CN106543860B

CN106543860B - Processing-free lithographic plate precursor and ultrashort pulse laser plate making method

Info

Publication number: CN106543860B
Application number: CN201510607548.7A
Authority: CN
Inventors: 王怀功; 张涛; 邵国安; 张刚; 杨青海; 王泳; 高英新
Original assignee: Beijing Aerospace Innovation Patent Investment Center (limited Partnership); Lucky Huaguang Graphics Co Ltd
Current assignee: Beijing Aerospace innovation patent investment center (limited partnership)
Priority date: 2015-09-23
Filing date: 2015-09-23
Publication date: 2020-04-10
Anticipated expiration: 2035-09-23
Also published as: CN106543860A

Abstract

A process-free lithographic printing plate precursor comprises a graining-treated metal substrate and a laser-ablatable ink-receptive resin layer or UV-curable resin layer on the metal substrate which does not contain any photosensitive substance. The coating of the plate material does not need a complex photosensitive system, only a layer of resin layer which can be etched, resists ink and is ink-loving is coated on a metal substrate which is subjected to graining treatment, the coating is subjected to ultrashort pulse laser engraving, blank parts in an original manuscript are ablated to form a hydrophilic area, and after image-text parts are left to form an ink-loving area, a real treatment-free lithographic plate which meets the water-ink balance required by lithographic printing can be manufactured, so that the production of the real environment-friendly pollution-free lithographic plate is realized.

Description

Processing-free lithographic plate precursor and ultrashort pulse laser plate making method

Technical Field

The invention belongs to the technical field of printing plate making, and relates to a treatment-free lithographic plate (CTP plate) precursor with real significance, an ultrashort pulse laser plate making machine and a plate making method; the process-free lithographic printing plate precursor is suitable for ultrashort pulse laser platemaking machines for making lithographic printing plates for printing.

Background

With the development of science and technology, CTP (computer to plate) technology directly prepared by a computer is widely applied, when a thermosensitive CTP plate, an ultraviolet CTP plate and the like are exposed, a light beam is used for crosslinking or decomposing a thermosensitive or photosensitive resin in a coating layer, a blank part of an original manuscript is changed into a material capable of being dissolved in a developing solution, and an image-text part is remained on a printing plate substrate, so that a lithographic printing plate meeting the requirement of ink-water balance is formed. The plate making of the lithographic printing plate does not need a film printing process, and the like, and the original can be directly transferred to the CTP plate by a computer, and the original can be printed on a machine after exposure and development. However, in the manufacturing process of the plate, a complex photosensitive chemical system is needed, the manufacturing difficulty of the plate is increased and the cost is increased due to the thermosensitive and photosensitive chemicals, and a developing process is needed when a printing plate is manufactured, and a developing solution of an alkaline substance and an organic solvent is needed, so that a certain waste liquid treatment problem is caused.

The 'treatment-free CTP' recently put on the market still needs a complex photosensitive system, and a lithographic plate required by printing is formed after exposure and development.

Disclosure of Invention

The present invention is directed to a process-free lithographic printing plate precursor and an ultrashort pulse laser platemaking method to overcome the disadvantages of the prior art.

The purpose of the invention is realized by the following technical scheme:

a process-free lithographic printing plate precursor comprises a graining-treated metal substrate and a laser-ablatable ink-receptive resin layer or UV-curable resin layer on the metal substrate which does not contain any photosensitive substance.

The ink-philic resin layer consists of an organic solvent, an organic pigment or dye dissolved and dispersed in the organic solvent, a high polymer, an adhesive and an auxiliary agent; the ultraviolet light curing resin layer is composed of organic pigment or dye, oligomer, active monomer and photoinitiator.

The metal substrate is any one of a pure aluminum plate, an aluminum alloy plate, an iron plate and a galvanized plate, and is subjected to electrolytic oxidation treatment or laser engraving treatment in advance to form grains with the surface average roughness of 0.1-0.9 um; the thickness of the ink-philic resin layer or the ultraviolet light curing resin layer is 0.5-5 um after being dried.

The organic solvent is selected from one or more of ethylene glycol ethyl ether, ethylene glycol methyl ether, glycerol methyl ether acetate, glycerol methyl ether, diethylene glycol methyl ether, methyl lactate, ethyl lactate, methyl ethyl ketone, methanol, ethanol, isopropanol and l-methoxy-2-propanol; the organic pigment or dye is selected from the group consisting of monoazo, disazo, lake, phthalocyanine, quinacridone, fused ring pigment, hansa yellow, pigment yellow 150, pigment yellow 151, pigment red 37, pigment red 149, pigment red 185, pigment violet 23, pigment blue 15: 1. pigment green 7, diarylamine red, diarylorange, lake red C, rose red, methyl violet and/or ethyl violet, wherein the mass fraction of the pigment green in the organic solvent is 0.1-25%; the high polymer is selected from any one or more than two of phenolic resin, urethane-modified phenolic resin, polyvinyl alcohol, acrylic resin, alkyd resin, polyamine resin and derivatives thereof, polyurethane, epoxy resin, organic silicon resin, cyanate resin, polyimide resin, polyacrylic acid and unsaturated polyester, and the mass fraction of the high polymer in an organic solvent is 5-65%; the adhesive is selected from one or a composition of more than two of phenolic resin, urethane-modified phenolic resin, nitrocellulose, oligomer or homopolymer of acrylic acid, polyamide and poly-polyol sugar alcohol, and the mass fraction of the adhesive in the organic solvent is 2-20%; the oligomer is selected from any one or a composition of more than two of epoxy acrylic resin, polyurethane acrylic resin, polyether ester acrylic resin and bisphenol A epoxy acrylic resin; the active monomer is selected from any one or a combination of more than two of 2-ethylhexyl acrylate, hexanediol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, trihydroxymethyl propane triacrylate, neopentyl glycol diacrylate, isoborneol acrylate and ethoxy ethyl acrylate EOEOEA; the photoinitiator is selected from one or more than two of Irgacure184, Irgacure651, Irgacure907, Irgacure369, Irgacure819, Darocur1173, TPO and ITX; the ultraviolet light curing resin layer comprises the following raw materials in parts by weight: 0.1-25 parts of organic pigment or dye, 2-15 parts of oligomer, 5-50 parts of active monomer and 3-30 parts of photoinitiator.

The auxiliary agent in the ink-philic resin layer organic solvent is one or the combination of more than two of a dispersant, a defoaming agent, a flatting agent and an antioxidant; the mass fractions of the dispersing agent, the defoaming agent, the flatting agent and the antioxidant in the organic solvent are respectively 0.05-3%, 0.05-5%, 0.05-3% and 0.1-10%; the ultraviolet light curing resin layer further comprises 0.5-5 parts of a dispersing agent.

The dispersing agent is selected from sodium carboxymethylcellulose, sodium oleate, sodium carboxylate, sulfate ester salt, sulfonate, octadecenylamine acetate, alkyl quaternary ammonium salt, aminopropylamine dioleate, quaternary ammonium salt, modified polyaminoamide phosphate, fatty acid ethylene oxide addition product, polyethylene glycol and polyethylene imine derivative, phosphate salt type high polymer, oleyl aminooleate, polyhexamethylene internal polyol-polyethylene imine block copolymer, low molecular weight polyester, polyurethane introducing anchoring groups and polyacrylate, the defoaming agent is selected from one or more than two of phenethyl alcohol oleate, lauryl phenylacetate, dimethyl silicone oil and polyether modified silicone oil defoaming agent, the leveling agent is selected from one or more than two of polydimethylsiloxane, polyether polyester modified organosiloxane, alkyl modified organosiloxane, terminal modified organosilicon and fluorine modified acrylate, the antioxidant is selected from diphenylamine, p-phenylenediamine, dihydroquinoline, butyl hydroxy anisole, dibutyl hydroxy toluene, propyl gallate, 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether, tetratetradecyl diphenol, 3-tert-butyl-4-hydroxyphenyl thioether, and tetratetradecyl diphenol.

The ultrashort pulse laser platemaking process with the said plate precursor includes etching to eliminate blank part with ultrashort pulse laser beam based on the digitalized content of the original to form hydrophilic area and leaving ink-philic image-text area to make the printing plate.

The ultrashort pulse laser beam is generated by picosecond, femtosecond or attosecond laser, and the laser pulse width is 10^-12～10^-18Second, pulse energy is 0.1-10J/cm²The center wavelength is 100-2000 nm, the repetition frequency is 1-100 kHz, and the moving etching width of the laser beam is 280-1600 mm.

An ultrashort pulse laser platemaking machine is a platemaking machine which uses ultrashort pulse laser and the platemaking method.

The treatment-free plate disclosed by the invention is a real 'treatment-free' plate precursor: because the coating (including an ink-loving resin layer or an ultraviolet light curing resin layer) of the plate material does not need a complex photosensitive system, only a layer of resin layer which can be etched, resists ink and is ink-loving is coated on a metal substrate which is subjected to graining treatment, after the coating is subjected to ultrashort pulse laser engraving, a blank part in an original manuscript is ablated to form a hydrophilic area, and an image-text part is left to form the ink-loving area, so that a real treatment-free lithographic plate which meets the water-ink balance required by lithographic printing can be manufactured, and the production of the real environment-friendly pollution-free lithographic plate is realized.

The ultrashort pulse laser has a pulse width of 10^-12~10^-18Laser light between seconds; compared with the conventional continuous laser or wide pulse laser, the ultrashort pulse laser has the following advantages: (1) the duration is short, and heat transfer cannot occur; because the pulse width of the laser is very narrow, after the laser is hit on the target material, the heat has not been transferred in time, and the laser is stopped; (2) the energy is high, the material can be vaporized instantly, even if the action time is very short, the energy is still enough to enable electrons to get rid of the constraint of atomic nuclei due to the very high energy of laser pulse, other materials form plasma, expand rapidly and fly away from the matrix at a very high speed, and absorbed heat is taken away to form so-called cold processing. (3) The active area is very small and adjustable, which is beneficial to manufacturing round or square mesh points about 20 um. Because the pulse laser is in Gaussian distribution, the laser energy can be adjusted along with the beam waist radius, the energy can be concentrated in a submicron or even nanometer range, and the target can be subjected to cold laser processing as long as the laser energy exceeds the ablation threshold value of the target.

CTP made by laser engraving principle is disclosed, but it is essentially different from this patent, mainly these printing plates either still use photosensitive coating or have different coating thickness. In the process of making the lithographic plate, the laser used is either a continuous laser or a broad pulse laser (meaning a pulse width greater than 10)^-10Second laser), the subsequent development treatment is required after the printing plate is manufactured, and no real treatment-free is realized.

The "lithographic plate" disclosed in CN 101018674a is different in that: the coating still contains photosensitive substances, and an oleophilic coating can be formed only after exposure under laser, so that a printing plate with very high contrast is formed.

The "laser ablation resist" disclosed in CN 101454720B differs in that: which coatings include organic solids and light-to-heat converting substances, require and be thermally removed by imagewise irradiation of the first layer of resist material to obtain a printing plate.

The "ablatable element for making flexographic printing plates" disclosed in CN 101668634a differs in that: its flexographic printing plate and other relief images can be formed from laser-engraveable elements having a laser-engraveable layer having a thickness of at least 20 um. Such thick coatings are not at all suitable for lithographic printing.

The differences between the "treatment-free printing plate material and the preparation method and application thereof" disclosed in CN 101612849A are as follows: this patent is a treatment-free printing plate obtained by coating a metal substrate, which is not clearly indicated as having been subjected to a graining treatment, with two layers, one layer being a substrate layer (aqueous solution containing a polymer resin and an inorganic substance) and the other layer being still a hydrophilic layer, with a YAG laser and CO laser₂Laser or fiber laser. The invention only has an ink-loving layer or an ultraviolet light solidified resin layer, which is coated on the metal thin plate after the graining treatment, and the laser type for engraving is different.

The difference from the "environmental-friendly anhydrous offset printing plate" disclosed in CN 103057294 a is that: although the ink-receptive layer is composed of the bottom hydrophilic layer and the upper ink-receptive layer, the upper ink-receptive layer contains diazonaphthoquinone photosensitive substances, and thus is different from the photosensitive-substance-free photosensitive substance of the patent.

The ultrashort pulse laser platemaking machine uses picosecond and attosecond laser as the laser beam, and the plate base hydrophilic layer is metal sheet treated through graining, and the ink-attracting layer is ink-attracting resin containing no photosensitive matter and being capable of carving and resisting ink.

The treatment-free lithographic plate manufactured by the invention has the following advantages:

(1) the ink-loving resin layer or the ultraviolet light curing resin layer does not contain photosensitive chemical substances, can be operated in a bright room, reduces the manufacturing difficulty and cost of the conventional CTP, and is favorable for transportation and storage of plates.

(2) In the plate making process, developing solution is not needed, only simple cleaning is needed, and environmental protection problems such as waste liquid treatment and the like do not exist.

(3) Because the ink-attracting layer contains the adhesive, the ink-attracting resin can be firmly adhered to the base plate, and the printing plate has much higher printing endurance than the traditional printing plate.

(4) Because the ultra-short pulse laser energy is high, the light beam is thin, and the heat transfer is hardly generated in the engraving process, the method is favorable for manufacturing the regular dot of about 20um, the dot reduction is very good, and the problem of dot deformation after the development of the traditional lithographic plate is solved.

(5) The lithographic plate manufactured by the invention can be directly suitable for the existing printing equipment without changing the existing printing machine.

Detailed Description

Example 1

The utility model provides a exempt from to handle lithographic printing plate precursor, but by the metal substrate of graining processing and the ink-philic resin layer or the ultraviolet curing resin layer of laser ablation on the metal substrate constitute, ink-philic resin layer or ultraviolet curing resin layer are 0.5 ~5 um. The metal substrate is selected from one of a pure aluminum plate, an aluminum alloy plate, an iron plate and a galvanized plate with the thickness of 0.1-0.5 mm, and is subjected to electrolytic oxidation treatment in advance or laser engraving treatment to form grains with the surface average roughness of 0.1-0.9 um so as to achieve the water retention performance and the friction-resistant hardness performance required by printing.

The ink-philic resin layer consists of an organic solvent, 0.1 to 25 mass percent of organic pigment or dye, 5 to 65 mass percent of high polymer, 2.0 to 20 mass percent of adhesive and auxiliary agent which are dissolved and dispersed in the organic solvent; the ultraviolet light curing resin layer is composed of 0.1-25 parts by weight of organic pigment or dye, 2-15 parts by weight of oligomer, 5-50 parts by weight of active monomer and 3-30 parts by weight of photoinitiator.

The organic solvent is selected from one or more of ethylene glycol ethyl ether, ethylene glycol methyl ether, glycerol methyl ether acetate, diethylene glycol methyl ether, methyl lactate ethyl lactate, methyl ethyl ketone, methanol, ethanol, isopropanol and l-methoxy-2-propanol; the organic pigment or dye is selected from the group consisting of monoazo, disazo, lake, phthalocyanine, quinacridone, fused ring pigment, hansa yellow, pigment yellow 150, pigment yellow 151, pigment red 37, pigment red 149, pigment red 185, pigment violet 23, pigment blue 15: 1. pigment green 7, diarylamine red, diarylorange, lake red C, rose bengal, methyl violet, ethyl violet or a combination of two or more of them; the high polymer is selected from one or a composition of more than two of phenolic resin, urethane-modified phenolic resin, polyvinyl alcohol, acrylic resin, alkyd resin, polyamine resin and derivatives thereof, polyurethane, epoxy resin, organic silicon resin, cyanate resin, polyimide resin, polyacrylic acid and unsaturated polyester; the adhesive is selected from one or a composition of more than two of phenolic resin, urethane-modified phenolic resin, nitrocellulose, oligomer or homopolymer of acrylic acid, polyamide and poly-polyol; the oligomer is selected from any one or a composition of more than two of epoxy acrylic resin, polyurethane acrylic resin, polyether ester acrylic resin and bisphenol A epoxy acrylic resin; the active monomer is selected from any one or a combination of more than two of acrylic acid-2-ethylhexyl ester, hexanediol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, trihydroxy methyl propane triacrylate, neopentyl glycol diacrylate, isoborneol acrylate and ethoxy ethyl acrylate EOEOEA; the photoinitiator is selected from one or more than two of Irgacure184, Irgacure651, Irgacure907, Irgacure369, Irgacure819, Darocur1173, TPO and ITX.

The auxiliary agent in the ink-philic resin layer organic solvent is any one or a composition of more than two of a dispersing agent, a defoaming agent, a flatting agent and an antioxidant; the mass fractions of the dispersing agent, the defoaming agent, the flatting agent and the antioxidant in the organic solvent are respectively 0.05-3%, 0.05-5%, 0.05-3% and 0.1-10%; the ultraviolet light curing resin layer further comprises 0.5-5 parts by weight of a dispersing agent.

The dispersing agent is selected from sodium carboxymethylcellulose, sodium oleate, sodium carboxylate, sulfate ester salt, sulfonate, octadecenylamine acetate, alkyl quaternary ammonium salt, aminopropylamine dioleate, quaternary ammonium salt, modified polyaminoamide phosphate, fatty acid ethylene oxide addition product, polyethylene glycol and polyethylene imine derivative, phosphate salt type high polymer, oleyl oleate, polycaprolactam polyol-polyethylene imine block copolymer, low molecular weight polyester, polyurethane introducing anchoring groups and polyacrylate, the defoaming agent is selected from any one or more than two of phenethyl alcohol oleate, lauryl phenylacetate, dimethyl silicone oil and polyether modified silicone oil defoaming agent, the leveling agent is selected from any one or more than two of polydimethylsiloxane, polyether polyester modified organosiloxane, alkyl modified organosiloxane, terminal modified organosilicon and fluorine modified acrylate, the antioxidant is selected from any one or more than two of diphenylamine, p-phenylenediamine, dihydroquinoline, butyl hydroxy anisole, dibutyl hydroxy toluene and propyl gallate, 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide, bis (3, 5-tert-butyl-4-phenyl) pentaerythritol ester, bis (3, tert-butyl-4-phenyl) pentaerythritol ester, bis (3, 5-tert-butyl phenyl) pentaerythritol ester and bis (tert-butyl-phenyl) propionate.

The molecular weight of the oligomer is 300-2000; the molecular weight of the high polymer is 1000-5 ten thousand.

The preparation method of the treatment-free lithographic printing plate precursor of the ink-philic resin layer comprises the following steps: weighing raw materials contained in an organic solvent, heating to 30-50 ℃ to dissolve and disperse the raw materials in the organic solvent to prepare a coating liquid, coating the coating liquid on a metal substrate, and drying to obtain the lithographic plate precursor.

The preparation method of the treatment-free lithographic printing plate precursor of the ultraviolet curing resin layer comprises the following steps: weighing raw materials in the ultraviolet curing resin layer, heating to 30-50 ℃ to dissolve and disperse the raw materials to prepare a coating liquid, coating the coating liquid on a metal substrate, and drying by using ultraviolet radiation to obtain the lithographic plate precursor.

The method for making the plate by using the processing-free lithographic printing plate precursor comprises the following steps of etching a blank part by using an ultrashort pulse laser beam according to the digital content of an original to form a hydrophilic layer; the non-etched part is an ink-attracting layer with a graph-text part so as to meet the ink balance requirement required by lithography.

The ultrashort pulse laser beam is generated by picosecond, femtosecond or attosecond laser, and the laser pulse width is 10^-12～10^-18Second, pulse energy is 0.1-10J/cm²The central wavelength is 100-2000 nm, the repetition frequency is 1-100 kHz, and the moving etching width of the laser beam is 280-1600 mm, so that the requirements of dot reduction, printing resistance and ultra-wide breadth required by printing and plate making are met.

Example 2

1.0% of acrylic acid oligomer, 10% of epoxy resin, 25% of phenolic resin, 0.1% of phenethyl alcohol oleate, 0.15% of ethyl violet, 0.8% of Butyl Hydroxy Anisole (BHA) and 2.0% of polydimethylsiloxane are dissolved and dispersed in 50L of ethylene glycol monoethyl ether, the mixture is heated to 30-50 ℃ to disperse and dissolve the substances to prepare a coating liquid, the prepared coating liquid is coated on an aluminum plate substrate with the roughness of 0.5 and the thickness of 0.2mm, the aluminum plate substrate is dried to obtain a lithographic plate original plate, and the thickness of the resin layer after drying is 2 um.

The coating liquid of the present invention had a viscosity of 2.8 cps, a surface tension of 22dyn/cm and a solid content of 5.2%.

The ultrashort pulse laser platemaking machine regenerates and amplifies a femtosecond laser beam by using a titanium gem mode locking, wherein the pulse width is 94fs, the repetition frequency is 1kHz, and the central wavelength is 700 nm. The beam control system comprises beam homogenization, energy and polarization regulating element of half wave plate and polaroid combinationAnd (3) a component. The working distance of a field lens of the high-speed scanning galvanometer is 63mm, and the diameter of a focusing light spot is 10 mu m. The scanning speed of the selected laser is 15mm/s, the scanning line spacing is 10 mu m, and the laser energy density is 0.5J/cm²Slightly larger than the engraving threshold of the coating on the original plate, and preparing the lithographic printing plate for printing.

The split lithographic plate manufactured by the method has good 1% dot reduction and obvious contrast, and is installed on an offset press for printing, the ink lifting speed is high, and the printing number reaches more than 8 thousands of prints.

Example 3

1.0% of sodium carboxymethylcellulose, 15% of modified acrylic resin, 30% of modified phenolic resin, 0.1% of lauryl phenylacetate, 0.18% of phthalocyanine, 2.0% of octadecylamine acetate, 1.0% of phenethyl alcohol oleate and 0.8% of 2, 6-tertiary butyl-4-methylphenol are dispersed and dissolved in 50L of ethylene glycol monoethyl ether and methyl ethyl ketone (2: 1) solution, the solution is heated to 30-50 ℃ to disperse, dissolve and disperse the substances to prepare a coating solution, the prepared coating solution is coated on an aluminum plate substrate with the roughness of 0.5 and the thickness of 0.2mm, the coating solution is coated and dried to obtain a flat printing plate precursor, and the thickness of the dried resin layer is 5 um.

The coating liquid of the present invention had a viscosity of 3.0 cps, a surface tension of 24dyn/cm and a solid content of 5.5%.

The titanium-doped sapphire ultrashort pulse laser platemaking machine is used, the wavelength of output laser is 800nm, the pulse width is 120fs, the repetition frequency is 1000Hz, horizontal polarization is realized, and the single pulse energy is adjustable within 0.1-1 mJ. The incident laser is reflected by a double-vibration mirror, and is focused on the surface of a sample from a focusing mirror with the focal length of 200mm, and the diameter of a light spot is about 10 mu m. The energy is changed by an attenuation mirror, the number of pulses is controlled by a time delay device, and the master plate is engraved to produce a lithographic plate for printing.

The split lithographic plate manufactured by the method has good 1% dot reduction and obvious contrast, and is installed on an offset press for printing, the ink lifting speed is high, and the printing number reaches more than 7 thousands of prints.

Example 4

1.0% of polyurethane, 15% of organic silicon resin, 25% of modified phenolic resin, 0.7% of polyether polyester modified organic siloxane, 0.18% of condensed ring pigment, 1.2% of lake red C and 0.7% of sulfate ester alkyl are dissolved and dispersed in 50L of 1-methoxy-2-propanol solution, the solution is heated to 30-50 ℃ to dissolve and disperse the substances to prepare a coating solution, the coating solution is coated on an aluminum plate substrate with the roughness of 0.5 and the thickness of 0.2mm, the coating solution is dried to obtain a lithographic plate original plate, and the thickness of the dried resin layer is 1.5 mu m.

The coating liquid of the present invention had a viscosity of 3.2 cps, a surface tension of 20dyn/cm and a solid content of 5.6%.

Placing the original plate in a liquid filled with water, wherein the distance between the liquid surface and the plate material is 0.5cm, adopting a femtosecond laser plate making machine with the wavelength of 750nm, the pulse width of 100 femtoseconds, the repetition frequency of 10KHz and the power of 1W to focus laser on the original plate through an objective lens with the numerical aperture of 0.1mm, adjusting the laser energy to ensure that the multiphoton absorption threshold value can be reached only at the position closest to the focus center (on the water and the original plate), and engraving to prepare the printing plate.

The split lithographic plate manufactured by the method has good 1% dot reduction and obvious contrast, and is installed on an offset press for printing, the ink lifting speed is high, and the printing number is more than 9 thousands of prints.

Example 5

Dissolving and dispersing 45% of phenolic resin, 0.6% of polydimethylsiloxane, 0.3% of condensed ring pigment, 1.8% of diaryl orange, 0.7% of alkyl quaternary ammonium salt, 0.6% of lauryl phenylacetate and 3.0% of propyl gallate in 50L of 1-methoxy-2-propanol solution, heating to 30-50 ℃ to dissolve and disperse the substances to prepare a coating solution, coating the coating solution on an aluminum plate master plate with the roughness of 0.5 and the thickness of 0.2mm, and drying to obtain a lithographic plate, wherein the thickness of the dried resin layer is 1 um.

The coating liquid of the present invention had a viscosity of 2.8 cps, a surface tension of 24dyn/cm and a solid content of 5.2%.

Placing the original plate in a liquid filled with water, wherein the distance between the liquid surface and the plate material is 0.5cm, adopting a femtosecond laser plate-making machine with the wavelength of 760nm, the pulse width of 180 femtoseconds, the repetition frequency of 20KHz and the power of 1.5W to focus laser on the original plate through an objective lens with the numerical aperture of 0.1mm, adjusting the laser energy to ensure that the multiphoton absorption threshold value can be reached only at the position closest to the focus center (on the water and the original plate), and engraving to prepare the lithographic plate printed with the original plate.

Example 6

Mixing 5 parts of pigment red 149, 25 parts of polyurethane acrylic resin, 20 parts of acrylic acid oligomer, 10 parts of isoborneol acrylate (IBOA), 10 parts of hexanediol diacrylate (HDDA), 10 parts of Irgacure651 and 1.0 part of oleyl aminooleate, heating to 30-50 ℃, dissolving the above substances to prepare a coating liquid, coating the coating liquid on an aluminum plate substrate with the roughness of 0.5 and the thickness of 0.2mm, radiating by ultraviolet light, drying to obtain a lithographic plate original, and drying to obtain the resin layer with the thickness of 3 um.

The coating liquid of the present invention had a viscosity of 12.1 cps and a surface tension of 28.5 dyn/cm.

The titanium-doped sapphire ultrashort pulse laser platemaking machine is used, the wavelength of output laser is 820nm, the pulse width is 120fs, the repetition frequency is 1KHz, horizontal polarization is realized, and the single pulse energy is adjustable within 0.1-1 mJ. The incident laser is reflected by a double-vibration mirror, and is focused on the surface of a sample from a focusing mirror with the focal length of 100mm, and the diameter of a light spot is about 10 mu m. The energy change is effected by means of an attenuation mirror, the number of pulses being controlled by means of a time delay. The master plate is engraved to produce a lithographic printing plate for printing.

The split lithographic printing plate manufactured by the method has good 1% dot reduction and obvious contrast, and is installed on an offset press for printing, the ink lifting speed is high, and the printing number reaches more than 10 thousands of prints.

Example 7

Dissolving and dispersing 5% ethyl violet and 60% phenolic resin in 50L of ethylene glycol ethyl ether solution, heating to 30-50 ℃ to dissolve and disperse the substances to prepare a coating liquid, coating the coating liquid on an aluminum plate substrate with the roughness of 0.1 and the thickness of 0.2mm, and drying to obtain a lithographic printing plate original plate, wherein the thickness of the dried resin layer is 3 um.

Using ultra-short pulses of titanium-doped sapphireThe laser platemaking machine outputs laser with wavelength of 100nm and pulse width of 10^-17s, repetition frequency of 40KHz, horizontal polarization, pulse energy of 1J/cm²Otherwise, the same procedure as in example 2 was repeated.

Example 8

Dissolving and dispersing 3% of pigment red 37 and 40% of urethane modified phenolic resin in 50L of mixed solution (volume ratio is 1: 1) of ethylene glycol methyl ether and isopropanol, heating to 30-50 ℃ to dissolve and disperse the substances to prepare coating liquid, coating the coating liquid on a steel plate substrate with the roughness of 0.3 and the thickness of 0.2mm, drying to obtain a lithographic plate original plate, and drying to obtain the resin layer with the thickness of 1 um.

Using titanium-doped sapphire ultrashort pulse laser platemaking machine, the output laser wavelength is 1000nm, and pulse width is 5X 10^- ¹³s, repetition frequency of 5KHz, horizontal polarization, pulse energy of 3.5J/cm²Otherwise, the same procedure as in example 2 was repeated.

Example 9

Dissolving and dispersing 10% of pigment red 185 and 30% of polyvinyl alcohol in 50L of a mixed solution (volume ratio is 1: 1) of ethylene glycol monomethyl ether and methanol, heating to 30-50 ℃ to dissolve and disperse the substances to prepare a coating liquid, coating the coating liquid on a steel plate substrate with the roughness of 0.9 and the thickness of 0.2mm, drying to obtain a lithographic plate original plate, and drying to obtain a resin layer with the thickness of 4 um.

The titanium-doped sapphire ultrashort pulse laser platemaking machine is used, the wavelength of output laser is 1300nm, and the pulse width is 10^-14s, repetition frequency of 35KHz, horizontal polarization, pulse energy of 10J/cm²Otherwise, the same procedure as in example 2 was repeated.

Example 10

Dissolving and dispersing 5% ethyl violet and 30% alkyd resin in 50L of mixed solution (volume ratio is 2: 1) of ethylene glycol methyl ether and methanol, heating to 30-50 ℃ to dissolve and disperse the substances to prepare coating liquid, coating the coating liquid on an aluminum alloy plate substrate with the roughness of 0.4 and the thickness of 0.2mm, drying to obtain a lithographic plate original plate, and drying to obtain the resin layer with the thickness of 4.5 um.

The ultra-short pulse laser platemaking machine doped with titanium sapphire is used, the wavelength of output laser is 1800nm, and the pulse width is 7 multiplied by 10^- ¹⁷s, repetition frequency of60KHz, horizontal polarization, pulse energy 1J/cm²Otherwise, the same procedure as in example 2 was repeated.

Example 11

Dissolving and dispersing 3% of pigment violet 23, 50% of acrylic resin and 0.05% of polyamide in 50L of mixed solution (volume ratio is 1:1: 1) of ethylene glycol ethyl ether, glycerol methyl ether acetate and methyl ethyl ketone, heating to 30-50 ℃ to dissolve and disperse the substances to prepare coating liquid, coating the coating liquid on a galvanized sheet substrate with the roughness of 0.5 and the thickness of 0.2mm, drying to obtain a lithographic printing plate original plate, and drying to obtain the resin layer with the thickness of 2.5 um.

Using titanium-doped sapphire ultrashort pulse laser platemaking machine, the wavelength of output laser is 500nm, and the pulse width is 1X 10^- ¹³s, repetition frequency of 20KHz, horizontal polarization, pulse energy of 6J/cm²Otherwise, the same procedure as in example 2 was repeated.

Example 12

20% of diarylamine red and 30% of polyvinyl alcohol are dissolved and dispersed in 50L of mixed solution (volume ratio is 1:1: 1) of ethylene glycol ethyl ether, glycerol methyl ether acetate and methyl ethyl ketone, the solution is heated to 30-50 ℃ to dissolve and disperse the substances to prepare coating liquid, the coating liquid is coated on an aluminum plate substrate with the roughness of 0.9 and the thickness of 0.2mm, a lithographic printing plate original plate is obtained by drying, and the thickness of the dried resin layer is 0.5 um.

Using titanium-doped sapphire ultrashort pulse laser platemaking machine, the wavelength of output laser is 1900nm, and the pulse width is 10^-18s, repetition frequency of 30KHz, horizontal polarization, pulse energy of 2J/cm²Otherwise, the same procedure as in example 2 was repeated.

Example 13

Mixing 2% of pigment blue 15: dissolving and dispersing 1, 30% of organic silicon resin, 30% of polyvinyl alcohol, 1% of acrylic acid homopolymer and 1% of acrylic acid oligomer in 50L of glycerol methyl ether and ethanol mixed solution (volume ratio is 8: 1), heating to 30-50 ℃ to dissolve and disperse the substances to prepare coating liquid, coating the coating liquid on a galvanized sheet substrate with the roughness of 0.8 and the thickness of 0.2mm, drying to obtain a lithographic printing plate original plate, and drying to obtain the resin layer with the thickness of 3.5 microns.

Using titanium-doped sapphire ultrashort pulse laser platemaking machine, the wavelength of output laser is 100nm, and the pulse width is5×10^- ¹⁶s, repetition frequency of 1KHz, horizontal polarization, pulse energy of 5.5J/cm²Otherwise, the same procedure as in example 2 was repeated.

Example 14

0.6% of pigment green 7, 25% of epoxy resin, 2% of phenolic resin and 0.1% of sodium carboxymethylcellulose are dissolved and dispersed in 50L of a mixed solution (volume ratio is 5: 1) of methyl ethyl ketone and ethanol, the solution is heated to 30-50 ℃ to dissolve and disperse the substances to prepare a coating solution, the coating solution is coated on a galvanized sheet substrate with the roughness of 0.8 and the thickness of 0.2mm, a lithographic printing original plate is obtained by drying, and the thickness of the resin layer after drying is 2 um.

The titanium-doped sapphire ultrashort pulse laser platemaking machine is used, the wavelength of output laser is 800nm, and the pulse width is 10^-12s, repetition frequency of 50KHz, horizontal polarization, pulse energy of 7J/cm²Otherwise, the same procedure as in example 2 was repeated.

Example 15

Dissolving and dispersing 1% of pigment blue 15:1, 40% of organic silicon resin, 10% of urethane modified phenolic resin and 0.5% of sodium oleate in 50L of mixed solution of methanol and diethylene glycol methyl ether (volume ratio is 2: 3), heating to 30-50 ℃ to dissolve and disperse the substances to prepare coating liquid, coating the coating liquid on an aluminum alloy plate substrate with the roughness of 0.4 and the thickness of 0.2mm, drying to obtain a lithographic plate original plate, and drying to obtain a resin layer with the thickness of 2 um.

The titanium-doped sapphire ultrashort pulse laser platemaking machine is used, the wavelength of output laser is 900nm, and the pulse width is 9 multiplied by 10^- ¹⁸s, repetition frequency of 45KHz, horizontal polarization, pulse energy of 5J/cm²Otherwise, the same procedure as in example 2 was repeated.

Example 16

A method for preparing the lithographic printing plate comprises the steps of dissolving and dispersing 5% of pigment green 7, 10% of urethane modified phenolic resin, 10% of alkyd resin, 10% of acrylic resin, 5% of polyamine resin and derivatives thereof, 20% of nitrocellulose, 0.5% of sulfate ester salt, 0.5% of phosphate ester type high polymer and 1% of dihydroquinoline in 50L of mixed solution of isopropanol and diethylene glycol methyl ether (volume ratio is 1: 3), heating to 30-50 ℃, dissolving and dispersing the substances to prepare a coating liquid, coating the coating liquid on an aluminum plate substrate with the roughness of 0.7 and the thickness of 0.2mm, drying to obtain a lithographic printing plate original plate, and enabling the thickness of the resin layer to be 0.5 mu m after drying.

Using titanium-doped sapphire ultrashort pulse laser platemaking machine, the wavelength of output laser is 1700nm, and the pulse width is 10^-12s, repetition frequency of 85KHz, horizontal polarization, pulse energy of 5J/cm²Otherwise, the same procedure as in example 2 was repeated.

Example 17

Dissolving and dispersing 3% of pigment red 149, 10% of cyanate ester resin, 5% of phenolic resin, 5% of urethane modified phenolic resin, 0.05% of sodium carboxylate and 3% of p-phenylenediamine in 50L of mixed solution (volume ratio is 1: 1), heating to 30-50 ℃ to dissolve and disperse the substances to prepare coating liquid, coating the coating liquid on an iron plate substrate with the roughness of 0.1 and the thickness of 0.2mm, drying to obtain a lithographic plate original plate, and drying to obtain a resin layer with the thickness of 5 um.

The titanium-doped sapphire ultrashort pulse laser platemaking machine is used, the wavelength of output laser is 2000nm, and the pulse width is 3 multiplied by 10^- ¹⁴s, repetition frequency of 70KHz, horizontal polarization, pulse energy of 4J/cm²Otherwise, the same procedure as in example 2 was repeated.

Example 18

Dissolving and dispersing 3% of lake red C, 15% of polyacrylic acid, 2% of acrylic acid oligomer, 0.3% of sulfonate, 0.4% of oleyl oleate and 0.5% of butyl hydroxy anisole in 50L of a mixed solution (volume ratio is 2: 1) of L-methoxy-2-propanol and isopropanol, heating to 30-50 ℃, dissolving and dispersing the substances to prepare a coating liquid, coating the coating liquid on an aluminum plate substrate with the roughness of 0.3 and the thickness of 0.2mm, drying to obtain a lithographic plate original plate, and drying to obtain the resin layer with the thickness of 0.5 um.

Using titanium-doped sapphire ultrashort pulse laser platemaking machine, the output laser wavelength is 1200nm, and the pulse width is 10^-18s, repetition frequency of 90KHz, horizontal polarization, pulse energy of 1.5J/cm²Otherwise, the same procedure as in example 2 was repeated.

Example 19

Dissolving and dispersing 12% of pigment yellow 150, 13% of pigment yellow 151, 10% of unsaturated polyester, 5% of phenolic resin, 2% of urethane modified phenolic resin, 3% of acrylic oligomer, 0.2% of octadecenylamine acetate, 0.3% of polycaprolactam polyol-polyethyleneimine block copolymer and 0.1% of dibutyl hydroxy toluene in 50L of a mixed solution (volume ratio is 2: 1), heating to 30-50 ℃, dissolving and dispersing the substances to prepare a coating liquid, coating the coating liquid on a galvanized plate substrate with the roughness of 0.2 and the thickness of 0.2mm, drying to obtain a lithographic plate original plate, and drying to obtain a resin layer with the thickness of 0.5 um.

Using titanium-doped sapphire ultrashort pulse laser platemaking machine, the wavelength of output laser is 1400nm, and the pulse width is 5X 10^- ¹⁷s, repetition frequency of 100KHz, horizontal polarization, pulse energy of 10J/cm²Otherwise, the same procedure as in example 2 was repeated.

Example 20

A lithographic printing plate precursor is prepared by dissolving and dispersing 5% of pigment yellow 151, 50% of urethane-modified phenolic resin, 15% of polyamide, 1% of alkyl quaternary ammonium salt, 2% of low molecular weight polyester and 1% of propyl gallate in 50L of ethylene glycol ether solution, heating to 30-50 ℃ to dissolve and disperse the above substances to prepare a coating liquid, coating the coating liquid on an aluminum alloy plate substrate with the roughness of 0.5 and the thickness of 0.2mm, drying to obtain the lithographic printing plate precursor, and drying to obtain the resin layer with the thickness of 0.5 um.

Using titanium-doped sapphire ultrashort pulse laser platemaking machine, the output laser wavelength is 200nm, and pulse width is 6X 10^- ¹⁵s, repetition frequency of 25KHz, horizontal polarization, pulse energy of 8J/cm²Otherwise, the same procedure as in example 2 was repeated.

Example 21

The organic solvent is a mixture (1: 1) of ethanol and glycerol monomethyl ether; organic pigment or dye is selected from 10 percent of lake; 10% of phenolic resin and 20% of alkyd resin are selected as high polymer; 5% of polyatomic sugar alcohol is selected as the adhesive; 0.2 percent of aminopropylamine dioleate and 0.1 percent of polyurethane introduced with an anchoring group are selected as a dispersant; the antioxidant is 0.3 percent of 2, 6-tertiary butyl-4-methylphenol; the rest is the same as example 2.

Example 22

The organic solvent is a mixed solvent (1: 1) of isopropanol and ethylene glycol monomethyl ether, the organic pigment or dye is pigment red 1853, the high polymer is ammonia esterification modified phenolic resin 15% and organic silicon resin 25%, the adhesive is phenolic resin 10%, the dispersant is quaternary ammonium salt 0.5% and polyacrylate 0.4%, the antioxidant is pentaerythritol tetrakis [ β - (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ] 5%, and the rest is the same as example 2.

Example 23

The organic solvent is a mixed solution of methanol and isopropanol (volume ratio is 1: 1); organic pigment or dye is 3% of phthalocyanine; 10% of polyvinyl alcohol and 10% of epoxy resin are selected as high polymers; 6% of urethane modified phenolic resin is selected as the adhesive; 0.8 percent of modified polyaminoamide phosphate is selected as a dispersant; the antioxidant is selected from 0.6 percent of bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether; the rest is the same as example 2.

Example 24

The organic solvent is a mixed solution of ethylene glycol monomethyl ether and ethyl lactate (volume ratio is 1: 2); the organic pigment or dye is selected from 10 percent of quinacridone; 5% of acrylic resin and 2% of unsaturated polyester are selected as high polymers; the adhesive is prepared from 3% of nitrocellulose, 10% of phenolic resin and 2% of acrylic acid homopolymer; the dispersant is 10% of fatty acid ethylene oxide adduct; 8% of tert-butyl hydroquinone is selected as the antioxidant; the rest is the same as example 2.

Example 25

The organic solvent is a mixed solution of l-methoxy-2-propanol and ethylene glycol monomethyl ether (volume ratio is 3: 1); the organic pigment or dye is 20 percent of fused cyclic ketone; 30% of alkyd resin and 20% of cyanate ester resin are selected as high polymers; the adhesive is prepared from 10% of amino esterification modified phenolic resin and 5% of acrylic acid oligomer; 2% of polyethylene glycol derivative is selected as the dispersant; 0.05% of phenethyl alcohol oleate is selected as the defoaming agent; the rest is the same as example 2.

Example 26

The organic solvent is a mixed solution of glycerol methyl ether acetate and l-methoxy-2-propanol (volume ratio is 5: 1); 10% of hansa yellow is selected as the organic pigment or dye; the high polymer is selected from 10% of polyamine resin and derivatives thereof and 40% of polyacrylic acid; the adhesive is 5% of phenolic resin and 5% of poly-polyhydric sugar alcohol; the dispersant is polyethyleneimine derivative 3%; 5% of lauryl phenylacetate is selected as the defoaming agent; the rest is the same as example 2.

Example 27

The organic solvent is diethylene glycol monomethyl ether and l-methoxy-2-propanol mixed solution (volume ratio is 3: 1), the organic pigment or dye is pigment yellow 1505, the high polymer is polyurethane 6% and unsaturated polyester 8%, the adhesive is nitrocellulose 2% and phenolic resin 3%, the antifoaming agent is simethicone 4%, the antioxidant is butyl hydroxy anisole 1%, 2, 6-tertiary butyl-4-methyl phenol 1%, tetra [ β - (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester 1%, and the rest is the same as example 2.

Example 28

The organic solvent is a mixed solution of methyl lactate and methanol (volume ratio is 1: 3); the organic pigment or dye is pigment yellow 15125%; the high polymer is prepared from 20% of epoxy resin and 20% of phenolic resin; the adhesive is composed of 10% of acrylic acid oligomer and 10% of nitrocellulose; 2% of polyether modified silicone oil is selected as the defoaming agent; the rest is the same as example 2.

Example 29

The organic solvent is a mixed solution of ethyl lactate and ethanol (volume ratio is 1: 6); 1% of diarylamine red is selected as the organic pigment or dye; the high polymer is selected from 12 percent of organic silicon resin and 18 percent of polyvinyl alcohol; the adhesive is composed of 10% of acrylic acid oligomer and 2% of acrylic acid homopolymer; the defoaming agent is composed of 1% of lauryl phenylacetate and 1% of dimethyl silicone oil; the antioxidant is selected from 4% of didodecyl alcohol ester; the rest is the same as example 2.

Example 30

The organic solvent is a mixed solution of methyl ethyl ketone and ethyl lactate (volume ratio is 1: 4); 3% of monoazo is selected as the organic pigment or dye; the high polymer is prepared from 15% of cyanate ester resin and 35% of acrylic resin; the adhesive is selected from 3% of polyamide and 4% of acrylic acid homopolymer; 0.1 percent of phenethyl alcohol oleate, 0.1 percent of dimethyl silicone oil and 0.1 percent of polyether modified silicone oil are selected as the defoaming agent; the antioxidant is 0.5 percent of ditetradecanol ester; the rest is the same as example 2.

Example 31

The organic solvent is a mixed solution of glycerol methyl ether and ethanol (volume ratio is 8: 1); the organic pigment or dye is selected from lake red C4%; the high polymer is selected from 8 percent of polyimide resin and 17 percent of urethane modified phenolic resin; the adhesive is selected from 2% of poly-polyhydric sugar alcohol and 2% of polyamide; 0.1 percent of phenethyl alcohol oleate is selected as the defoaming agent; 0.05% of polydimethylsiloxane is selected as the leveling agent; the antioxidant is 0.1 percent of dioctadecyl alcohol ester; the rest is the same as example 2.

Example 32

The organic solvent is a mixed solution of ethanol and glycerol methyl ether acetate (volume ratio is 9: 1); the organic pigment or dye is rose bengal 17%; polyacrylic acid is selected to be 20 percent; 5% of phenolic resin is selected as the adhesive; 0.5 percent of lauryl phenylacetate is selected as the defoaming agent; 0.1 percent of polyether polyester modified organic siloxane is selected as the flatting agent; the rest is the same as example 2.

Example 33

The organic solvent is a mixed solution of isopropanol and glycerol monomethyl ether (volume ratio is 1: 1); the organic pigment or dye is methyl violet 6%; the high polymer is prepared from 10% of phenolic resin, 15% of urethane-modified phenolic resin and 8% of unsaturated polyester; the adhesive is composed of 5% of acrylic acid oligomer and 1% of polyamide; 1% of sulfate salt is selected as the dispersant; 1% of dimethyl silicone oil is selected as the defoaming agent; 0.08 percent of alkyl modified organic siloxane is selected as the leveling agent; the rest is the same as example 2.

Example 34

The organic solvent is a mixed solution of glycerol methyl ether and ethanol (volume ratio is 1: 1); organic pigment or dye is 5% of phthalocyanine; the high polymer is prepared from 25% of cyanate ester resin and 10% of polyacrylic acid; the adhesive is selected from 10% of phenolic resin and 10% of polyamide; 0.9 percent of sulfonate is selected as a dispersant; 2% of polyether modified silicone oil is selected as the defoaming agent; 1% of end group modified organic siloxane is selected as the leveling agent; the antioxidant is composed of diphenylamine 0.2%, p-phenylenediamine 0.3%, and dihydroquinoline 0.5%; other same implementation

Example 35

The organic solvent is a mixed solution of ethylene glycol diethyl ether and methanol (volume ratio is 10: 1); the organic pigment or dye is 156% of pigment blue; 5% of polyvinyl alcohol, 10% of alkyd resin and 20% of polyimide resin are selected as high polymers; 7% of acrylic acid homopolymer is selected as the adhesive; 0.5 percent of octadecylamine acetate is selected as a dispersant; 0.5 percent of fluorine modified acrylate is selected as the leveling agent; the rest is the same as example 2.

Example 36

The organic solvent is a mixed solution of ethylene glycol monomethyl ether and ethanol (volume ratio is 1: 1); 2% of ethyl violet is selected as the organic pigment or dye; the high polymer is prepared from 10% of acrylic resin, 18% of organic silicon resin and 10% of epoxy resin; 7% of nitrocellulose is selected as the adhesive; 0.5 percent of alkyl quaternary ammonium salt is selected as the dispersant; 0.5 percent of diphenylamine is selected as the antioxidant; the rest is the same as example 2.

Example 37

The organic solvent is a mixed solution of glycerol methyl ether and isopropanol (volume ratio is 1: 2); 3% of ethyl violet is selected as the organic pigment or dye; the high polymer is selected from 5% of polyamine resin and derivatives thereof, 20% of polyurethane and 20% of phenolic resin; 0.6 percent of aminopropylamine dioleate is selected as a dispersant; 6% of p-phenylenediamine is selected as the antioxidant; the rest is the same as example 2.

Example 38

The organic solvent is a mixed solution of l-methoxy-2-propanol and isopropanol (volume ratio is 1: 1); 1% of ethyl violet is selected as the organic pigment or dye; the high polymer is prepared from 10% of phenolic resin, 5% of organic silicon resin, 10% of cyanate ester resin and 10% of urethane modified phenolic resin; 3% of dihydroquinoline is selected as an antioxidant; the rest is the same as example 2.

Example 39

The organic solvent is a mixed solution of diethylene glycol monomethyl ether and glycerol monomethyl ether acetate (volume ratio is 5: 1); the organic pigment or dye is pigment violet 232 percent; the high polymer is selected from 30% of polyimide resin; 5% of nitrocellulose is selected as the adhesive; the antioxidant is 2% of butyl hydroxy anisole; the rest is the same as example 2.

Example 40

The organic solvent is a mixed solution of methyl lactate and ethyl lactate (volume ratio is 1: 1); 6 percent of bisazo is selected as the organic pigment or dye; the high polymer is selected from 10 percent of polyvinyl alcohol, 20 percent of unsaturated polyester, 10 percent of polyimide resin and 10 percent of polyacrylic acid; the adhesive is 12% of nitrocellulose; the defoaming agent is composed of 1% of phenethyl alcohol oleate, 1% of lauryl phenylacetate and 1% of simethicone; the antioxidant is 0.5 percent of butyl hydroxy anisole; the rest is the same as example 2.

EXAMPLE 41

The organic solvent is a mixed solution of ethyl lactate and ethanol (volume ratio is 1: 3); 3% of methyl violet is selected as the organic pigment or dye; 20% of polyurethane and 30% of epoxy resin are selected as high polymers; the antioxidant is propyl gallate 6%; the rest is the same as example 2.

Example 42

The organic solvent is a mixed solution of methyl ethyl ketone and methyl lactate (volume ratio is 1: 6); 1% of hansa yellow is selected as the organic pigment or dye; 65% of phenolic resin is selected as the high polymer; the antioxidant is 0.5 percent of 2, 6-tertiary butyl-4-methylphenol; the rest is the same as example 2.

Example 43

The organic solvent is a mixed solution of methanol and glycerol methyl ether acetate (volume ratio is 1: 4), the organic pigment or dye is diaryl orange 3%, the high polymer is urethane modified phenolic resin 60%, the antifoaming agent is phenethyl alcohol oleate 2%, the antioxidant is pentaerythritol tetrakis [ β - (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ] 7%, and the rest is the same as in example 2.

Example 44

The organic solvent is a mixed solution of ethanol and glycerol methyl ether acetate (volume ratio is 1: 2); the organic pigment or dye is 370.8 percent of pigment red; 25% of polyvinyl alcohol is selected as the high polymer; 4% of polyatomic sugar alcohol is selected as the adhesive; 0.09 percent of lauryl phenylacetate is selected as the defoaming agent; the antioxidant is selected from 0.1 percent of bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether; the rest is the same as example 2.

Example 45

The organic solvent is a mixed solution of isopropanol and diethylene glycol methyl ether (volume ratio is 9: 1); the organic pigment or dye is 0.18 percent of fused cyclic ketone; acrylic resin 35% is selected as the high polymer; 10% of phenolic resin is selected as the adhesive; 1% of dimethyl silicone oil is selected as the defoaming agent; 2% of tert-butyl hydroquinone is selected as the antioxidant; the rest is the same as example 2.

Example 46

The organic solvent is a mixed solution of l-methoxy-2-propanol and diethylene glycol methyl ether (the volume ratio is 1: 1); 1% of hansa yellow is selected as the organic pigment or dye; 10% of alkyd resin is selected as the high polymer; the adhesive is composed of 3% of acrylic acid homopolymer, 3% of acrylic acid oligomer and 10% of phenolic resin; 0.4 percent of polyether modified silicone oil is selected as the defoaming agent; 1% of polydimethylsiloxane is selected as the leveling agent; the antioxidant is 2% of didodecyl alcohol ester; the rest is the same as example 2.

Example 47

The organic solvent is a mixed solution of ethanol and methyl lactate (the volume ratio is 2: 1); the organic pigment or dye is selected from 1% of methyl violet and 1% of ethyl violet; the high polymer is selected from polyamine resin and derivatives thereof 30%; the adhesive is selected from 3% of poly-polyhydric sugar alcohol and 4% of nitrocellulose; 0.09 percent of polyether polyester modified organic siloxane is selected as the flatting agent; the antioxidant is 1% of ditetradecanol ester; the rest is the same as example 2.

Example 48

The organic solvent is a mixed solution of ethylene glycol ethyl ether, glycerol methyl ether acetate and methyl ethyl ketone (volume ratio is 1:1: 1); the organic pigment or dye is prepared from 370.8% of pigment red and 1490.7% of pigment red; 30% of polyurethane is selected as the high polymer; the adhesive is 16% of acrylic acid oligomer; 2.6 percent of sulfate salt is selected as the dispersant; 3% of alkyl modified organic siloxane is selected as the leveling agent; the antioxidant is selected from dioctadecyl alcohol ester 4 percent; the rest is the same as example 2.

Example 49

The organic solvent is selected from ethylene glycol methyl ether, diethylene glycol methyl ether and methanol mixed solution (volume ratio is 1:2: 2); the organic pigment or dye is selected from 150.6 percent of pigment blue and 1850.6 percent of pigment red; 45% of epoxy resin is selected as the high polymer; the adhesive is 13% of acrylic acid homopolymer; 2% of sulfonate is selected as a dispersant; 2% of end group modified organic siloxane is selected as the leveling agent; the rest is the same as example 2.

Example 50

The organic solvent is a mixed solution of glycerol methyl ether, isopropanol and methyl lactate (the volume ratio is 2:1: 3); the organic pigment or dye is pigment red 1851%; 20% of organic silicon resin is selected as the high polymer; 4% of polyamide is selected as the adhesive; 0.05 percent of octadecylamine acetate is selected as a dispersant; 0.6 percent of fluorine modified acrylate is selected as the leveling agent; the rest is the same as example 2.

Example 51

The organic solvent is a mixed solution of glycerol methyl ether acetate, l-methoxy-2-propanol and ethanol (the volume ratio is 3:1: 1); organic pigment or dye is rose red 0.3%; 10% of cyanate ester resin is selected as the high polymer; 2% of polyatomic sugar alcohol is selected as the adhesive; 0.06 percent of alkyl quaternary ammonium salt is selected as the dispersant; the antioxidant is selected from 0.1 percent of ditetradecanol ester and 0.1 percent of dioctadecyl alcohol ester; the rest is the same as example 2.

Example 52

The organic solvent is a mixed solution of diethylene glycol methyl ether, glycerol methyl ether and isopropanol (volume ratio is 4:1: 2); the organic pigment or dye is selected from Hansa yellow 2%, pigment yellow 1503% and pigment yellow 1513%; 5% of polyimide resin is selected as the high polymer; 10% of phenolic resin is selected as the adhesive; 0.05 percent of aminopropylamine dioleate is selected as a dispersant; 0.1 percent of phenethyl alcohol oleate is selected as the defoaming agent; the rest is the same as example 2.

Example 53

The organic solvent is a mixed solution of methyl lactate, methyl ethyl ketone and ethylene glycol methyl ether (volume ratio is 1:1: 1); organic pigment or dye selected from 0.1% of lake; polyacrylic acid is selected to be 20 percent; 5% of urethane modified phenolic resin is selected as the adhesive; 0.3 percent of lauryl phenylacetate is selected as the defoaming agent; the antioxidant is selected from 0.2 percent of diphenylamine and 0.1 percent of docosanol ester; the rest is the same as example 2.

Example 54

The organic solvent is a mixed solution of ethyl lactate, glycerol methyl ether and ethanol (volume ratio is 1:2: 3); the organic pigment or dye is selected from pigment red 372%; 60% of unsaturated polyester is selected as the high polymer; the adhesive is 8% of nitrocellulose; 3% of dimethyl silicone oil is selected as the defoaming agent; the antioxidant is selected from 2% of p-phenylenediamine and 3% of bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether; the rest is the same as example 2.

Example 55

The organic solvent is a mixed solution of methyl ethyl ketone and isopropanol (volume ratio is 1: 2); 3% of monoazo and 4% of disazo are selected as the organic pigment or dye; 5% of polyacrylic acid is selected as the high polymer; 2% of acrylic acid oligomer is selected as the adhesive; 0.05 percent of polyether modified silicone oil is selected as the defoaming agent; 0.05% of alkyl modified organic siloxane and 0.05% of polyether polyester modified organic siloxane are selected as flatting agents; 0.1% of dihydroquinoline is selected as an antioxidant; the rest is the same as example 2.

Example 56

The organic solvent is a mixed solution of methanol, glycerol methyl ether acetate and isopropanol (volume ratio is 2:3: 1); 3% of bisazo is selected as the organic pigment or dye; 30% of phenolic resin is selected as the high polymer; 0.7 percent of phenethyl alcohol oil is selected as the defoaming agent; the rest is the same as example 2.

Example 57

The organic solvent is a mixed solution of ethanol, glycerol monomethyl ether acetate and isopropanol (volume ratio is 5:1: 2); the organic pigment or dye is selected from quinacridone 8%; 40% of urethane modified phenolic resin is selected as the high polymer; 6% of polyamide is selected as the adhesive; the antioxidant is 1% of dibutyl hydroxy toluene; the rest is the same as example 2.

Example 58

The organic solvent is selected from isopropanol and ethanol mixed solution (volume ratio is 1: 2); 4% of organic pigment or dye selected from lake; 10% of polyvinyl alcohol is selected as the high polymer; 2% of polyatomic sugar alcohol is selected as the adhesive; the antioxidant is 0.5% of propyl gallate; the rest is the same as example 2.

Example 59

The organic solvent is a mixed solution of methanol and diethylene glycol methyl ether (volume ratio is 1: 2); the organic pigment or dye is selected from 10 percent of monoazo; 20% of acrylic resin is selected as the high polymer; the adhesive is prepared from 10% of amino esterification modified phenolic resin and 5% of nitrocellulose; 0.5 percent of alkyl modified organic siloxane is selected as the flatting agent; the rest is the same as example 2.

Example 60

The organic solvent is a mixed solution of ethanol and diethylene glycol methyl ether (volume ratio is 1: 1); the organic pigment or dye is 5% of diaryl orange; 50% of alkyd resin is selected as the high polymer; the adhesive is 10% of acrylic acid homopolymer; 0.8 percent of phenylacetic acid is selected as a dispersing agent; the rest is the same as example 2.

Example 61

Mixing 2 parts of phthalocyanine, 2 parts of epoxy acrylic resin, 10 parts of acrylic acid-2-ethylhexyl ester and 10 parts of Irgacure184, heating to 30-50 ℃, dissolving and dispersing the substances to prepare a coating liquid, coating the coating liquid on an aluminum plate substrate with the roughness of 0.6 and the thickness of 0.2mm, radiating by ultraviolet light, drying to obtain a lithographic plate original plate, and drying to obtain a resin layer with the thickness of 5 mu m.

The ultra-short pulse laser platemaking machine doped with titanium sapphire is used, the wavelength of output laser is 700nm, and the pulse width is 5 multiplied by 10^-13Second, repetition frequency of 50KHz, and pulse energy of 4.5J/cm²Otherwise, the same procedure as in example 6 was repeated.

Example 62

4 parts of quinacridone, 6 parts of polyurethane acrylic resin, 5 parts of hexanediol diacrylate, 10 parts of trihydroxymethylpropane triacrylate, 10 parts of neopentyl glycol diacrylate, 5 parts of Irgacure819 and 10 parts of Irgacure651 are mixed to prepare a coating liquid, the coating liquid is coated on an aluminum alloy plate substrate with the roughness of 0.9 and the thickness of 0.2mm, the aluminum alloy plate substrate is irradiated by ultraviolet light and then dried to obtain a lithographic plate original edition, and the thickness of the dried resin layer is 3.5 microns.

Using titanium-doped sapphire ultrashort pulse laser platemaking machine, the wavelength of output laser is 1600nm, and the pulse width is 10^-12Second, repetition frequency of 1KHz, and pulse energy of 0.1J/cm²Otherwise, the same procedure as in example 6 was repeated.

Example 63

3 parts of fused cyclic ketone, 5 parts of polyurethane acrylic resin, 5 parts of polyether ester acrylic resin, 5 parts of tripropylene glycol diacrylate and 3 parts of Irgacure907 are mixed to prepare a coating liquid, the coating liquid is coated on a galvanized sheet substrate with the roughness of 0.7 and the thickness of 0.2mm, the coating liquid is subjected to ultraviolet radiation and then dried to obtain a lithographic plate original plate, and the thickness of the dried resin layer is 1.5 mu m.

Using titanium-doped sapphire ultrashort pulse laser platemaking machine, the wavelength of output laser is 500nm, and the pulse width is 10^-12Second, repetition frequency of 55KHz, pulse energy of 3J/cm²Otherwise, the same procedure as in example 6 was repeated.

Example 64

5 parts of hansa yellow, 3 parts of bisphenol A epoxy acrylic resin, 8 parts of dipropylene glycol diacrylate, 2 parts of Irgacure369, 3 parts of ITX and 0.5 part of sodium carboxylate are mixed to prepare a coating liquid, the coating liquid is coated on a galvanized sheet substrate with the roughness of 0.6 and the thickness of 0.2mm, the coating liquid is subjected to ultraviolet radiation and then dried to obtain a lithographic original plate, and the thickness of the dried resin layer is 4 microns.

Using titanium-doped sapphire ultrashort pulse laser platemaking machine, the output laser wavelength is 2000nm, pulse width of 3X 10^-16Second, repetition frequency of 15KHz, pulse energy of 6.5J/cm²Otherwise, the same procedure as in example 6 was repeated.

Example 65

6 parts of pigment yellow 150, 4 parts of bisphenol A epoxy acrylic resin, 8 parts of epoxy acrylic resin, 40 parts of trihydroxy methyl propane triacrylate, 20 parts of Irgacure819, 1 part of sulfate ester salt, 2 parts of polyacrylate and 1 part of polyhexamethylene internal polyol-polyethyleneimine block copolymer are mixed to prepare a coating liquid, the coating liquid is coated on an aluminum plate substrate with the roughness of 0.1 and the thickness of 0.2mm, the aluminum plate substrate is subjected to ultraviolet radiation and then dried to obtain a lithographic plate original plate, and the thickness of the dried resin layer is 3 microns.

Using titanium-doped sapphire ultrashort pulse laser platemaking machine, the output laser wavelength is 1100nm, and pulse width is 4X 10^-17Second, repetition frequency of 75KHz, pulse energy of 2.5J/cm²Otherwise, the same procedure as in example 6 was repeated.

Example 66

10 parts of pigment yellow 151, 7 parts of epoxy acrylic resin, 15 parts of neopentyl glycol diacrylate, 15 parts of 2-ethylhexyl acrylate, 14 parts of Darocur1173 and 1 part of sulfonate are mixed to prepare a coating liquid, the coating liquid is coated on an aluminum substrate with the roughness of 0.2 and the thickness of 0.2mm, the coating liquid is subjected to ultraviolet radiation and then dried to obtain a lithographic printing plate original plate, and the thickness of the dried resin layer is 2.5 microns.

Using titanium-doped sapphire ultrashort pulse laser platemaking machine, the wavelength of output laser is 300nm, and the pulse width is 7X 10^-15Second, repetition frequency of 10KHz, pulse energy of 1J/cm²Otherwise, the same procedure as in example 6 was repeated.

Example 67

1 part of diarylamine red, 4 parts of polyurethane acrylic resin, 30 parts of isoborneol acrylate, 20 parts of tripropylene glycol diacrylate, 20 parts of TPO, 10 parts of Irgacure184 and 3 parts of octadecenylamine acetate are mixed to prepare a coating liquid, the coating liquid is coated on a galvanized plate substrate with the roughness of 0.7 and the thickness of 0.2mm, the coating liquid is subjected to ultraviolet radiation and then dried to obtain a lithographic plate original edition, and the thickness of the dried resin layer is 4.5 microns.

Using titanium-doped sapphire ultrashort pulse laser platemaking machine, the output laser wavelength is 100nm, pulse width of 10^-15Second, repetition frequency of 100KHz, pulse energy of 9J/cm²Otherwise, the same procedure as in example 6 was repeated.

Example 68

0.5 part of pigment red 185, 12 parts of polyether ester acrylic resin, 6 parts of acrylic acid-2-ethylhexyl ester, 3 parts of ITX, 1 part of Irgacure907 and 1 part of alkyl quaternary ammonium salt are mixed to prepare a coating liquid, the coating liquid is coated on an aluminum alloy plate substrate with the roughness of 0.4 and the thickness of 0.2mm, the aluminum alloy plate substrate is subjected to ultraviolet radiation and then dried to obtain a lithographic plate original plate, and the thickness of the resin layer after drying is 5 microns.

Using titanium-doped sapphire ultrashort pulse laser platemaking machine, the wavelength of output laser is 600nm, and the pulse width is 10^-16Second, repetition frequency of 80KHz, pulse energy of 2J/cm²Otherwise, the same procedure as in example 6 was repeated.

Example 69

Organic pigment or dye is selected from lake red C2; the oligomer is bisphenol A epoxy acrylic resin 15 parts; the active monomer is selected from 20 parts of hexanediol diacrylate and 15 parts of dipropylene glycol diacrylate; irgacure18425 parts of photoinitiator and 5 parts of aminopropylamine dioleate as dispersant are used, and the rest is the same as in example 6.

Example 70

1.5 parts of rose bengal is selected as the organic pigment or dye; the oligomer is prepared from 3 parts of epoxy acrylic resin, 3 parts of bisphenol A epoxy acrylic resin and 3 parts of polyether ester acrylic resin; 25 parts of tripropylene glycol diacrylate is selected as the active monomer; 65110 parts of Irgacure as the photoinitiator, 1 part of quaternary ammonium salt and 1.5 parts of oil amino oleate as the dispersant, and the rest is the same as example 6.

Example 71

3 parts of methyl violet is selected as the organic pigment or dye; 5 parts of polyurethane acrylic resin is selected as the oligomer; the active monomer is selected from 20 parts of dipropylene glycol diacrylate; the photoinitiator is ITX6 parts and Darocur 11735 parts, and the dispersant is modified polyaminoamide phosphate 2 parts; the rest is the same as example 6.

Example 72

6 parts of phthalocyanine is selected as the organic pigment or dye; 10 parts of polyether ester acrylic resin is selected as the oligomer; 8 parts of trihydroxy methyl propane triacrylate is selected as an active monomer; irgacure 3692 parts and Darocur 11733 parts are selected as the photoinitiator, and 0.8 part of fatty acid ethylene oxide adduct is selected as the dispersant; the rest is the same as example 6.

Example 73

233 parts of pigment violet is selected as the organic pigment or dye; 2 parts of polyurethane acrylic resin and 3 parts of bisphenol A epoxy acrylic resin are selected as the oligomer; 5 parts of neopentyl glycol diacrylate is selected as the active monomer; irgacure 8193 parts of photoinitiator, 0.5 part of polyethylene glycol derivative and 0.5 part of fatty acid ethylene oxide adduct as dispersant; the rest is the same as example 6.

Example 74

2 parts of ethyl violet is selected as the organic pigment or dye; 11 parts of epoxy acrylic resin is selected as the oligomer; active monomer is 10 parts of isoborneol acrylate; the photoinitiator is Darocur 11736 parts, and the dispersant is polyethyleneimine derivative 1 part; the rest is the same as example 6.

Example 75

5 parts of ethyl violet is selected as the organic pigment or dye; 13 parts of epoxy acrylic resin is selected as the oligomer; the active monomer is 7 parts of acrylic acid-2-ethylhexyl ester; 3 parts of TPO (thermoplastic polyolefin) are selected as a photoinitiator, 0.3 part of polyurethane introduced with an anchoring group and 0.4 part of low molecular weight polyester are selected as a dispersant; the rest is the same as example 6.

Example 76

3.5 portions of lake red C are selected as organic pigment or dye; 7 parts of polyurethane acrylic resin is selected as the oligomer; the active monomer is selected from 3 parts of hexanediol diacrylate and 14 parts of isoborneol acrylate; 2 parts of TPO, 2 parts of Darocur11734 parts of Darocur 8193 parts of Irgacure; 1.5 parts of phosphate type high polymer is selected as the dispersant; the rest is the same as example 6.

Example 77

3.5 parts of rose bengal is selected as the organic pigment or dye; 8 parts of epoxy acrylic resin is selected as the oligomer; the active monomer is selected from 10 parts of tripropylene glycol diacrylate, 5 parts of neopentyl glycol diacrylate and 7 parts of acrylic acid-2-ethylhexyl ester; the photoinitiator is Irgacure 18412 parts; 1 part of sodium carboxymethylcellulose and 0.2 part of sodium oleate are selected as dispersing agents; the rest is the same as example 6.

Example 78

2 parts of disazo is selected as the organic pigment or dye; 2 parts of bisphenol A epoxy acrylic resin and 10 parts of polyether ester acrylic resin are selected as the oligomer; 28 parts of dipropylene glycol diacrylate is selected as the active monomer; 17 parts of ITX is used as a photoinitiator; 3 parts of sodium carboxymethylcellulose is selected as a dispersing agent; the rest is the same as example 6.

Example 79

3 parts of phthalocyanine and 1 part of diaryl orange are selected as the organic pigment or dye; the oligomer is prepared from 6 parts of polyurethane acrylic resin and 3 parts of epoxy acrylic resin; 7 parts of trihydroxy methyl propane triacrylate and 5 parts of isoborneol acrylate are selected as active monomers; irgacure 9078 parts of a photoinitiator; 1 part of sodium oleate is selected as the dispersing agent; the rest is the same as example 6.

Example 80

1 part of hansa yellow is selected as the organic pigment or dye; the oligomer is selected from 1 part of polyether ester acrylic resin and 1 part of epoxy acrylic resin; 5 parts of neopentyl glycol diacrylate is selected as the active monomer; irgacure 3693 parts of photoinitiator are selected; the rest is the same as example 6.

Claims

1. A process-free lithographic printing plate precursor characterized by: the resin comprises a metal substrate subjected to graining treatment and a laser-ablatable ink-philic resin layer or an ultraviolet light curing resin layer which does not contain any photosensitive substance and is arranged on the metal substrate;

2. The process-free lithographic printing plate precursor of claim 1 wherein: the metal substrate is any one of a pure aluminum plate, an aluminum alloy plate, an iron plate and a galvanized plate, and is subjected to electrolytic oxidation treatment or laser engraving treatment in advance to form grains with the surface average roughness of 0.1-0.9 um; the thickness of the ink-philic resin layer or the ultraviolet light curing resin layer is 0.5-5 um after being dried.

3. The process-free lithographic printing plate precursor of claim 1 wherein: the organic solvent is selected from one or more of ethylene glycol ethyl ether, ethylene glycol methyl ether, glycerol monomethyl ether, glycerol methyl ether acetate, diethylene glycol methyl ether, methyl lactate, ethyl lactate, methyl ethyl ketone, methanol, ethanol, isopropanol and l-methoxy-2-propanol; the organic pigment or dye is selected from monoazo, disazo, lake, phthalocyanine, quinacridone, fused ring pigment, hansa yellow, pigment yellow 150, pigment yellow 151, pigment red 37, pigment red 149, pigment red 185, pigment violet 23, pigment blue 15: 1. pigment green 7, diarylamine red, diarylorange, lake red C, rose red, methyl violet and/or ethyl violet, wherein the mass fraction of the pigment green in the organic solvent is 0.1-25%; the high polymer is selected from any one or more than two of phenolic resin, urethane-modified phenolic resin, polyvinyl alcohol, acrylic resin, alkyd resin, polyamine resin and derivatives thereof, polyurethane, epoxy resin, organic silicon resin, cyanate resin, polyimide resin, polyacrylic acid and unsaturated polyester, and the mass fraction of the high polymer in an organic solvent is 5-65%; the adhesive is selected from one or a composition of more than two of phenolic resin, urethane-modified phenolic resin, nitrocellulose, oligomer or homopolymer of acrylic acid, polyamide and poly-polyol sugar alcohol, and the mass fraction of the adhesive in the organic solvent is 2-20%; the oligomer is selected from any one or a composition of more than two of epoxy acrylic resin, polyurethane acrylic resin, polyether ester acrylic resin and bisphenol A epoxy acrylic resin; the active monomer is selected from any one or a combination of more than two of 2-ethylhexyl acrylate, hexanediol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, trihydroxymethyl propane triacrylate, neopentyl glycol diacrylate, isoborneol acrylate and ethoxy ethyl acrylate EOEOEA; the photoinitiator is selected from one or more than two of Irgacure184, Irgacure651, Irgacure907, Irgacure369, Irgacure819, Darocur1173, TPO and ITX; the ultraviolet light curing resin layer comprises the following raw materials in parts by weight: 0.1-25 parts of organic pigment or dye, 2-15 parts of oligomer, 5-50 parts of active monomer and 3-30 parts of photoinitiator.

4. The process-free lithographic printing plate precursor of claim 1 wherein: the auxiliary agent in the ink-philic resin layer organic solvent is one or the combination of more than two of a dispersant, a defoaming agent, a flatting agent and an antioxidant; the mass fractions of the dispersing agent, the defoaming agent, the flatting agent and the antioxidant in the organic solvent are respectively 0.05-3%, 0.05-5%, 0.05-3% and 0.1-10%; the ultraviolet light curing resin layer further comprises 0.5-5 parts of a dispersing agent.

5. The non-treatment lithographic printing plate precursor according to claim 4, wherein the dispersant is selected from the group consisting of sodium carboxymethylcellulose, sodium oleate, sodium carboxylates, sulfate ester salts, sulfonates, octadecenylamine acetate, alkyl quaternary ammonium salts, aminopropylamine dioleate, quaternary ammonium salts, modified polyaminoamide phosphates, fatty acid ethylene oxide adducts, polyethylene glycol and polyethyleneimine derivatives, phosphate-type high polymers, oleyl aminooleate, polyhexamethylene internal polyol-polyethyleneimine block copolymers, low molecular weight polyesters, polyurethanes incorporating anchor groups, and polyacrylates, wherein the antifoaming agent is selected from the group consisting of phenethyl alcohol oleate, lauryl phenylacetate, dimethicone, and any one or more of a polyether-modified silicone oil antifoaming agent, wherein the leveling agent is selected from the group consisting of polydimethylsiloxane, polyether-polyester-modified organosiloxane, alkyl-modified organosiloxane, terminal-modified silicone, fluorine-modified acrylate, and wherein the antioxidant is selected from the group consisting of diphenylamine, p-phenylenediamine, dihydroquinoline, butylhydroxyanisole, dibutylhydroxytoluene, propyl gallate, 2, 6-methylbutyl-4-methyl-butyl-phenol, bis (3-tert-butyl-phenyl) phenol, bis (3-tert-butyl-4-phenyl-tetradecylphenol), bis (3-tert-butyl-phenyl) phenyl-5-pentaerythritol ester, bis (3-tert-butyl-5-tetradecylphenyl) propionate, bis (3-dodecylphenyl) and any one or more tertiary butyl-5-bis (tert-dodecylphenyl) pentaerythritol ester.

6. A process for ultrashort pulse laser lithography using the process-free lithographic printing plate precursor according to any of claims 1 to 5, wherein: according to the digitalized content of the original, the blank part is etched away by using an ultrashort pulse laser beam to form a hydrophilic area, and an image-text area which can be ink-loving is left, so that the printing plate is manufactured.

7. The ultrashort pulse laser platemaking method of claim 6, wherein: the ultrashort pulse laser beam is generated by picosecond, femtosecond or attosecond laser, and the laser pulse width is 10^-12～10^-18Second, pulse energy is 0.1-10J/cm²The center wavelength is 100-2000 nm, the repetition frequency is 1-100 kHz, and the moving etching width of the laser beam is 280-1600 mm.

8. An ultrashort pulse laser platemaking machine is characterized in that: a plate-making machine using an ultra-short pulse laser and using the plate-making method according to claim 7.