Nano composite material modified high-sensitivity treatment-free negative image CTP plate material and preparation method thereof

Abstract

The invention relates to the technical field of lithographic printing plate making, and particularly discloses a nano composite material modified high-sensitivity treatment-free negative image CTP plate material and a preparation method of the nano composite material modified high-sensitivity treatment-free negative image CTP plate material. A photosensitive layer of the plate comprises the following components in percentage by mass: 0.5-3% of a nano composite material, 10-14% of an iodonium salt photoinitiator, 32-38% of a cross-linking agent, 0.1-0.3% of a dispersing agent and the balance of an acrylic copolymer (Tg is equal to 85 DEG C); the added nano composite material is used for loading graphene and particles to improve the dispersion compatibility of the graphene, and then a compound is chemically grafted: a modified dye is grafted to the surface of the graphene through esterification and other reactions (the grafting rate is greater than or equal to 85%) to form a photothermal conversion unit with a local surface plasma effect, so that the photothermal conversion effect is improved. The prepared treatment-free negative image CTP plate material has excellent properties such as high sensitivity and high thermal conductivity, the printing endurance rate is greater than 200,000 (improved by 50%), and the dot reproducibility reaches 99%.

Description

Technical Field

[0001] This invention relates to the field of offset printing plate making technology, specifically to a nanocomposite material modified high-sensitivity, pre-treated negative CTP plate and its preparation method. Background Technology

[0002] Currently, there are four types of CTP plates on the market: thermal CTP plates, silver halide CTP plates, photopolymer CTP plates, and pre-processed CTP plates. Pre-processed negative CTP plates refer to plates that, after exposure and imaging on direct-to-plate (DTP) equipment, can be directly printed without subsequent processing steps such as chemical development. The advantages of pre-processed negative CTP plates include increased production efficiency by eliminating post-processing steps, reduced energy consumption during exposure due to the absence of chemical development, lower overall plate-making costs, shorter plate-making cycle, and no environmental pollution. Existing pre-processed negative CTP plates often employ a double-layer structure design (such as a hydrophilic layer + photosensitive layer), relying on infrared absorbers (such as cyanine dyes) to achieve photothermal conversion. However, they still have the following drawbacks: insufficient quantum efficiency of the infrared absorber, resulting in low photosensitivity (typical value >200mJ / cm²). 2 Uneven heat diffusion within the coating leads to incomplete polymer curing; and the coating's scratch resistance and storage stability are difficult to balance.

[0003] Literature CN113655690B improves development speed by regulating hydrophilicity through a double-layer resin, but does not address the improvement of photothermal conversion efficiency. Based on the above issues, this solution proposes to overcome the existing bottlenecks through nanomaterial composite technology. Summary of the Invention

[0004] Based on the shortcomings of existing unprocessed negative CTP plates in terms of photosensitivity and thermal conversion efficiency, this invention solves the above-mentioned technical problems. This invention provides a nanocomposite material modified high photosensitivity unprocessed negative CTP plate, which is composed of an aluminum substrate and a photosensitive layer.

[0005] The photosensitive layer comprises the following components by weight percentage: 0.5-3% nanocomposite material, 10-14% iodonium salt photoinitiator, 32-38% crosslinking agent, 0.1-0.3% dispersant, and the balance being acrylic copolymer (Tg = 85℃);

[0006] The photosensitive layer comprises the following components by weight percentage: 2% nanocomposite material, 12% iodonium salt photoinitiator, 35% crosslinking agent, 0.2% dispersant, and the balance being acrylic copolymer (Tg = 85℃);

[0007] The crosslinking agent is a mixture of pentaerythritol tetraacrylate and propoxylated glycerol acrylate in a mass ratio of 11-13:1-3. Pentaerythritol tetraacrylate can highly crosslink and improve the heat resistance and mechanical properties of the resin, while propoxylated glycerol acrylate can crosslink rapidly and has high light transmittance, reducing the shrinkage rate of the resin. The combination of the two can improve the performance of the resin.

[0008] The dispersant is a polyether-modified polysiloxane leveling agent;

[0009] The nanocomposite material is prepared by mixing graphene oxide and microparticles in a mixed acid to form a suspension, and then reacting it with a modified dye.

[0010] The preparation method of the nanocomposite material includes the following steps:

[0011] (1) Graphene oxide and microparticles were combined in a mass ratio of 11-14:2-6 to form a composite. The composite was placed in a mixed acid (H2SO4 / HNO3 = 3:1) and ultrasonically exfoliated to obtain a suspension with a solid content of 0.5-3.0 wt%. (2) The suspension was mixed with a modified dye at 40-55℃ to obtain a reaction mixture. The amount of modified dye was 1.5-2.0% of the mass of the composite. 1-2 wt% of EDC / NHS catalyst was added to the reaction mixture. After reacting for 11-13 h, the mixture was centrifuged and washed to obtain a nanocomposite material.

[0012] The microparticles are formed by grinding and mixing silicon dioxide and Tween 80 in a molar ratio of 5:1-3 and then drying them. They have long-chain alkyl groups, which can be loaded onto graphene to form a uniform composite structure, overcoming the problem of low dispersion compatibility of single graphene and improving the thermal conductivity and mechanical properties of graphene.

[0013] The modified dye is prepared by dispersing butanetetracarboxylic acid and an equimolar amount of aminosilane in a dimethyl sulfoxide solution and heating to obtain a modified solution. After cooling, IR-820 dye is added to the modified solution at a solid-liquid ratio of 1:3-6 g / mL and reacted at 55-65℃ for 15-20 min. After drying, the modified dye is obtained. The volume ratio of dimethyl sulfoxide solution to aminosilane is 10:1-2.

[0014] The heating reaction is carried out at 70-80℃ for 20-30 minutes;

[0015] Heating promotes the hydrolysis of aminosilane, generating catalytically active silanol groups, which promotes the grafting copolymerization of IR-820 dye with butanetetracarboxylic acid and aminosilane into a conjugated system, enhancing light absorption. The increased aminocarboxyl groups improve fluorescence stability and self-dispersion properties. The modified dye can be modified with graphene composite materials through esterification and charge interaction, resulting in a high grafting rate. The core-shell structure formed on the surface of the graphene composite material creates a photothermal conversion unit with localized surface plasmon effects.

[0016] This invention also provides a method for preparing a high-sensitivity, pre-processed negative CTP plate modified with nanocomposite materials, comprising the following steps:

[0017] Step 1: Preparation of aluminum substrate: The aluminum plate is roughened by electrolysis and then anodized to form an aluminum oxide layer with a pore size of 20-50nm;

[0018] Step 2: Coating: The raw materials of the photosensitive layer are mixed according to the mass percentage and then subjected to ultrasonic centrifugation to obtain the coating material. The coating material is then coated onto the photosensitive layer using a microgravure plate at a linear speed of 7-9 m / min. After drying, the coating thickness is 1.2 ± 0.1 μm.

[0019] The ultrasonic centrifugation process involves sonicating the photosensitive layer material at an ultrasonic frequency of 10-20 kHz for 10-20 minutes, followed by centrifugation at 500-600 rpm for 1-3 minutes.

[0020] The beneficial effects of this invention are as follows: This invention provides a nanocomposite modified high-sensitivity, pre-treated negative CTP plate. This invention loads graphene with microparticles containing long-chain alkyl groups to form a uniform composite structure with good dispersion and compatibility. Then, through chemical grafting of the composite, modified dyes are grafted onto the graphene surface via esterification and other reactions (grafting rate ≥ 85%). The resulting nanocomposite material has a specific surface area > 600 m². 2 / g, the thermal conductivity is increased to 5300W / mK, which promotes rapid heat conduction and forms photothermal conversion units with local surface plasma effect in the photosensitive layer. The resulting untreated negative CTP plate has excellent properties such as high photosensitivity and high thermal conductivity, with a print durability of >200,000 impressions (an improvement of 50%) and dot reproducibility of 99%.

[0021] This invention provides a method for preparing a high-sensitivity, pre-treated negative CTP plate modified with nanocomposite materials. Through inorganic / organic hybrid interface design, it achieves a synergistic improvement in photothermal conversion efficiency and mechanical strength, breaking through the existing patent barriers. In the preparation process of the photosensitive layer, the ultrasonic-centrifugation method is used to achieve a vertical gradient distribution of nanocomposite materials in the acrylic resin matrix (surface concentration > bottom layer 20%), optimizing the heat transfer path. Detailed Implementation

[0022] The present invention will be further described in detail below through specific implementation examples. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of protection of the present invention. After reading the present invention, any modifications of the present invention in various equivalent forms by those skilled in the art fall within the scope of the appended claims.

[0023] In this invention, numerical ranges are involved. Unless otherwise specified, the numerical ranges are considered continuous and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe features or characteristics, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are included.

[0024] In this invention, there are no particular limitations on the specific dispersion and stirring methods.

[0025] Unless otherwise specified, the experimental methods used in this invention are conventional methods; unless otherwise specified, the materials and reagents used are commercially available.

[0026] Example 1

[0027] A method for preparing a nanocomposite modified high-sensitivity, pre-processed negative CTP plate

[0028] Step 1: Preparation of aluminum substrate: The aluminum plate is roughened by electrolysis and then anodized to form an aluminum oxide layer with a pore size of 20-50nm;

[0029] Step 2: Coating: Mix the photosensitive layer raw materials according to the mass percentage, sonicate at an ultrasonic frequency of 15kHz for 15min, and then centrifuge at 550rpm for 2min to obtain the coating material. Coating the photosensitive layer with the coating material using a microgravure plate at a linear speed of 8m / min. After drying, the coating thickness is 1.2±0.1μm.

[0030] The photosensitive layer comprises the following components by weight percentage: 2% nanocomposite material, 12% iodonium salt photoinitiator, 35% crosslinking agent, 0.2% polyether-modified polysiloxane leveling agent, and the balance being acrylic copolymer (Tg = 85℃);

[0031] The crosslinking agent is composed of pentaerythritol tetraacrylate and propoxylated glycerol acrylate in a mass ratio of 12:2.

[0032] The preparation method of the nanocomposite material includes the following steps:

[0033] (1) A composite of graphene oxide and microparticles in a mass ratio of 13:4 was placed in a mixed acid (H2SO4 / HNO3 = 3:1) and ultrasonically exfoliated to obtain a suspension with a solid content of 1.5 wt%.

[0034] (2) The suspension was mixed with the modified dye at 50°C to obtain a reaction mixture. The amount of modified dye was 1.8% of the mass of the composite. 1 wt% of EDC / NHS catalyst was added to the reaction mixture. After reacting for 12 h, the mixture was centrifuged and washed to obtain the nanocomposite material. The microparticles were formed by grinding and mixing silica and Tween 80 at a molar ratio of 5:2 and then drying. The modified dye was obtained by dispersing butanetetracarboxylic acid and an equimolar amount of aminosilane in a dimethyl sulfoxide solution and heating at 75°C for 25 min to obtain a modified solution. After cooling, IR-820 dye was added to the modified solution at a solid-liquid ratio of 1:5 g / mL and reacted at 60°C for 18 min. After drying, the modified dye was obtained. The volume ratio of dimethyl sulfoxide solution to aminosilane was 10:1.

[0035] Example 2

[0036] A method for preparing a nanocomposite modified high-sensitivity, pre-processed negative CTP plate

[0037] Step 1: Preparation of aluminum substrate: The aluminum plate is roughened by electrolysis and then anodized to form an aluminum oxide layer with a pore size of 20nm;

[0038] Step 2: Coating: Mix the photosensitive layer raw materials according to the mass percentage, sonicate at an ultrasonic frequency of 10kHz for 10min, and then centrifuge at 500rpm for 1min to obtain the coating material. Coating the photosensitive layer with the coating material using a microgravure plate at a linear speed of 7m / min. After drying, the coating thickness is 1.2±0.1μm.

[0039] The photosensitive layer comprises the following components by weight percentage: 0.5% nanocomposite material, 10% iodonium salt photoinitiator, 32% crosslinking agent, 0.1% polyether-modified polysiloxane leveling agent, and the balance being acrylic copolymer (Tg = 85℃);

[0040] The crosslinking agent is composed of pentaerythritol tetraacrylate and propoxylated glycerol acrylate in a mass ratio of 11:1;

[0041] The preparation method of the nanocomposite material includes the following steps:

[0042] (1) A composite of graphene oxide and microparticles in a mass ratio of 11:2 was placed in a mixed acid (H2SO4 / HNO3 = 2:1) and ultrasonically exfoliated to obtain a suspension with a solid content of 0.5wt%.

[0043] (2) The suspension was mixed with the modified dye at 40°C to obtain a reaction mixture. The amount of modified dye was 1.5% of the mass of the composite. 1 wt% of EDC / NHS catalyst was added to the reaction mixture. After reacting for 11 h, the mixture was centrifuged and washed to obtain the nanocomposite material. The microparticles were formed by grinding and mixing silica and Tween 80 at a molar ratio of 5:1 and then drying. The modified dye was obtained by dispersing butanetetracarboxylic acid and an equimolar amount of aminosilane in a dimethyl sulfoxide solution and heating at 70°C for 20 min to obtain a modified solution. After cooling, IR-820 dye was added to the modified solution at a solid-liquid ratio of 1:3 g / mL and reacted at 55°C for 15 min. After drying, the modified dye was obtained. The volume ratio of dimethyl sulfoxide solution to aminosilane was 10:1.

[0044] Example 3

[0045] A method for preparing a nanocomposite modified high-sensitivity, pre-processed negative CTP plate

[0046] Step 1: Preparation of aluminum substrate: The aluminum plate is roughened by electrolysis and then anodized to form an aluminum oxide layer with a pore size of 20-50nm;

[0047] Step 2: Coating: Mix the photosensitive layer raw materials according to the mass percentage, sonicate at an ultrasonic frequency of 20kHz for 20min, and then centrifuge at 600rpm for 3min to obtain the coating material. Coating the photosensitive layer with the coating material using a microgravure plate at a linear speed of 9m / min. After drying, the coating thickness is 1.2±0.1μm.

[0048] The photosensitive layer comprises the following components by weight percentage: 3% nanocomposite material, 14% iodonium salt photoinitiator, 38% crosslinking agent, 0.3% polyether-modified polysiloxane leveling agent, and the balance being acrylic copolymer (Tg = 85℃);

[0049] The crosslinking agent is composed of pentaerythritol tetraacrylate and propoxylated glycerol acrylate in a mass ratio of 11:1;

[0050] The preparation method of the nanocomposite material includes the following steps:

[0051] (1) A composite of graphene oxide and microparticles in a mass ratio of 14:6 was placed in a mixed acid (H2SO4 / HNO3 = 4:1) and ultrasonically exfoliated to obtain a suspension with a solid content of 3.0 wt%.

[0052] (2) The suspension was mixed with the modified dye at 55°C to obtain a reaction mixture. The amount of modified dye was 2.0% of the mass of the composite. 2 wt% of EDC / NHS catalyst was added to the reaction mixture. After reacting for 13 h, the mixture was centrifuged and washed to obtain the nanocomposite material. The microparticles were formed by grinding and mixing silica and Tween 80 at a molar ratio of 5:3 and then drying. The modified dye was obtained by dispersing butanetetracarboxylic acid and an equimolar amount of aminosilane in a dimethyl sulfoxide solution and heating at 80°C for 30 min to obtain a modified solution. After cooling, IR-820 dye was added to the modified solution at a solid-liquid ratio of 1:6 g / mL and reacted at 55-65°C for 20 min. After drying, the modified dye was obtained. The volume ratio of dimethyl sulfoxide solution to aminosilane was 10:2.

[0053] Example 4

[0054] A method for preparing a nanocomposite modified high-sensitivity, pre-processed negative CTP plate

[0055] Step 1: Preparation of aluminum substrate: The aluminum plate is roughened by electrolysis and then anodized to form an aluminum oxide layer with a pore size of 20-50nm;

[0056] Step 2: Coating: Mix the photosensitive layer raw materials according to the mass percentage, sonicate at an ultrasonic frequency of 20kHz for 10min, and then centrifuge at 600rpm for 1min to obtain the coating material. Coating the photosensitive layer with the coating material using a microgravure plate at a linear speed of 9m / min. After drying, the coating thickness is 1.2±0.1μm.

[0057] The photosensitive layer comprises the following components by weight percentage: 0.5% nanocomposite material, 14% iodonium salt photoinitiator, 32% pentaerythritol tetraacrylate, 0.3% polyether-modified polysiloxane leveling agent, and the balance being acrylic copolymer (Tg = 85℃);

[0058] The crosslinking agent is composed of pentaerythritol tetraacrylate and propoxylated glycerol acrylate in a mass ratio of 13:3.

[0059] The preparation method of the nanocomposite material includes the following steps:

[0060] (1) A complex of graphene oxide and microparticles in a mass ratio of 11:6 was placed in a mixed acid (H2SO4 / HNO3 = 2:1) and ultrasonically exfoliated to obtain a suspension with a solid content of 1 wt%.

[0061] (2) The suspension was mixed with the modified dye at 55°C to obtain a reaction mixture. The amount of modified dye was 1.6% of the mass of the composite. 1 wt% of EDC / NHS catalyst was added to the reaction mixture. After reacting for 13 h, the mixture was centrifuged and washed to obtain the nanocomposite material. The microparticles were formed by grinding and mixing silica and Tween 80 at a molar ratio of 5:1 and then drying. The modified dye was obtained by dispersing butanetetracarboxylic acid and an equimolar amount of aminosilane in a dimethyl sulfoxide solution and heating at 70°C for 30 min to obtain a modified solution. After cooling, IR-820 dye was added to the modified solution at a solid-liquid ratio of 1:3 g / mL and reacted at 65°C for 15 min. After drying, the modified dye was obtained. The volume ratio of dimethyl sulfoxide solution to aminosilane was 10:2.

[0062] Comparative Example 1

[0063] The difference between Comparative Example 1 and Example 1 is that no microparticles were added during the preparation of the nanocomposite material of Comparative Example 1, while everything else remained the same.

[0064] Comparative Example 2

[0065] The difference between Comparative Example 2 and Example 1 is that the modified dye was replaced with an equimolar amount of IR-820 dye in the nanocomposite material of Comparative Example 2, while other aspects remained unchanged.

[0066] Comparative Example 3

[0067] The difference between Comparative Example 3 and Example 1 is that the photosensitive layer of the negative CTP plate in Comparative Example 3 is not mixed by ultrasonic centrifugation, but by direct stirring, while other aspects remain unchanged.

[0068] Comparative Example 4

[0069] The difference between Comparative Example 3 and Example 1 is that the crosslinking agent in Comparative Example 4 is an equimolar amount of propoxylated glycerol acrylate, while other aspects remain unchanged.

[0070] The performance of the nanocomposites prepared in Example 1 and Comparative Example 1, as well as the graphene oxide, is shown in Table 1.

[0071] Table 1 Properties of Nanocomposites

[0072]

[0073] As shown in Table 1, the nanocomposite material of the present invention has a larger specific surface area and thermal conductivity than ordinary graphene oxide. Compared with Comparative Example 1, the nanocomposite material of the present invention first forms a composite material with graphene oxide and long-chain alkyl microparticles, which improves the structural uniformity and dispersibility, reduces material agglomeration, and thus improves the specific surface area and thermal conductivity of the nanocomposite material.

[0074] The negative CTP plates prepared in the examples and comparative examples were tested for photosensitivity, thermal diffusivity, development latitude, and scratch resistance, respectively. The testing methods are as follows:

[0075] (1) Photometric sensitivity testing method: Applicable standard: ISO 12492:2020

[0076] The absorbance of the material at different wavelengths is determined using a spectrophotometer (such as UV-Vis). An exposure gradient sample is generated using the step-and-repeat exposure method. The sensitivity threshold is calculated by measuring the residual film thickness or resolution after development.

[0077] (2) Thermal diffusivity test method: ASTM E1461-22;

[0078] The surface of a sample is heated by a laser pulse, and the relationship between the penetration depth of the temperature wave and time is measured.

[0079] (3) Development tolerance: Applicable standard: ISO 3687:2021; Prepare 5 sets of development conditions (time ±10%, concentration ±5%), observe the integrity of the pattern after development by SEM, and calculate the tolerance index (WI): WI = \frac{acceptable condition range}{total test condition range}\times 100\).

[0080] (4) Scratch level testing method: Pencil hardness method: GB / T 6739-2021.

[0081] (5) Perform printing tests on CTP.

[0082] The performance of the negative CTP plates prepared in the examples and comparative examples is shown in Table 1.

[0083] Table 2 Performance of Negative CTP Plates

[0084]

[0085]

[0086] As shown in Table 2, the negative CTP board prepared by this invention has better photosensitivity, better thermal conductivity, greater development tolerance, stronger mechanical properties, higher scratch resistance, a print durability of >200,000 impressions (an improvement of 50%), and a dot reproducibility of 99% compared to traditional boards.

[0087] As shown in Comparative Example 1, adding microparticles to graphene in nanocomposite materials can increase the dispersion performance of graphene and improve the compatibility between graphene and resin.

[0088] As shown in Comparative Example 2, the addition of modified dyes to nanocomposites, compared with single dyes, extends the conjugated system through coupling modification reactions, resulting in stronger light absorption performance, increased grafting activity of graphene composites, and thus improved overall performance of nanocomposites.

[0089] As can be seen from Comparative Example 3, the ultrasonic centrifugation of the present invention can promote the formation of different concentration gradients in the photosensitive layer of the nanocomposite material, and can improve the thermal conductivity and other properties of the photosensitive layer.

[0090] As can be seen from Comparative Example 4, the crosslinking agent in this embodiment of the invention is composed of pentaerythritol tetraacrylate and propoxylated glycerol acrylate added in proportion. Compared with the addition of propoxylated glycerol acrylate alone, it has a stronger crosslinking effect on the resin and improves the mechanical properties of the photosensitive layer.

[0091] Furthermore, it should be understood that although this specification describes embodiments, it is not...

[0092] Each implementation contains only one independent technical solution; this narrative style in the specification is only...

[0093] For clarity only, those skilled in the art should consider the specification as a whole, with each part distinct.

[0094] The technical solutions in the examples can also be appropriately combined to form a combination that can be understood by those skilled in the art.

[0095] Other implementation methods.

Claims

1. A nanocomposite material modified high-sensitivity, pre-processed negative CTP plate, characterized in that, It consists of an aluminum substrate and a photosensitive layer; The photosensitive layer comprises the following components by weight percentage: 0.5-3% nanocomposite material, 10-14% iodonium salt photoinitiator, 32-38% crosslinking agent, 0.1-0.3% dispersant, and the balance being acrylic copolymer (Tg = 85℃); The nanocomposite material is prepared by mixing graphene oxide and microparticles in a mixed acid to form a suspension, and then reacting it with a modified dye.

2. The nanocomposite material modified high-sensitivity, pre-processed negative CTP plate according to claim 1, characterized in that, The photosensitive layer comprises the following components by weight percentage: 2% nanocomposite material, 12% iodonium salt photoinitiator, 35% crosslinking agent, 0.2% dispersant, and the balance being acrylic copolymer (Tg = 85°C).

3. The nanocomposite material modified high-sensitivity, pre-processed negative CTP plate according to claim 1, characterized in that, The preparation method of the nanocomposite material includes the following steps: (1) placing graphene oxide and microparticles in a mass ratio of 11-14:2-6 to form a composite and ultrasonically exfoliating it in a mixed acid (H2SO4 / HNO3=3:1) to obtain a suspension with a solid content of 0.5-3.0wt%; (2) mixing the suspension with a modified dye at 40-55℃ to obtain a reaction mixture, wherein the amount of modified dye is 1.5-2.0% of the mass of the composite material, adding 1-2wt% of EDC / NHS catalyst to the reaction mixture, reacting for 11-13h, and then centrifuging and washing to obtain the nanocomposite material.

4. The nanocomposite material modified high-sensitivity, pre-processed negative CTP plate according to claim 3, characterized in that, The microparticles are formed by grinding and mixing silicon dioxide and Tween 80 in a molar ratio of 5:1-3 and then drying them.

5. The nanocomposite material modified high-sensitivity, pre-processed negative CTP plate according to claim 3, characterized in that, The modified dye is prepared by dispersing butanetetracarboxylic acid and an equimolar amount of aminosilane in a dimethyl sulfoxide solution and heating to obtain a modified solution. After cooling, IR-820 dye is added to the modified solution at a solid-liquid ratio of 1:3-6 g / mL and reacted at 55-65℃ for 15-20 min. After drying, the modified dye is obtained. The volume ratio of dimethyl sulfoxide solution to aminosilane is 10:1-2.

6. The nanocomposite material modified high-sensitivity, pre-processed negative CTP plate according to claim 5, characterized in that, The heating reaction is carried out at 70-80℃ for 20-30 minutes.

7. The nanocomposite material modified high-sensitivity, pre-treated negative CTP plate according to claim 1, characterized in that, The crosslinking agent is composed of pentaerythritol tetraacrylate and propoxylated glycerol acrylate in a mass ratio of 11-13:1-3.

8. The nanocomposite material modified high-sensitivity, pre-processed negative CTP plate according to claim 1, characterized in that, The dispersant is a polyether-modified polysiloxane leveling agent.

9. A method for preparing a nanocomposite-modified high-sensitivity, pre-treated negative CTP plate, used to prepare the nanocomposite-modified high-sensitivity, pre-treated negative CTP plate according to any one of claims 1-8, characterized in that, Includes the following steps: Step 1: Preparation of aluminum substrate: The aluminum plate is roughened by electrolysis and then anodized to form an aluminum oxide layer with a pore size of 20-50nm; Step 2: Coating: Mix the raw materials of the photosensitive layer according to the mass percentage and then perform ultrasonic centrifugation to obtain the coating material. Coating the photosensitive layer with the coating material using a microgravure plate at a linear speed of 7-9 m / min. After drying, the coating thickness is 1.2±0.1 μm.

10. The method for preparing a nanocomposite modified high-sensitivity, pre-processed negative CTP plate according to claim 9, characterized in that, The ultrasonic centrifugation process involves sonicating the photosensitive layer material at an ultrasonic frequency of 10-20 kHz for 10-20 minutes, followed by centrifugation at 500-600 rpm for 1-3 minutes.

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