A photoresist for processless heat sensitive CTP and a method for preparing the same

Abstract

The application relates to G03F 7 / 004, and particularly relates to a photoresist for a processing-free heat-sensitive CTP and a preparation method thereof. The photoresist comprises the following raw materials in parts by weight: 2-5 parts of infrared dye, 1-3 parts of basic dye, 8-12 parts of iodonium salt, 30-50 parts of acrylic acid and derivatives thereof, 50-60 parts of polyurethane acrylic resin, and 0.9-1.3 parts of antioxidant. The photoresist for a processing-free heat-sensitive CTP and the preparation method thereof have the advantages that the photoresist obtained by the method has good resolution, high printing resistance and good mechanical properties.

Description

Technical Field

[0001] This invention relates to G03F 7 / 004, specifically to a photoresist for processing-free thermal CTP and its preparation method. Background Technology

[0002] With the development of modern electronic products, such as mobile phones and computers, the size of these products is getting smaller and smaller, and the requirements for imaging technology are also getting higher and higher. Traditional PS printing technology can no longer meet people's needs, and CTP has emerged.

[0003] Existing photoresists have low resolution, making them unsuitable for high-precision devices. Furthermore, substrates inevitably develop scratches and unevenness with repeated use, and photoresists have poor adaptability to these surface irregularities, resulting in poor adhesion and coatability. Researchers, in their pursuit of high image sensitivity and resolution, often neglect the mechanical properties of photoresists, leading to the inability to form a continuous and uniform film on CTP surfaces, thus reducing resolution. Summary of the Invention

[0004] To address the aforementioned technical problems, a first aspect of the present invention provides a photoresist for a process-free thermal CTP, comprising the following raw materials, by weight: 2-5 parts infrared dye, 1-3 parts basic dye, 8-12 parts iodonium salt, 30-50 parts acrylic acid and its derivatives, 50-60 parts polyurethane acrylic resin, and 0.9-1.3 parts antioxidant.

[0005] Preferably, the infrared dye comprises benzenesulfonate and / or antimonate.

[0006] Preferably, the absorption wavelength of the infrared dye is 750-800 nm.

[0007] Preferably, the basic dye is hexamethyl p-fuchsine chloride.

[0008] Preferably, the iodonium salt comprises 4-isobutylphenyl-4-methylphenyliodonium hexafluorophosphate and diaryliodonium salt. The weight ratio of 4-isobutylphenyl-4-methylphenyliodonium hexafluorophosphate to diaryliodonium salt is (5-8):(1-3).

[0009] Preferably, the acrylic acid and its derivatives include at least one of n-octyl acrylate, methacrylate, benzyl methacrylate, n-butyl acrylate, hydroxyethyl methacrylate, 1,6-hexanediol diacrylate, glycidyl methacrylate, N,N-dihexylacrylamide, 4-methacryloylaminobenzenesulfonamide, and N,N-bis(2-hydroxyethyl)acrylamide.

[0010] Preferably, the acrylic acid and its derivatives include n-octyl acrylate, methacrylate, hydroxyethyl methacrylate, 1,6-hexanediol diacrylate, and 4-methacrylamide. The weight ratio of n-octyl acrylate, methacrylate, hydroxyethyl methacrylate, 1,6-hexanediol diacrylate, and 4-methacrylamide is (5-8):(5-8):(2-5):1:(1-2).

[0011] An unexpected study of this invention revealed that the combination of acrylic acid and its derivatives, including n-octyl acrylate, methacrylate, hydroxyethyl methacrylate, 1,6-hexanediol diacrylate, and 4-methacrylamide, can significantly improve the adhesion and abrasion resistance of photoresists. This is presumably due to the synergistic effect of different functional groups among the acrylic acid and its derivatives, which can partially embed between the hinge molecular chains, increasing the hardness of the photoresist film. Simultaneously, the flexible segments reduce the coefficient of friction, allowing the photoresist film to effectively adhere to the substrate surface. In particular, when the weight ratio of n-octyl acrylate, methacrylate, hydroxyethyl methacrylate, 1,6-hexanediol diacrylate, and 4-methacrylamide is (5-8):(5-8):(2-5):1:(1-2), the intermolecular forces within the system are balanced, and the cohesive energy is moderate, effectively improving the adhesion and abrasion resistance of the photoresist.

[0012] Preferably, the functionality of the polyurethane acrylic resin is 1-3.

[0013] More preferably, the polyurethane acrylate resin includes a first polyurethane acrylate resin and a second polyurethane acrylate resin.

[0014] Preferably, the viscosity of the first polyurethane acrylic resin at 25°C is 20,000-30,000, and the molecular weight of the polyurethane acrylic resin is 8,000-9,000.

[0015] Preferably, the second polyurethane acrylic resin has a viscosity of 20,000-30,000 at 25°C, and the molecular weight of the polyurethane acrylic resin is 1,500-2,500.

[0016] The inventors unexpectedly discovered that the presence of polyurethane acrylic resin within the system can effectively complicate the cross-linked network structure. Simultaneously, the photoresist undergoes a graded dissolution process during exposure and imaging. The molecular chains of the first and second polyurethane acrylic resins (with a viscosity of 20,000-30,000 and a molecular weight of 8,000-9,000 at 25°C), as well as acrylic acid and its derivatives, can effectively achieve molecular chain entanglement, reducing the difference in dissolution rate between the photoresist and the unexposed portion, thereby improving resolution. Furthermore, the presence of the second polyurethane acrylic resin (with a viscosity of 20,000-30,000 and a molecular weight of 1,500-2,500 at 25°C) avoids the rough cross-section phenomenon caused by the disappearance of large molecular chains during the photoresist dissolution process, further improving the photoresist's resolution.

[0017] Preferably, the antioxidant comprises at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, and citric acid.

[0018] Preferably, the raw material further includes 0.5-1.5 parts of phosphate.

[0019] The second aspect of the present invention provides a method for preparing a photoresist for a process-free thermal CTP, comprising the following steps: weighing the raw materials according to the formula and adding them to a solvent, stirring, reacting and filtering to obtain a photoresist for a process-free thermal CTP.

[0020] Preferably, the solvent includes at least one of propylene glycol methyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, N,N-dimethyldiamide, 4-methyl-2-pentanone, 4-hydroxybenzophenone, acetone, and butanone.

[0021] More preferably, the solvent comprises propylene glycol methyl ether acetate, ethylene glycol monoethyl ether, and N,N-dimethyldiamide. The mass ratio of propylene glycol methyl ether acetate, ethylene glycol monoethyl ether, and N,N-dimethyldiamide is (3-5):(3-5):(1-3).

[0022] Preferably, the photoresist of the treatment-free thermal CTP has a viscosity of 25-35 cps at 25°C.

[0023] Beneficial effects:

[0024] 1. The photoresist for heat-sensitive CTP without processing provided by the present invention and the preparation method thereof produce a photoresist with good image sensitivity and resolution and high printing durability.

[0025] 2. The photoresist for heat-sensitive CTP and its preparation method provided by the present invention have high adhesion, good scratch resistance and good mechanical properties.

[0026] 3. The photoresist for heat-sensitive CTP and its preparation method provided by this invention have a short development time and low price, which can fully meet the needs of consumers. Detailed Implementation

[0027] The present invention will now be described in detail through embodiments. It should be noted that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention still fall within the scope of protection of the present invention.

[0028] In addition, unless otherwise stated, all raw materials used are commercially available.

[0029] Example

[0030] Example 1

[0031] A photoresist for processing-free thermal CTP comprises the following raw materials, by weight: 3 parts infrared dye, 2 parts basic dye, 10 parts iodonium salt, 40 parts acrylic acid and its derivatives, 55 parts polyurethane acrylic resin, and 1.1 parts antioxidant.

[0032] The infrared dye is a benzenesulfonate, and its absorption wavelength is 775 nm. The grade is JADEWINANCTP-2, purchased from Qingdao Jiedejia New Material Technology Co., Ltd.

[0033] The basic dye is hexamethyl p-fuchsine chloride.

[0034] The iodonium salts comprise 4-isobutylphenyl-4-methylphenyliodonium hexafluorophosphate and diaryliodonium salt. The weight ratio of 4-isobutylphenyl-4-methylphenyliodonium hexafluorophosphate to diaryliodonium salt is 7:2. The 4-isobutylphenyl-4-methylphenyliodonium hexafluorophosphate is Irgacure 250, and the diaryliodonium salt is PAS 33. All iodonium salts were purchased from Shenzhen Youyang Technology Co., Ltd.

[0035] The acrylic acid and its derivatives include n-octyl acrylate, methacrylate, hydroxyethyl methacrylate, 1,6-hexanediol diacrylate, and 4-methacrylamide. The weight ratio of n-octyl acrylate, methacrylate, hydroxyethyl methacrylate, 1,6-hexanediol diacrylate, and 4-methacrylamide is 6:7:2.5:1:1.5.

[0036] The polyurethane acrylate resin has a functionality of 2. The polyurethane acrylate resin comprises a first polyurethane acrylate resin and a second polyurethane acrylate resin. The first polyurethane acrylate resin has a viscosity of 25,000 and a molecular weight of 8,500. Its grade is GP-5102. The second polyurethane acrylate resin has a viscosity of 25,000 and a molecular weight of 1,900. Its grade is Trust 7060. All polyurethane acrylate resins were purchased from Shenzhen Youyang Technology Co., Ltd.

[0037] The antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0038] The raw materials also include 1 part of phosphate, which was purchased from Shenzhen Youyang Technology Co., Ltd., brand name: CTI-200.

[0039] The second aspect of the present invention provides a method for preparing a photoresist for a process-free thermal CTP, comprising the following steps: weighing the raw materials according to the formula and adding them to a solvent, stirring, reacting and filtering to obtain a photoresist for a process-free thermal CTP.

[0040] The solvent comprises propylene glycol methyl ether acetate, ethylene glycol monoethyl ether, and N,N-dimethyldiamide; the mass ratio of propylene glycol methyl ether acetate, ethylene glycol monoethyl ether, and N,N-dimethyldiamide is 4:4:2. The photoresist of the treatment-free thermal CTP has a viscosity of 27 cps at 25°C.

[0041] Example 2

[0042] A photoresist for processing-free thermal CTP, the specific implementation method is the same as in Example 1, except that the raw materials include 2 parts infrared dye, 1 part basic dye, 8 parts iodonium salt, 30 parts acrylic acid and its derivatives, 50 parts polyurethane acrylic resin, and 0.93 parts antioxidant.

[0043] Example 3

[0044] A photoresist for heat-sensitive CTP without processing, the specific implementation is the same as in Example 1, except that the weight ratio of n-octyl acrylate, methacrylate, hydroxyethyl methacrylate, 1,6-hexanediol diacrylate, and 4-methacrylamide is 8:8:5:1:2.

[0045] Comparative Example 1

[0046] A photoresist for processing-free thermal CTP, with the same specific implementation as in Example 1, except that the viscosity of the first polyurethane acrylic resin is 25000 and the molecular weight of the polyurethane acrylic resin is 2500. Grade: GP-5120.

[0047] Comparative Example 2

[0048] A photoresist for processing-free thermal CTP, with the specific implementation method the same as in Example 1, except that the viscosity of the second polyurethane acrylate resin is 35000 and the molecular weight of the polyurethane acrylate resin is 1500. Brand: Trust 7050.

[0049] Comparative Example 3

[0050] A photoresist for heat-sensitive CTP without processing, the specific implementation is the same as in Example 1, except that the weight ratio of n-octyl acrylate, methacrylate, hydroxyethyl methacrylate, 1,6-hexanediol diacrylate, and 4-methacrylamide benzenesulfonamide is 6:7:2.5:1:0.5.

[0051] Performance testing

[0052] 1. Adhesion test: Tested according to GB / T 9286-1998.

[0053] 2. Abrasion resistance test: The exposed and developed board is made into an 8cm*20cm sample, fixed in a 1000ml sealed container, and abrasion resistance test reagent (5 3cm rubber balls, 35g of carborundum, 10ml of phosphoric acid, and 230ml of water) is added. The sample is rotated continuously for 20 minutes to test the density loss.

[0054] 3. Resolution test: Observe the resolution of the photoresist using a scanning electron microscope.

[0055] Table 1 Performance Test Results

[0056]

[0057] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any other way. Any person skilled in the art may make changes or equivalent modifications to the above-disclosed technical content. However, any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A photoresist for a processless heat sensitive CTP, characterized in that, The raw materials include the following, by weight, infrared dye 2-5 parts, basic dye 1-3 parts, iodonium salt 8-12 parts, acrylic acid and its derivatives 30-50 parts, polyurethane acrylic resin 50-60 parts, antioxidant 0.9-1.3 parts; the acrylic acid and its derivatives include n-octyl acrylate, methyl methacrylate, hydroxyethyl methacrylate, 1,6-hexanediol diacrylate, 4-methyl acrylamido phenyl sulfonamide in a weight ratio of (5-8): (5-8): (2-5): 1: (1-2); the polyurethane acrylic resin includes a first polyurethane acrylic resin and a second polyurethane acrylic resin, the viscosity of the first polyurethane acrylic resin at 25℃ is 20000-30000, the molecular weight of the first polyurethane acrylic resin is 8000-9000, the viscosity of the second polyurethane acrylic resin at 25℃ is 20000-30000, the molecular weight of the second polyurethane acrylic resin is 1500-2500.

2. A photoresist for processless heat sensitive CTP according to claim 1, characterized in that, The iodonium salt includes 4-isobutylphenyl-4-methylphenyl iodonium hexafluorophosphate and diaryl iodonium salt.

3. The photoresist for processless thermal sensitive CTP according to claim 1, wherein, The functionality of the polyurethane acrylic resin is 1-3.

4. The photoresist for processless thermal sensitive CTP according to claim 1, wherein, The antioxidant includes at least one of tetra[β- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, β- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecanol ester, 1, 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, citric acid.

5. The photoresist for processless thermal sensitive CTP according to claim 1, wherein, The raw materials further include phosphate 0.5-1.5 parts.

6. A method of preparing a photoresist for processless thermal sensitive CTP according to any one of claims 1-5, characterized in that, The method includes the following steps: weighing the raw materials according to the formula, stirring, filtering, and obtaining a photoresist for treatment-free heat-sensitive CTP. The raw materials include the following, by weight, infrared dye 2-5 parts, basic dye 1-3 parts, iodonium salt 8-12 parts, acrylic acid and its derivatives 30-50 parts, polyurethane acrylic resin 50-60 parts, antioxidant 0.9-1.3 parts; the acrylic acid and its derivatives include n-octyl acrylate, methyl methacrylate, hydroxyethyl methacrylate, 1,6-hexanediol diacrylate, 4-methyl acrylamido phenyl sulfonamide in a weight ratio of (5-8): (5-8): (2-5): 1: (1-2); the polyurethane acrylic resin includes a first polyurethane acrylic resin and a second polyurethane acrylic resin, the viscosity of the first polyurethane acrylic resin at 25℃ is 20000-30000, the molecular weight of the first polyurethane acrylic resin is 8000-9000, the viscosity of the second polyurethane acrylic resin at 25℃ is 20000-30000, the molecular weight of the second polyurethane acrylic resin is 1500-2500. The iodonium salt includes 4-isobutylphenyl-4-methylphenyl iodonium hexafluorophosphate and diaryl iodonium salt. The functionality of the polyurethane acrylic resin is 1-3. The antioxidant includes at least one of tetra[β- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, β- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecanol ester, 1, 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, citric acid. The raw materials further include phosphate 0.5-1.5 parts. The method includes the following steps: weighing the raw materials according to the formula, stirring, filtering, and obtaining a photoresist for treatment-free heat-sensitive CTP.

Images