patent Nos. 3,231,378; 3,285,745; and 3,409,487. These plates contain a photosensitive composition comprising a phenolic resin, an ethylene oxide polymer and a photosensitizer. When exposed to actinic radiation, the phenolic resin oxidizes, thereby increasing ink receptivity. The disadvantage of these plates is that they tend to lose ink affinity during the printing process, so that strict control of the ink/water balance on the printing press is required to ensure proper printing, and sometimes the plate becomes inoperable. US Patent No. 3,793,033 discloses the addition of hydroxyethyl cellulose esters to the composition. The resulting printing plate will not be blinded (ie the plate is free from ink, loss of image when printing) and requires less control of the ink/water balance on the printing press. An obvious disadvantage of this composition is the phenolic resin that needs to be cured to obtain suitable press runs. In this way, a two-layer system needs to be formed on the obtained printing plate precursor, that is, a sensitizer layer should be added on the phenolic resin-containing layer. If the sensitizer layer is not applied after curing then the phenolic resin will decompose upon curing.

Another class of negative-working plates that do not require processing between imaging and printing are those based on multiple photosensitive layers. Typically, as described in U.S. Patent Nos. 4,600,679 and 4,104,072 and European Patent Publication No. 450,199, these structures have a hydrophilic photosensitive layer closest to the plate, an additional layer for photohardening and connect. These structures usually use negative-type photosensitive compositions based on aromatic diazo compounds as the hydrophilic layer closest to the plate base. A disadvantage of these plates is their tendency to smudge (ie, ink the background area) and contaminate the printing press. This disadvantage requires that the printing plate be cleaned with a suitable cleaning agent (ie fountain solution) before printing. Therefore, the addition of diazo compounds and resins is detrimental to the printing plate used for the "no treatment" plate. The printing plate disclosed in PCT Application No. 93-05446 has no diazo component in the hydrophilic layer, thereby eliminating the problem of printing press contamination due to residual unreacted diazo species. The plate comprises a plate/base, a photopolymeric hydrophilic layer proximate to the base, and a second, spaced photopolymeric hydrophobic layer proximate to the base. The photosensitive hydrophilic layer is based on a polymerizable substance free of diazo compounds. The functionality of the plate is achieved by exposure of the two layers to loss of water solubility and hardening by exposure to actinic radiation. The plate requires only a printing press with ink and fountain solution to get a good print after exposure, without prewashing the plate before printing. Since the structure has an external hydrophobic layer, the same water and inking performance as a conventional plate cannot be obtained if the background portion is not treated to remove the hydrophobic substance before printing.

Contents of the invention

The purpose of the present invention is to provide a suitable screen with high sensitivity, good resiliency of dots, which can be directly washed with tap water or printed on the machine without any washing process after exposure to ultraviolet light source, and can obtain high printing durability. A chemical-free negative-working photosensitive composition for UV-CTP, a lithographic plate made with it, and a method for making the lithographic plate.

The object of the present invention can be achieved through the following measures:

The chemical-free negative photosensitive composition suitable for UV-CTP of the present invention mainly includes the following six components: (1) an unsaturated water-soluble polymer of -(X)-(Y)-(Z)-structure , and (2) a photopolymerizable prepolymer, and (3) a polyfunctional monomer, and (4) one or more photopolymerization initiators, and (5) one or one More than one kind of dyes or pigments, and (6) one or more solvents; wherein, X represents a copolymerization unit containing a sulfonic acid group, and Y represents a branched carboxylic acid copolymerization unit containing two unsaturated double bonds , Z represents an acrylate copolymerized unit containing an unsaturated double bond branch.

X is selected from vinylsulfonic acid, styrenesulfonic acid, 2-hydroxy-3-allyloxy-1-propylsulfonic acid, allyloxy Benzenesulfonic acid, 2-acrylamido-2-methylpropylsulfonic acid, isoprenesulfonic acid. X accounts for 10% to 30% molar ratio of the copolymer. Y is a branched acrylic or methacrylic copolymerized unit containing two unsaturated double bonds. Alternatively, Y is a GMA grafted acrylic or methacrylic copolymerized unit containing one unsaturated double bond substitution. Y accounts for 20%-40% molar ratio of the copolymer. Z is an acrylate or methacrylic copolymer unit containing an unsaturated double bond substituting group. Z accounts for 30%-50% molar ratio of the copolymer. In the unsaturated water-soluble polymer with -(X)-(Y)-(Z)-structure, the total number of unsaturated double bonds accounts for 60-80% mole ratio of the polymer. The photopolymerizable prepolymer is a urethane acrylic prepolymer. Photopolymerizable monomers are polyfunctional monomers. The photopolymerization initiator is selected from halogen-substituted triazine compounds. The chemical-free negative photosensitive composition suitable for UV-CTP also contains any one or a combination of phenolic resin, acrylic resin, and polyurethane resin as an additional component.

The lithographic printing plate made of the chemical-free negative photosensitive composition suitable for UV-CTP of the present invention comprises: (1) an aluminum base support, and (2) the above-mentioned - (X)-(Y)-(Z)-The hydrophilic layer of the unsaturated water-soluble polymer of structure, and (3) the above-mentioned suitable on the same side of the aluminum plate as the hydrophilic layer and on the hydrophilic layer Chemical-free negative photosensitive composition coating layer for UV-CTP.

In the lithographic printing plate of the present invention, the support body of the lithographic printing plate is an aluminum plate base which has undergone electrolytic roughening, anodic oxidation and sealing treatment, and the average thickness of the center line is 0.4-0.6um. The dry weight of the hydrophilized coating is 5-50 mg/dm ² .

The preparation method of the lithographic printing plate of the present invention is to coat the above-mentioned chemical-free negative photosensitive composition suitable for UV-CTP on the aluminum plate base after electrolytic roughening, anodic oxidation and sealing treatment.

In the method for making a lithographic printing plate in the present invention, before coating the above-mentioned chemical-free negative photosensitive composition suitable for UV-CTP on the aluminum plate base after electrolytic roughening, anodic oxidation and sealing treatment, use this Invention-(X)-(Y)-(Z)-structural unsaturated water-soluble polymer is used to hydrophilize the aluminum plate base. The lithographic plate is suitable for plate making using UV-CTP plate making machine. After the lithographic printing plate is scanned and exposed by using a UV-CTP plate making machine, it can be developed without using a developing solution and washed with tap water to obtain a printable lithographic printing plate. After the lithographic printing plate is scanned and exposed by using a UV-CTP plate-making machine, it can be directly mounted on a printing machine for printing without any treatment.

Because the present invention adopts components and methods, it has many advantages, and the specific comparison data are as follows: (the advantages are summarized, please sort out to the next place) the sensitivity is high, the network dot resignation is good, and it can be directly washed with tap water after being exposed with ultraviolet light source Or it can be printed on the machine without any processing steps. The graphic part of the printing plate has good lipophilicity, the blank part is not dirty, and can obtain high printing durability, especially suitable for UV-CTP plate making machines.

Its properties are listed in the following Table 1 (the embodiment in the table refers to the embodiment of the second part of the embodiment).

Table I

Description of drawings

Accompanying drawing is the cross-sectional structure schematic diagram of planographic printing plate among the present invention;

Detailed ways

The present invention is described in detail below in conjunction with accompanying drawing and embodiment:

The first part of the embodiment

Example 1

The chemical-free negative photosensitive composition suitable for UV-CTP of the present invention mainly includes the following six components: (1) an unsaturated water-soluble polymer of -(X)-(Y)-(Z)-structure , and (2) a photopolymerizable prepolymer, and (3) a polyfunctional monomer, and (4) one or more photopolymerization initiators, and (5) one or one More than one kind of dyes or pigments, and (6) one or more solvents; wherein, X represents a copolymerization unit containing a sulfonic acid group, and Y represents a branched carboxylic acid copolymerization unit containing two unsaturated double bonds , Z represents an acrylate copolymerized unit containing an unsaturated double bond branch.

X is selected from vinylsulfonic acid, styrenesulfonic acid, 2-hydroxyl-3-allyloxy-1-propylsulfonic acid, allyloxy Benzenesulfonic acid, 2-acrylamido-2-methylpropylsulfonic acid, isoprenesulfonic acid. X accounts for 10% molar ratio of the copolymer. Y is a branched acrylic or methacrylic copolymerized unit containing two unsaturated double bonds. Alternatively, Y is a GMA grafted acrylic or methacrylic copolymerized unit containing one unsaturated double bond substitution. Y accounts for 20% molar ratio of the copolymer. Z is an acrylate or methacrylic copolymer unit containing an unsaturated double bond substituting group. Z accounts for 30% molar ratio of the copolymer. In the unsaturated water-soluble polymer with -(X)-(Y)-(Z)-structure, the total number of unsaturated double bonds accounts for 60% of the molar ratio of the polymer. The photopolymerizable prepolymer is a urethane acrylic prepolymer. Photopolymerizable monomers are polyfunctional monomers. The photopolymerization initiator is selected from halogen-substituted triazine compounds. The chemical-free negative photosensitive composition suitable for UV-CTP also contains any one or a combination of phenolic resin, acrylic resin, and polyurethane resin as an additional component.

The lithographic printing plate made of the chemical-free negative photosensitive composition suitable for UV-CTP of the present invention comprises: (1) an aluminum plate base support (marker 3, the same as others), and (2) an aluminum plate base The hydrophilic layer of the unsaturated water-soluble polymer containing the above-mentioned -(X)-(Y)-(Z)-structure on the support (marking number 2 is the same as others), and (3) and the hydrophilic layer on the aluminum plate base On the same side and above the hydrophilic layer, the above-mentioned chemical-free negative photosensitive composition coating layer suitable for UV-CTP (reference number 3 others).

In the lithographic printing plate of the present invention, the support body of the lithographic printing plate is an aluminum plate base which has undergone electrolytic roughening, anodic oxidation and sealing treatment, and the average thickness of the center line is 0.4um. The dry weight of the hydrophilized coating was 5 mg/dm ² .

The preparation method of the lithographic printing plate of the present invention is to coat the above-mentioned chemical-free negative photosensitive composition suitable for UV-CTP on the aluminum plate base after electrolytic roughening, anodic oxidation and sealing treatment.

In the method for making a lithographic printing plate in the present invention, before coating the above-mentioned chemical-free negative photosensitive composition suitable for UV-CTP on the aluminum plate base after electrolytic roughening, anodic oxidation and sealing treatment, use this Invention-(X)-(Y)-(Z)-structural unsaturated water-soluble polymer is used to hydrophilize the aluminum plate base. The lithographic plate is suitable for plate making using UV-CTP plate making machine. After the lithographic printing plate is scanned and exposed by using a UV-CTP plate making machine, it can be developed without using a developing solution and washed with tap water to obtain a printable lithographic printing plate. After the lithographic printing plate is scanned and exposed by using a UV-CTP plate-making machine, it can be directly mounted on a printing machine for printing without any treatment.

Example 2

The chemical-free negative photosensitive composition suitable for UV-CTP of the present invention mainly includes the following six components: (1) an unsaturated water-soluble polymer of -(X)-(Y)-(Z)-structure , and (2) a photopolymerizable prepolymer, and (3) a polyfunctional monomer, and (4) one or more photopolymerization initiators, and (5) one or one More than one kind of dyes or pigments, and (6) one or more solvents; wherein, X represents a copolymerization unit containing a sulfonic acid group, and Y represents a branched carboxylic acid copolymerization unit containing two unsaturated double bonds , Z represents an acrylate copolymerized unit containing an unsaturated double bond branch.

X is selected from vinylsulfonic acid, styrenesulfonic acid, 2-hydroxyl-3-allyloxy-1-propylsulfonic acid, allyloxy Benzenesulfonic acid, 2-acrylamido-2-methylpropylsulfonic acid, isoprenesulfonic acid. X accounts for 15% molar ratio of the copolymer. Y is a branched acrylic or methacrylic copolymerized unit containing two unsaturated double bonds. Alternatively, Y is a GMA grafted acrylic or methacrylic copolymerized unit containing one unsaturated double bond substitution. Y accounts for 25% molar ratio of the copolymer. Z is an acrylate or methacrylic copolymer unit containing an unsaturated double bond substituting group. Z accounts for 35% molar ratio of the copolymer. In the unsaturated water-soluble polymer with -(X)-(Y)-(Z)-structure, the total number of unsaturated double bonds accounts for 65% of the molar ratio of the polymer. The photopolymerizable prepolymer is a urethane acrylic prepolymer. Photopolymerizable monomers are polyfunctional monomers. The photopolymerization initiator is selected from halogen-substituted triazine compounds. The chemical-free negative photosensitive composition suitable for UV-CTP also contains any one or a combination of phenolic resin, acrylic resin, and polyurethane resin as an additional component.

The lithographic printing plate made of the chemical-free negative photosensitive composition suitable for UV-CTP of the present invention comprises: (1) an aluminum base support, and (2) the above-mentioned - (X)-(Y)-(Z)-The hydrophilic layer of the unsaturated water-soluble polymer of structure, and (3) the above-mentioned suitable on the same side of the aluminum plate as the hydrophilic layer and on the hydrophilic layer Chemical-free negative photosensitive composition coating layer for UV-CTP.

In the lithographic printing plate of the present invention, the support body of the lithographic printing plate is an aluminum plate base that has undergone electrolytic roughening, anodic oxidation and sealing treatment, and the average thickness of the center line is 0.45um. The dry weight of the hydrophilized coating was 15 mg/dm ² .

The preparation method of the lithographic printing plate of the present invention is to coat the above-mentioned chemical-free negative photosensitive composition suitable for UV-CTP on the aluminum plate base after electrolytic roughening, anodic oxidation and sealing treatment.

In the method for making a lithographic printing plate in the present invention, before coating the above-mentioned chemical-free negative photosensitive composition suitable for UV-CTP on the aluminum plate base after electrolytic roughening, anodic oxidation and sealing treatment, use this Invention-(X)-(Y)-(Z)-structural unsaturated water-soluble polymer is used to hydrophilize the aluminum plate base. The lithographic plate is suitable for plate making using UV-CTP plate making machine. After the lithographic printing plate is scanned and exposed by using a UV-CTP plate making machine, it can be developed without using a developing solution and washed with tap water to obtain a printable lithographic printing plate. After the lithographic printing plate is scanned and exposed by using a UV-CTP plate-making machine, it can be directly mounted on a printing machine for printing without any treatment.

Example 3

The chemical-free negative photosensitive composition suitable for UV-CTP of the present invention mainly includes the following six components: (1) an unsaturated water-soluble polymer of -(X)-(Y)-(Z)-structure , and (2) a photopolymerizable prepolymer, and (3) a polyfunctional monomer, and (4) one or more photopolymerization initiators, and (5) one or one More than one kind of dyes or pigments, and (6) one or more solvents; wherein, X represents a copolymerization unit containing a sulfonic acid group, and Y represents a branched carboxylic acid copolymerization unit containing two unsaturated double bonds , Z represents an acrylate copolymerized unit containing an unsaturated double bond branch.

X is selected from vinylsulfonic acid, styrenesulfonic acid, 2-hydroxyl-3-allyloxy-1-propylsulfonic acid, allyloxy Benzenesulfonic acid, 2-acrylamido-2-methylpropylsulfonic acid, isoprenesulfonic acid. X accounts for 20% molar ratio of the copolymer. Y is a branched acrylic or methacrylic copolymerized unit containing two unsaturated double bonds. Alternatively, Y is a GMA grafted acrylic or methacrylic copolymerized unit containing one unsaturated double bond substitution. Y accounts for 30% molar ratio of the copolymer. Z is an acrylate or methacrylic copolymer unit containing an unsaturated double bond substituting group. Z accounts for 40% molar ratio of the copolymer. In the unsaturated water-soluble polymer with -(X)-(Y)-(Z)-structure, the total number of unsaturated double bonds accounts for 70% of the molar ratio of the polymer. The photopolymerizable prepolymer is a urethane acrylic prepolymer. Photopolymerizable monomers are polyfunctional monomers. The photopolymerization initiator is selected from halogen-substituted triazine compounds. The chemical-free negative photosensitive composition suitable for UV-CTP also contains any one or a combination of phenolic resin, acrylic resin, and polyurethane resin as an additional component.

The lithographic printing plate made of the chemical-free negative photosensitive composition suitable for UV-CTP of the present invention comprises: (1) an aluminum base support, and (2) the above-mentioned - (X)-(Y)-(Z)-The hydrophilic layer of the unsaturated water-soluble polymer of structure, and (3) the above-mentioned suitable on the same side of the aluminum plate as the hydrophilic layer and on the hydrophilic layer Chemical-free negative photosensitive composition coating layer for UV-CTP.

In the lithographic printing plate of the present invention, the support body of the lithographic printing plate is an aluminum plate base which has undergone electrolytic roughening, anodic oxidation and sealing treatment, and the average thickness of the center line is 0.5um. The dry weight of the hydrophilized coating was 30 mg/dm ² .

The preparation method of the lithographic printing plate of the present invention is to coat the above-mentioned chemical-free negative photosensitive composition suitable for UV-CTP on the aluminum plate base after electrolytic roughening, anodic oxidation and sealing treatment.

In the method for making a lithographic printing plate in the present invention, before coating the above-mentioned chemical-free negative photosensitive composition suitable for UV-CTP on the aluminum plate base after electrolytic roughening, anodic oxidation and sealing treatment, use this Invention-(X)-(Y)-(Z)-structural unsaturated water-soluble polymer is used to hydrophilize the aluminum plate base. The lithographic plate is suitable for plate making using UV-CTP plate making machine. After the lithographic printing plate is scanned and exposed by using a UV-CTP plate making machine, it can be developed without using a developing solution and washed with tap water to obtain a printable lithographic printing plate. After the lithographic printing plate is scanned and exposed by using a UV-CTP plate-making machine, it can be directly mounted on a printing machine for printing without any treatment.

Example 4

The chemical-free negative photosensitive composition suitable for UV-CTP of the present invention mainly includes the following six components: (1) an unsaturated water-soluble polymer of -(X)-(Y)-(Z)-structure , and (2) a photopolymerizable prepolymer, and (3) a polyfunctional monomer, and (4) one or more photopolymerization initiators, and (5) one or one More than one kind of dyes or pigments, and (6) one or more solvents; wherein, X represents a copolymerization unit containing a sulfonic acid group, and Y represents a branched carboxylic acid copolymerization unit containing two unsaturated double bonds , Z represents an acrylate copolymerized unit containing an unsaturated double bond branch.

X is selected from vinylsulfonic acid, styrenesulfonic acid, 2-hydroxyl-3-allyloxy-1-propylsulfonic acid, allyloxy Benzenesulfonic acid, 2-acrylamido-2-methylpropylsulfonic acid, isoprenesulfonic acid. X accounts for 25% molar ratio of the copolymer. Y is a branched acrylic or methacrylic copolymerized unit containing two unsaturated double bonds. Alternatively, Y is a GMA grafted acrylic or methacrylic copolymerized unit containing one unsaturated double bond substitution. Y accounts for 35% molar ratio of the copolymer. Z is an acrylate or methacrylic copolymer unit containing an unsaturated double bond substituting group. Z accounts for 45% molar ratio of the copolymer. In the unsaturated water-soluble polymer with -(X)-(Y)-(Z)-structure, the total number of unsaturated double bonds accounts for 75% of the molar ratio of the polymer. The photopolymerizable prepolymer is a urethane acrylic prepolymer. Photopolymerizable monomers are polyfunctional monomers. The photopolymerization initiator is selected from halogen-substituted triazine compounds. The chemical-free negative photosensitive composition suitable for UV-CTP also contains any one or a combination of phenolic resin, acrylic resin, and polyurethane resin as an additional component.

The lithographic printing plate made of the chemical-free negative photosensitive composition suitable for UV-CTP of the present invention comprises: (1) an aluminum base support, and (2) the above-mentioned - (X)-(Y)-(Z)-The hydrophilic layer of the unsaturated water-soluble polymer of structure, and (3) the above-mentioned suitable on the same side of the aluminum plate as the hydrophilic layer and on the hydrophilic layer Chemical-free negative photosensitive composition coating layer for UV-CTP.

In the lithographic printing plate of the present invention, the support body of the lithographic printing plate is an aluminum plate base that has undergone electrolytic roughening, anodic oxidation and sealing treatment, and the average thickness of the center line is 0.55um. The dry weight of the hydrophilized coating was 40 mg/dm ² .

The preparation method of the lithographic printing plate of the present invention is to coat the above-mentioned chemical-free negative photosensitive composition suitable for UV-CTP on the aluminum plate base after electrolytic roughening, anodic oxidation and sealing treatment.

In the method for making a lithographic printing plate in the present invention, before coating the above-mentioned chemical-free negative photosensitive composition suitable for UV-CTP on the aluminum plate base after electrolytic roughening, anodic oxidation and sealing treatment, use this Invention-(X)-(Y)-(Z)-structural unsaturated water-soluble polymer is used to hydrophilize the aluminum plate base. The lithographic plate is suitable for plate making using UV-CTP plate making machine. After the lithographic printing plate is scanned and exposed by using a UV-CTP plate making machine, it can be developed without using a developing solution and washed with tap water to obtain a printable lithographic printing plate. After the lithographic printing plate is scanned and exposed by using a UV-CTP plate-making machine, it can be directly mounted on a printing machine for printing without any treatment.

Example 5

The chemical-free negative photosensitive composition suitable for UV-CTP of the present invention mainly includes the following six components: (1) an unsaturated water-soluble polymer of -(X)-(Y)-(Z)-structure , and (2) a photopolymerizable prepolymer, and (3) a polyfunctional monomer, and (4) one or more photopolymerization initiators, and (5) one or one More than one kind of dyes or pigments, and (6) one or more solvents; wherein, X represents a copolymerization unit containing a sulfonic acid group, and Y represents a branched carboxylic acid copolymerization unit containing two unsaturated double bonds , Z represents an acrylate copolymerized unit containing an unsaturated double bond branch.

X is selected from vinylsulfonic acid, styrenesulfonic acid, 2-hydroxyl-3-allyloxy-1-propylsulfonic acid, allyloxy Benzenesulfonic acid, 2-acrylamido-2-methylpropylsulfonic acid, isoprenesulfonic acid. X accounts for 30% molar ratio of the copolymer. Y is a branched acrylic or methacrylic copolymerized unit containing two unsaturated double bonds. Alternatively, Y is a GMA grafted acrylic or methacrylic copolymerized unit containing one unsaturated double bond substitution. Y accounts for 40% molar ratio of the copolymer. Z is an acrylate or methacrylic copolymer unit containing an unsaturated double bond substituting group. Z accounts for 50% molar ratio of the copolymer. In the unsaturated water-soluble polymer with -(X)-(Y)-(Z)-structure, the total number of unsaturated double bonds accounts for 80% of the molar ratio of the polymer. The photopolymerizable prepolymer is a urethane acrylic prepolymer. Photopolymerizable monomers are polyfunctional monomers. The photopolymerization initiator is selected from halogen-substituted triazine compounds. The chemical-free negative photosensitive composition suitable for UV-CTP also contains any one or a combination of phenolic resin, acrylic resin, and polyurethane resin as an additional component.

The lithographic printing plate made of the chemical-free negative photosensitive composition suitable for UV-CTP of the present invention comprises: (1) an aluminum base support, and (2) the above-mentioned - (X)-(Y)-(Z)-The hydrophilic layer of the unsaturated water-soluble polymer of structure, and (3) the above-mentioned suitable on the same side of the aluminum plate as the hydrophilic layer and on the hydrophilic layer Chemical-free negative photosensitive composition coating layer for UV-CTP.

In the lithographic printing plate of the present invention, the support body of the lithographic printing plate is an aluminum plate base which has undergone electrolytic roughening, anodic oxidation and sealing treatment, and the average thickness of the center line is 0.6um. The dry weight of the hydrophilized coating was 50 mg/dm ² .

The preparation method of the lithographic printing plate of the present invention is to coat the above-mentioned chemical-free negative photosensitive composition suitable for UV-CTP on the aluminum plate base after electrolytic roughening, anodic oxidation and sealing treatment.

In the method for making a lithographic printing plate in the present invention, before coating the above-mentioned chemical-free negative photosensitive composition suitable for UV-CTP on the aluminum plate base after electrolytic roughening, anodic oxidation and sealing treatment, use this Invention-(X)-(Y)-(Z)-structural unsaturated water-soluble polymer is used to hydrophilize the aluminum plate base. The lithographic plate is suitable for plate making using UV-CTP plate making machine. After the lithographic printing plate is scanned and exposed by using a UV-CTP plate making machine, it can be developed without using a developing solution and washed with tap water to obtain a printable lithographic printing plate. After the lithographic printing plate is scanned and exposed by using a UV-CTP plate-making machine, it can be directly mounted on a printing machine for printing without any treatment.

Example 6

The chemical-free negative photosensitive composition suitable for UV-CTP of the present invention mainly includes the following six components: (1) an unsaturated water-soluble polymer of -(X)-(Y)-(Z)-structure , and (2) a photopolymerizable prepolymer, and (3) a polyfunctional monomer, and (4) one or more photopolymerization initiators, and (5) one or one More than one kind of dyes or pigments, and (6) one or more solvents; wherein, X represents a copolymerization unit containing a sulfonic acid group, and Y represents a branched carboxylic acid copolymerization unit containing two unsaturated double bonds , Z represents an acrylate copolymerized unit containing an unsaturated double bond branch.

X is selected from vinylsulfonic acid, styrenesulfonic acid, 2-hydroxy-3-allyloxy-1-propylsulfonic acid, allyloxy Benzenesulfonic acid, 2-acrylamido-2-methylpropylsulfonic acid, isoprenesulfonic acid. X accounts for 10% to 30% molar ratio of the copolymer. Y is a branched acrylic or methacrylic copolymerized unit containing two unsaturated double bonds. Alternatively, Y is a GMA grafted acrylic or methacrylic copolymerized unit containing one unsaturated double bond substitution. Y accounts for 20%-40% molar ratio of the copolymer. Z is an acrylate or methacrylic copolymer unit containing an unsaturated double bond substituting group. Z accounts for 30%-50% molar ratio of the copolymer. In the unsaturated water-soluble polymer with -(X)-(Y)-(Z)-structure, the total number of unsaturated double bonds accounts for 60-80% mole ratio of the polymer. The photopolymerizable prepolymer is a urethane acrylic prepolymer. Photopolymerizable monomers are polyfunctional monomers. The photopolymerization initiator is selected from halogen-substituted triazine compounds. The chemical-free negative photosensitive composition suitable for UV-CTP also contains any one or a combination of phenolic resin, acrylic resin, and polyurethane resin as an additional component.

The lithographic printing plate made of the chemical-free negative photosensitive composition suitable for UV-CTP of the present invention comprises: (1) an aluminum base support, and (2) the above-mentioned - (X)-(Y)-(Z)-The hydrophilic layer of the unsaturated water-soluble polymer of structure, and (3) the above-mentioned suitable on the same side of the aluminum plate as the hydrophilic layer and on the hydrophilic layer Chemical-free negative photosensitive composition coating layer for UV-CTP.

In the lithographic printing plate of the present invention, the support body of the lithographic printing plate is an aluminum plate base which has undergone electrolytic roughening, anodic oxidation and sealing treatment, and the average thickness of the center line is 0.4-0.6um. The dry weight of the hydrophilized coating is 5-50 mg/dm ² .

The preparation method of the lithographic printing plate of the present invention is to coat the above-mentioned chemical-free negative photosensitive composition suitable for UV-CTP on the aluminum plate base after electrolytic roughening, anodic oxidation and sealing treatment.

In the method for making a lithographic printing plate in the present invention, before coating the above-mentioned chemical-free negative photosensitive composition suitable for UV-CTP on the aluminum plate base after electrolytic roughening, anodic oxidation and sealing treatment, use this Invention-(X)-(Y)-(Z)-structural unsaturated water-soluble polymer is used to hydrophilize the aluminum plate base. The lithographic plate is suitable for plate making using UV-CTP plate making machine. After the lithographic printing plate is scanned and exposed by using a UV-CTP plate making machine, it can be developed without using a developing solution and washed with tap water to obtain a printable lithographic printing plate. After the lithographic printing plate is scanned and exposed by using a UV-CTP plate-making machine, it can be directly mounted on a printing machine for printing without any treatment. Each of the above parameters can take any value within its range as required.

The second part of the embodiment

The lithographic printing plate of the invention has high sensitivity and good dot resolution, and can be directly washed with tap water or printed on a machine without any washing steps after being exposed to an ultraviolet light source. The graphic part of the printing plate has good lipophilicity, the blank part is not dirty, and can obtain high printing force, especially suitable for UV-CTP plate making machine-made plates. The lithographic printing plate of the invention does not contain diazonium salt and has a single photosensitive layer structure. The lithographic printing plate of the present invention has high sensitivity and good dot resolution, and can be directly washed with tap water or printed on the machine without any washing process after exposure to ultraviolet light sources, and can obtain high printing resistance, especially suitable for UV- CTP platemaking machine. The object of the present invention can be achieved through the following measures:

The chemical-free negative photosensitive composition suitable for UV-CTP of the present invention (referred to as the photosensitive composition, the same as others) comprises: (1) an unsaturated water-soluble compound with the structure -(X)-(Y)-(Z) A permanent polymer, characterized in that X represents a copolymerization unit containing a sulfonic acid group, Y represents a carboxylic acid copolymerization unit containing two unsaturated double bond branches, and Z represents an acrylate copolymerization unit containing an unsaturated double bond branch. unit, and (2) a photopolymerizable prepolymer, and (3) a polyfunctional monomer, and (4) one or more photopolymerization initiators, and (5) one or More than one dye or pigment.

The lithographic printing plate of the present invention is obtained by using the aluminum plate base that has been electrolytically roughened, anodized and sealed as a support, and coated with the photosensitive composition of the present invention. The centerline average thickness of the support is 0.4-0.6um. Before coating the photosensitive composition of the present invention, the solution of the water-soluble resin of the -(X)-(Y)-(Z)-structure of the present invention is used for plate alignment The base is hydrophilized.

The -(X)-(Y)-(Z)-structure polymer in the photosensitive composition of the present invention is a water-soluble polymer containing unsaturated double bonds. Wherein, X represents a copolymerization unit containing sulfonic acid groups, Y represents a carboxylic acid copolymerization unit containing two unsaturated double bond branches, and Z represents an acrylate copolymerization unit containing one unsaturated double bond branch chain.

As the copolymerized unit represented by X, any compound may be used as long as it is a compound containing an ethylenically unsaturated group and a sulfonic acid group. The ethylenically unsaturated group guarantees copolymerization with other units, and the sulfonic acid group ensures better water solubility. X may be selected from vinylsulfonic acid, styrenesulfonic acid, 2-hydroxy-3-allyloxy-1-propylsulfonic acid, allyloxybenzenesulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, isoprene sulfonic acid, etc. The proportion of X in the whole polymer is in the range of 10%-30% molar ratio, preferably 15%-25%. When it is lower than 10%, the blank part of the printing plate is easy to leave a bottom, and when it is higher than 30%, the ink affinity of the printing plate is not good.

The copolymerized unit represented by Y is a branched acrylic or methacrylic copolymerized unit containing two unsaturated double bonds. The branched chain containing two unsaturated double bonds is achieved by first grafting GMA monomer on acrylic acid or methacrylic acid, and then grafting ethylenically unsaturated double bonds on GMA. The ethylenically unsaturated monomers that can be used for grafting can be selected from acryloyl chloride, methacryloyl chloride, allyl isocyanate, isocyanatoethyl methacrylate, and the like. Y plays the role of adjusting hydrophilicity and photocrosslinking curing speed in the whole polymer. By introducing two unsaturated groups on Y, the ratio of unsaturated double bonds in the polymer can be greatly improved. In the present invention, according to the needs Even the proportion of unsaturated double bonds in the entire polymer can reach 150%, which can greatly increase the photocuring speed while ensuring sufficient hydrophilicity. The proportion of Y in the whole polymer is preferably within the molar ratio range of 20%-40%, preferably 25%-30%.

As the copolymerized unit represented by Z, Z is an acrylate or methacrylic copolymerized unit having an unsaturated double bond substituent group. Usable acrylates may be selected from beta hydroxyethyl acrylate, beta hydroxyethyl methacrylate, methyl hydroxymethacrylate, and the like. Available grafting monomers include acryloyl chloride, methacryloyl chloride, allyl isocyanate, and isocyanatoethyl methacrylate. The proportion of Z in the whole copolymer is preferably in the range of 30%-50% molar ratio, preferably 35%-45%.

In the unsaturated water-soluble polymer with -(X)-(Y)-(Z)-structure, the total number of unsaturated double bonds accounts for 60-80% molar ratio of the polymer, preferably 65-75%. When it is lower than 60%, high curing speed and high crosslinking density cannot be obtained; when it is higher than 80%, it is unfavorable for the storage stability of the resin.

The unsaturated water-soluble polymer of -(X)-(Y)-(Z)-structure accounts for 40%-80% of the dry weight of the entire photosensitive layer, preferably 50%-70%. When it is lower than 40%, the coating on the blank part is not easy to erase, and it is easy to get dirty on the blank part; when it is higher than 80%, the ink affinity of the coating is not good, and it is easy to blind the plate.

The photopolymerizable prepolymer of the present invention can use various types of prepolymers, such as polyester acrylates, epoxy acrylates, polyurethane acrylates, polyether acrylates, silicone prepolymers polymers, etc., among which polyurethane acrylic prepolymer is preferred. The prepolymer preferably accounts for 1-50% of the dry weight of the coating film in the photosensitive coating, preferably 5%-30%. When the dosage is less than 1%, the curing speed is low, and the ink affinity of the coating is not good; when the dosage exceeds 50%, the dot reduction is not good, and the coating is easy to stick.

The photopolymerizable monomers of the present invention can use various types of monomers, such as: monofunctional monomers, such as (meth)acrylic acid esters such as ethyl acrylate, butyl acrylate, allyl acrylate, etc.; Functional group monomers, including diacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate and tetraacrylate, 1,3,5-tri-(2-acryloyloxyethyl)isocyanuric acid Ester, hydroxypropyl glyceryl triacrylate, hydroxyethyl trimethylolpropane triacrylate, polyethylene glycol dimethacrylate, etc.; isocyanate-based monomers, including 2-isocyanate methacrylic acid Ethyl ester and dimethyl-m-isopropenyl benzyl isocyanate and so on. Preferably multifunctional monomers are used. The multifunctional monomer preferably accounts for 1-80% of the dry weight of the coating film in the photosensitive coating, preferably 10%-50%.

The photoinitiator of the present invention can be a single compound or a combination of two or more components. Preferably, photoinitiators are used which initiate crosslinking by generating free radicals upon exposure. Preferred photoinitiators are active upon exposure to 200 to 500 nm (eg, ultraviolet, visible and infrared radiation). The best photoinitiators are active at 300 to 450 nm. Suitable visible and UV-induced photoinitiators include, ketones such as benzils, benzoins and azoins, for example, 2,2-dimethoxy-2-phenylacetophenone, 2-benzyl - 2-N, N-dimethylamino-1-(4-morpholinated benzyl)-1-butanone and benzoin methyl ester (2-methoxy-2-phenylacetophenone), etc. ; Sensitized diaryl iodonium salts and triaryl sulfonium salts, etc.; chromophore-substituted halomethyl-1, 3, 5-triazine compounds, etc. All of these photoinitiators are used alone or together with suitable accelerators (such as amines, peroxides, and phosphorus compounds) and/or suitable photosensitizers (such as ketones or alpha-diketone compounds such as camphorquinone) use. The photoinitiator is preferably present in the structures of the invention in sufficient amount to obtain the desired degree of polymerization. This amount depends on the efficiency of the photoinitiator and the thickness of the photoactive layer. Usually the content of photoinitiator is 0.01 to 20 (weight) based on the dry weight of the coating. The preferred content of photoinitiator in the present invention is 0.5% to 15%, preferably 0.5% to 10% of the dry weight of the coating.

An optional component of a lithographic plate in the present invention is a colorant and/or a dye or dye system. In order to have a visible image after exposure, a colorant and/or dye or dye system may be added. A suitable compound or system can change color or shade when it is exposed to actinic radiation or when it contacts a product from an exposed photoinitiator. Suitable compounds or systems include (but are not limited to), such as leuco-dyes, such as acyl-protected thiazines, diazines and oxazines, dimerized water molecules (such as Michler's dimerized water molecules), indolenes and Triarylmethane lactones (such as Crystal Violet lactone). The level of dye in the lithographic plates of this invention should be sufficient to obtain the desired contrast between exposed and unexposed portions of the plate. The preferred level of dye is from 0 to 10% by weight of the coating.

Also, the photosensitive composition of the present invention may contain various materials in combination with the essential components of the present invention. For example, pigments, organic or inorganic particles, sensitized dyes, plasticizers, binders, surfactants, antioxidants, coating aids, antistabilizers, waxes, UV or visible light absorbers and brighteners can be used The invention does not affect its performance.

The plate base used in the present invention is an aluminum plate base after electrolytic roughening, anodic oxidation and sealing treatment, and the average thickness of the center line is 0.4-0.6um. Preferably 0.3-0.5um. Such plates can be prepared by various electrolytic roughening methods. The aluminum plate base of the present invention is a high-purity aluminum plate, and its aluminum content is preferably above 99%. Suitable aluminum bases are (but not limited to): 0.1%-0.5% iron, 0.03%-0.3% silicon, 0.003%-0.03% copper, and 0.01%-0.1% titanium. The electrolytic solution used for electrolytic roughening may be an aqueous solution of acid, alkali or salt or an aqueous solution containing an organic solvent. Among them, an aqueous solution of hydrochloric acid, nitric acid or their salts is preferably used as the electrolytic solution. First, put the aluminum plate in an aqueous solution of 1% to 30% sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, etc., and perform chemical corrosion for 5 to 250 seconds at a temperature of 20 to 80°C. Then neutralize in 10-30% nitric acid or sulfuric acid at a temperature of 20-70°C to remove ash. In this way, the cleaned aluminum plate, at a temperature of 10-60°C, uses a rectangular wave, a table wave or a sine wave with alternating positive and negative, and a current density of 5-100A/ ^dm2 in nitric acid or hydrochloric acid. Electrolytic treatment in the electrolyte solution for 10 to 300 seconds. Next, the electrolytic aluminum plate is anodized. Anodizing is usually done by the sulfuric acid method. The concentration of sulfuric acid used is 5-30%, the current density is 1-15A/dm ² , the oxidation temperature is 20-60°C, and the oxidation time is 5-250 seconds to form an oxide film of 1-10g/m ² . The oxide film formed in this way usually has relatively high oxide film micropores, strong adsorption capacity, and is easy to adhere to dirt. Therefore, sealing is usually required. Various methods can be used for the sealing treatment, and it is better to achieve 50% to 80% volume of the micropores of the sealed oxide film.

The photosensitive composition of the present invention is usually coated on the plate base by techniques known in the art (eg, knife coating, blade coating, bar coating, roller coating, press coating, etc.). The photosensitive composition of the present invention is dissolved in an appropriate solvent or/and water to form a coating solution. Suitable solvents are: ethylene glycol ethyl ether, ethylene glycol methyl ether, diethylene glycol methyl ether, methyl lactate, ethyl lactate, methyl ethyl ketone, 1-methoxy-2-propanol, etc. The dry weight of the coating is 0.2-10g/m ² . The optimal coating amount of the photosensitive composition coating is 0.5g/m ² -3g/m ² .

Before coating the photosensitive composition of the present invention, it is preferable to coat the unsaturated water-soluble polymer of the present invention-(X)-(Y)-(Z)-structure on the plate base that has been sealed. As the coating method, various methods such as knife coating, knife coating, bar coating, roll coating, press coating, slot die coating and the like can be used. Before coating, the -(X)-(Y)-(Z)-structure polymer is dissolved in water to make an appropriate concentration, or various coating aids are added to adjust to the appropriate coating parameters. The dry weight of the hydrophilized coating is preferably in the range of 0.01-100 mg/dm ² , preferably 5-50 mg/dm ² . If it is less than 0.01mg/dm ² , the expected effect will not be achieved; if it exceeds 50mg/dm ² , the bonding force between the coating and the plate base will decrease, which will easily cause plate drop and other disadvantages.

The invention is illustrated below by way of examples, but is not limited to these strengths.

Synthesis Example 1

In a 500 ml three-neck flask, 210 ml of DMF was added as a solvent, and then 14.4 g of acrylic acid, 32.6 g of β-hydroxyethyl methacrylate and 10.35 g of 2-acrylamido-2-methylpropanesulfonic acid were added. Such a solution was heated up while stirring under the condition of feeding N ₂ , when the temperature rose to 80° C., 0.3 g of AIBN was added, and the reaction was kept at this temperature for 4.5 hours. Thereafter, 10.66 g of GMA, 0.1 g of p-methoxyphenol and 8.22 g of tetramethylammonium chloride were added to the solution, and the reaction was continued for 4.5 hours while maintaining at 80°C. Subsequently, the temperature of the above solution was lowered to 30°C, and then 29.41 g of acryloyl chloride, 0.3 g of p-methoxyphenol, and 32.89 g of triethylamine were added, and the reaction was maintained at a temperature of 30°C for 1.5 hours. Finally, the above solution was dispersed in methyl lactate and dried to obtain about 90 g of the water-soluble polymer 1 of the present invention.

Synthesis example 2

210 ml of DMF was added as a solvent into a 500 ml three-necked flask, and then 7.2 g of acrylic acid, 32.6 g of β-hydroxyethyl methacrylate and 31.05 g of 2-acrylamido-2-methylpropanesulfonic acid were added respectively. Such a solution was heated up while stirring under the condition of feeding N ₂ , when the temperature rose to 80° C., 0.3 g of AIBN was added, and the reaction was kept at this temperature for 4.5 hours. Afterwards, 3.55 grams of GMA, 0.04 grams of p-methoxyphenol and 2.74 grams of tetramethylammonium chloride were added to such a solution, and the reaction was continued for 4.5 hours at 80° C. Subsequently, the temperature of the above solution was lowered to 30°C, and 24.89 g of acryloyl chloride, 0.25 g of p-methoxyphenol, and 27.83 g of triethylamine were added, and the reaction was maintained at 30°C for 1.5 hours. Finally, the above solution was dispersed in methyl lactate and dried to obtain about 92 grams of the water-soluble polymer 2 of the present invention.

Synthesis example 3

In a 500 ml three-neck flask, 210 ml of DMF was added as a solvent, and then 14.4 g of acrylic acid, 17.41 g of β-hydroxyethyl acrylate and 31.05 g of 2-acrylamido-2-methylpropanesulfonic acid were added. Such a solution was heated up while stirring under the condition of feeding N ₂ , when the temperature rose to 80° C., 0.3 g of AIBN was added, and the reaction was kept at this temperature for 4.5 hours. Then, 17.77 g of GMA, 0.18 g of p-methoxyphenol, and 13.70 g of tetramethylammonium chloride were added to this solution, and the reaction was continued for 4.5 hours while maintaining at 80°C. Subsequently, the temperature of the above solution was lowered to 30°C, and 24.89 g of acryloyl chloride, 0.25 g of p-methoxyphenol, and 27.83 g of triethylamine were added, and the reaction was maintained at 30°C for 1.5 hours. Finally, the above solution was dispersed in methyl lactate and dried to obtain about 88 grams of the water-soluble polymer 3 of the present invention.

Synthesis Example 4

In a 500 ml three-neck flask, 210 ml of DMF was added as a solvent, and then 10.8 g of acrylic acid, 26.11 g of β-hydroxyethyl acrylate and 25.88 g of 2-acrylamido-2-methylpropanesulfonic acid were added respectively. Such a solution was heated up while stirring under the condition of feeding N ₂ , when the temperature rose to 80° C., 0.3 g of AIBN was added, and the reaction was kept at this temperature for 4.5 hours. After that, 8.89 g of GMA, 0.1 g of p-methoxyphenol and 6.85 g of tetramethylammonium chloride were added to such a solution, and the reaction was continued for 4.5 hours at 80° C. Subsequently, the temperature of the above solution was lowered to 30°C, and then 26.06 g of acryloyl chloride, 0.26 g of p-methoxyphenol, and 29.15 g of triethylamine were added, and the reaction was maintained at 30°C for 1.5 hours. Finally, the above solution was dispersed in methyl lactate and dried to obtain about 90 grams of the water-soluble polymer 4 of the present invention.

Synthesis Example 5

210 ml of DMF was added as a solvent in a 500 ml three-neck flask, and then 14.4 g of acrylic acid, 23.21 g of β-hydroxyethyl acrylate and 20.7 g of 2-acrylamido-2-methylpropanesulfonic acid were added respectively. Such a solution was heated up while stirring under the condition of feeding N ₂ , when the temperature rose to 80° C., 0.3 g of AIBN was added, and the reaction was kept at this temperature for 4.5 hours. Then, 14.22 g of GMA, 0.15 g of p-methoxyphenol, and 11 g of 4-methylammonium chloride were added to such a solution, and the reaction was continued for 4.5 hours while maintaining at 80° C. Subsequently, the temperature of the above solution was lowered to 30°C, and then 27.15 g of acryloyl chloride, 0.3 g of p-methoxyphenol, and 30.36 g of triethylamine were added, and the reaction was maintained at 30°C for 1.5 hours. Finally, the above solution was dispersed in methyl lactate and dried to obtain about 86 grams of the water-soluble polymer 5 of the present invention.

Example 1

Preparation of plate base: A1050 rolled aluminum plate with a purity of 99.5% and a thickness of 0.3mm was etched in 5% sodium hydroxide aqueous solution at 70°C for 20 seconds, rinsed with running water, and immediately neutralized with 1% nitric acid aqueous solution. Then in 1% hydrochloric acid aqueous solution, at 40°C, use sine wave alternating current with a current density of 50A/ ^dm2 for 16 seconds. Next, at 40° C., neutralize with a 5% aqueous sodium hydroxide solution for 10 seconds. wash. Finally, at 30°C, use 20% sulfuric acid aqueous solution to anodize for 20 seconds at a current density of 15A/dm ² . wash. Seal the holes with 5% sodium silicate aqueous solution for 18 seconds at 80°C. wash. dry. The plate base obtained in this way has an average centerline thickness of 0.5um and an oxide film weight of 3.0g/dm ² .

Hydrophilic treatment: on the plate base obtained above, coat 0.1% aqueous solution of the water-soluble resin of the present invention, and dry at 100° C. for 20 seconds to obtain a coating dry weight of 20 mg/m ² .

Extrude-coat the following photosensitive solution on the above-mentioned hydrophilized plate base, and then dry at 120° C. for 30 seconds. A coating dry weight of 1.5 g/m ² was obtained.

Photosensitive solution 1 (each component is by weight)

Water-soluble polymer 1 of the present invention 1.6

Polyurethane Acrylic Prepolymer 0.64

Pentaerythritol triacrylate 0.86

2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine 0.03

p-methoxyphenol 0.03

BYK-306 0.012

Phthalocyanine blue dye 0.032

1-methoxy-2-propylene 32.80

The plate material obtained in this way was exposed with a light value of 60 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without rinsing with tap water. Its properties are listed in Table 1 below.

Example 2

Use the same method as above to prepare the plate base, hydrophilic layer and coating photosensitive liquid. Photosensitive liquid with the following components:

Photosensitive solution 2 (each component is by weight)

Water-soluble polymer 2 of the present invention 1.6

Polyurethane Acrylic Prepolymer 0.64

Pentaerythritol triacrylate 0.86

2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine 0.03

p-methoxyphenol 0.03

BYK-306 0.012

Phthalocyanine blue dye 0.032

1-methoxy-2-propanol                                                                            

The plate material obtained in this way was exposed with a light value of 80 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without washing with tap water. Its properties are listed in Table 1 below.

Example 3

Use the same method above to prepare the plate base, hydrophilic layer and coating photosensitive liquid. Photosensitive liquid with the following components:

Photosensitive liquid 3 (each component is by weight)

Water-soluble polymer 3 of the present invention 1.6

Polyurethane Acrylic Prepolymer 0.64

Pentaerythritol triacrylate 0.86

2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine 0.03

p-Methoxyphenol 0.03

BYK-306 0.012

Phthalocyanine blue dye 0.032

1-methoxy-2-propylene 32.80

The plate material obtained in this way was exposed with a light value of 60 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without washing with tap water. Its properties are listed in Table 1 below.

Example 4

Use the same method above to prepare the plate base, hydrophilic layer and coating photosensitive liquid. Photosensitive liquid with the following components:

Photosensitive liquid 4 (each component is by weight)

Water-soluble polymer 4 of the present invention 1.6

Polyurethane Acrylic Prepolymer 0.64

Pentaerythritol triacrylate 0.86

2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine 0.03

p-Methoxyphenol 0.03

BYK-306 0.012

Phthalocyanine blue dye 0.032

1-methoxy-2-propylene 32.80

The plate material obtained in this way was exposed with a light value of 70 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without washing with tap water. Its properties are listed in Table 1 below.

Example 5

Use the same method as above to prepare the plate base, hydrophilic layer and coating photosensitive liquid. Photosensitive liquid with the following components:

Photosensitive liquid 5 (each component is by weight)

Water-soluble polymer 5 of the present invention 1.6

Polyurethane Acrylic Prepolymer 0.64

Pentaerythritol triacrylate 0.86

2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine 0.03

p-Methoxyphenol 0.03

BYK-306 0.012

Phthalocyanine blue dye 0.032

1-methoxy-2-propylene 32.80

The plate material obtained in this way was exposed with a light value of 60 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without washing with tap water. Its properties are listed in Table 1 below.

Example 6

Prepare plate base, hydrophilic layer and coating photosensitive liquid with the same method as Example 1. Just adjust the electrolytic power to make the average thickness of the center line of the plate base be 0.4um.

The plate material obtained in this way was exposed with a light value of 60 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without washing with tap water. Its properties are listed in Table 1 below.

Example 7

Prepare plate base, hydrophilic layer and coating photosensitive liquid with the same method as Example 1. Just adjust the electrolytic power to make the average thickness of the centerline of the plate base be 0.6um.

The plate material obtained in this way was exposed with a light value of 60 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without washing with tap water. Its properties are listed in Table 1 below.

Example 8

Prepare plate base, hydrophilic layer and coating photosensitive liquid with the same method as Example 1. Just adjust the dry weight of the hydrophilic layer to 5 mg/dm ² .

The plate material obtained in this way was exposed with a light value of 60 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without washing with tap water. Its properties are listed in Table 1 below.

Example 9

Prepare plate base, hydrophilic layer and coating photosensitive liquid with the same method as Example 1. Just adjust the dry weight of the hydrophilic layer to 50 mg/dm ² .

The plate material obtained in this way was exposed with a light value of 60 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without washing with tap water. Its properties are listed in Table 1 below.

Comparative example 1

Prepare plate base, hydrophilic layer and coating photosensitive liquid with the same method as Example 1. Just photosensitive liquid with the following components:

Photosensitive liquid 6 (each component is by weight)

Water-soluble polymer 1 of the present invention 1.6

Acrylic prepolymer 0.64

Pentaerythritol triacrylate 0.86

2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine 0.03

p-Methoxyphenol 0.03

BYK-306 0.012

Phthalocyanine blue dye 0.032

1-methoxy-2-propylene 32.80

The plate material obtained in this way was exposed with a light value of 120 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without washing with tap water. Its properties are listed in Table 1 below.

Comparative example 2

Prepare plate base, hydrophilic layer and coating photosensitive liquid with the same method as Example 1. Just photosensitive liquid with the following components:

Photosensitive liquid 7 (each component is by weight)

Water-soluble polymer 1 of the present invention 1.6

Polyurethane Acrylic Prepolymer 0.64

Ethyl Acrylate 0.86

2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine 0.03

p-Methoxyphenol 0.03

BYK-306 0.012

Phthalocyanine blue dye 0.032

1-methoxy-2-propylene 32.80

The plate material obtained in this way was exposed with a light value of 110 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without washing with tap water. Its properties are listed in Table 1 below.

Comparative example 3

Prepare plate base, hydrophilic layer and coating photosensitive liquid with the same method as Example 1. Just photosensitive liquid with the following components:

Photosensitive liquid 8 (each component is by weight)

Water-soluble polymer of the present invention 1 1.6

Polyurethane Acrylic Prepolymer 0.64

Pentaerythritol triacrylate 0.86

1-Hydroxyketone (DAROCUR4265) 0.03

p-methoxyphenol 0.03

BYK-306 0.012

Phthalocyanine blue dye 0.032

1-methoxy-2-propanol                                                                                                                                     

The plates obtained in this way were exposed with a light value of 150 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without washing with tap water. Its properties are listed in Table 1 below.

Comparative example 4

Prepare plate base, hydrophilic layer and coating photosensitive liquid with the same method as Example 1. Just adjust the electrolytic power to make the average thickness of the center line of the plate base be 0.3um.

The plate material obtained in this way was exposed with a light value of 60 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without washing with tap water. Its properties are listed in Table 1 below.

Comparative Example 5

Prepare plate base, hydrophilic layer and coating photosensitive liquid with the same method as Example 1. Just adjust the electrolytic power to make the average thickness of the center line of the plate base be 0.7um.

The plate material obtained in this way was exposed with a light value of 60 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without washing with tap water. Its properties are listed in Table 1 below.

Comparative example 6

Prepare plate base, hydrophilic layer and coating photosensitive liquid with the same method as Example 1. Just photosensitive liquid with the following components:

Photosensitive solution 1 (each component is by weight)

PVP(K60) 1.6

Polyurethane Acrylic Prepolymer 0.64

Pentaerythritol triacrylate 0.86

2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine 0.03

p-Methoxyphenol 0.03

BYK-306 0.012

Phthalocyanine blue dye 0.032

1-methoxy-2-propylene 32.80

The plates obtained in this way were exposed with a light value of 200 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without washing with tap water. Its properties are listed in Table 1 below.

Comparative Example 7

Prepare plate base, hydrophilic layer and coating photosensitive liquid with the same method as Example 1. Just adjust the dry weight of the hydrophilic layer to 3 mg/dm ² .

The plate material obtained in this way was exposed with a light value of 60 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without washing with tap water. Its properties are listed in Table 1 below.

Comparative Example 8

Prepare plate base, hydrophilic layer and coating photosensitive liquid with the same method as Example 1. Just adjust the dry weight of the hydrophilic layer to 70 mg/dm ² .

The plate material obtained in this way was exposed with a light value of 60 on a UC-SETTER741 UV-CTP plate-making machine. Then, rinse with pure tap water for 30 to 50 seconds at a temperature of 40°C in a MASTER VIEW developing machine, and then mount and print. It can also be directly loaded onto the printing machine for printing without washing with tap water. Its properties are listed in Table 1 below.

Table I

Claims (21)

1. A chemical-free negative photosensitive composition suitable for UV-CTP, characterized in that: it mainly comprises the following six components: (1) a -(X)-(Y)-(Z)- structure of unsaturated water-soluble polymers, and (2) a photopolymerizable prepolymer, and (3) a multifunctional monomer, and (4) one or more photopolymerization initiators, And (5) one or more than one dyes or pigments, and (6) one or more than one solvents; wherein, X represents a copolymerization unit containing a sulfonic acid group, and Y represents a compound containing two unsaturated double bonds A branched carboxylic acid copolymerization unit, Z represents an acrylate copolymerization unit containing an unsaturated double bond branch. 2. The chemical-free negative photosensitive composition suitable for UV-CTP according to claim 1, wherein said X is selected from ethylene sulfonic acid, styrene sulfonic acid, 2-hydroxyl-3-allyloxy Base-1-propylsulfonic acid, allyloxybenzenesulfonic acid, 2-acrylamido-2-methylpropylsulfonic acid, isoprenesulfonic acid. 3. The chemical-free negative photosensitive composition suitable for UV-CTP according to claim 2, characterized in that X accounts for 10%-30% of the molar ratio of the copolymer. 4. The chemical-free negative photosensitive composition suitable for UV-CTP according to claim 1, wherein Y is a branched acrylic acid or methacrylic acid copolymerization unit containing two unsaturated double bonds. 5 . The chemical-free negative photosensitive composition suitable for UV-CTP according to claim 4 , wherein Y is a GMA-grafted acrylic acid or methacrylic acid copolymer unit containing one unsaturated double bond substitution. 6 . The chemical-free negative photosensitive composition suitable for UV-CTP according to claim 5 , wherein Y accounts for 20% to 40% of the molar ratio of the copolymer. 7 . The chemical-free negative photosensitive composition suitable for UV-CTP according to claim 1 , wherein Z is an acrylate or methacrylic copolymer unit containing an unsaturated double bond substituting group. 8 . The chemical-free negative photosensitive composition suitable for UV-CTP according to claim 7 , wherein Z accounts for 30% to 50% of the molar ratio of the copolymer. 9. The chemical-free negative photosensitive composition suitable for UV-CTP according to claim 1, characterized in that: in the unsaturated water-soluble polymer of -(X)-(Y)-(Z)-structure, The total number of unsaturated double bonds accounts for 60-80% molar ratio of the polymer. 10. The chemical-free negative photosensitive composition suitable for UV-CTP according to claim 1, wherein the photopolymerizable prepolymer is a polyurethane acrylic prepolymer. 11. The chemical-free negative photosensitive composition suitable for UV-CTP according to claim 1, wherein the photopolymerizable monomer is a multifunctional monomer. 12. The chemical-free negative photosensitive composition suitable for UV-CTP according to claim 1, wherein the photopolymerization initiator is selected from halogen-substituted triazine compounds. 13. The chemical-free negative photosensitive composition suitable for UV-CTP according to claim 1, characterized in that: the chemical-free negative photosensitive composition suitable for UV-CTP also contains phenolic resin, acrylic resin , Polyurethane resin, any one or a combination of them as an added component. 14. A lithographic printing plate made of the chemical-free negative photosensitive composition suitable for UV-CTP according to any one of claims 1 to 13, characterized in that: it comprises: (1) aluminum plate base support, and (2) the hydrophilic layer containing the unsaturated water-soluble polymer of the above-(X)-(Y)-(Z)-structure on the aluminum plate base support, and (3) with the hydrophilic The water layer is on the same side of the aluminum plate base and above the hydrophilic layer is the coating layer of the chemical-free negative photosensitive composition suitable for UV-CTP. 15. according to the described lithographic printing plate of claim 14, it is characterized in that, the support body of this lithographic printing plate is the aluminum plate base that carries out sealing treatment through electrolytic roughening and anodic oxidation, and its central line average thickness is between 0.4- 0.6um. 16. The lithographic printing plate according to claim 14, characterized in that the dry weight of the hydrophilic treatment coating is 5-50 mg/dm ² . 17. A method for making a lithographic printing plate as claimed in any one of claims 14 to 19, characterized in that: coating the above-mentioned A chemical-free negative working photosensitive composition suitable for UV-CTP. 18. The method for making a lithographic printing plate according to claim 17, characterized in that: the above-mentioned chemical-free coating suitable for UV-CTP is applied on the aluminum plate base after electrolytic roughening, anodic oxidation and sealing treatment. Before treating the negative photosensitive composition, the aluminum plate base is hydrophilized with the unsaturated water-soluble polymer of the -(X)-(Y)-(Z)-structure of the present invention. 19. The lithographic printing plate according to claim 17, characterized in that, the lithographic printing plate is suitable for using a UV-CTP plate making machine. 20. The lithographic printing plate according to claim 17, characterized in that, after the lithographic printing plate is scanned and exposed using a UV-CTP plate-making machine, it can be rinsed with tap water without using a developing solution to obtain a printable lithographic printing plate . 21. The lithographic printing plate according to claim 17, characterized in that, after scanning and exposing the lithographic printing plate using a UV-CTP plate-making machine, it can be directly mounted on a printing machine for printing without any treatment.

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