Photosensitive resin composition and application thereof

Abstract

The invention discloses a photosensitive resin composition and application thereof. The photosensitive resin composition comprises the following raw material components in parts by mass: 30-50 parts of resin, 30-50 parts of a monomer compound, 1-10 parts of an initiator, 0.1-5 parts of a cross-linking agent and 0.01-1 part of an interfacial agent, the resin comprises aliphatic polyester type polyurethane acrylate and epoxy acrylic resin. According to the photosensitive resin composition and the application thereof provided by the invention, the aliphatic polyester type urethane acrylate is introduced into the epoxy acrylic system photosensitive resin composition, so that the elastic recovery rate of photoresist can be improved, and the process yield can be improved. The photosensitive resin composition can form a photocuring pattern with excellent elastic recovery rate and high-resolution pattern developing property after being cured, and has huge application potential in the formation of spacer patterns and the manufacturing of image display devices.

Description

Technical Field

[0001] The present invention belongs to the technical field of photosensitive materials, and particularly relates to a photosensitive resin composition and its application. Background Art

[0002] In the early stage of the development of lithography technology, the resolution of photoresists was relatively low. At that time, PS (gap column) photoresists were mainly based on some traditional resin systems, such as phenolic resins. With the continuous development of material science, new resin materials began to be applied to PS photoresists. Epoxy acrylate resin is a special polymer system that combines the advantages of epoxy resin and acrylate resin. Epoxy resin has good adhesion, chemical stability and heat resistance, and can provide strong mechanical properties and good adhesion to the substrate. Acrylate resin has good optical properties, flexibility and processability. Currently, under the epoxy acrylate resin system, the resolution of the high-resolution Fine PS photoresist for Mobile can reach 7μm (Top)-9μm (Bot), and the resolution of the lower-resolution Normal PS photoresist for TV also reaches 12μm (Top)-20μm (Bot). However, with the increasing demand for the manufacture of smaller-sized PS photoresists, higher requirements are also placed on the resolution of PS photoresists. Therefore, Ultra Fine PS photoresists have emerged, with a resolution as high as 5μm (Top)-7μm (Bot). However, high-resolution photoresists usually require thinner film layers and finer structures, which may affect the mechanical properties of the materials. This is because high resolution may require a higher crosslinking density, making the material more prone to breakage during development, and the elastic recovery rate naturally decreases, thus affecting the performance and reliability of semiconductor devices or display panels. Therefore, it is necessary to develop a photoresist with high resolution and high elastic recovery rate. Summary of the Invention

[0003] In order to overcome the problems existing in the above-mentioned prior art, one of the purposes of the present invention is to provide a photosensitive resin composition. Another purpose of the present invention is to provide the application of the above-mentioned photosensitive resin composition. A third purpose of the present invention is to provide a photosensitive film. A fourth purpose of the present invention is to provide a circuit board.

[0004] In order to achieve the above purposes, the technical solutions adopted by the present invention are as follows:

[0005] The first aspect of the present invention provides a photosensitive resin composition, which comprises raw material components in the following parts by mass: 30-50 parts of resin, 30-50 parts of monomer compound, 1-10 parts of initiator, 0.1-5 parts of crosslinking agent, and 0.01-1 part of surfactant; the resin comprises aliphatic polyester type polyurethane acrylate and epoxy acrylate resin; the mass ratio of the aliphatic polyester type polyurethane acrylate to the epoxy acrylate resin is (1-5):3.

[0006] Preferably, the structural formula of the aliphatic polyester type polyurethane acrylate is as shown in Formula A:

[0007]

[0008] In Formula A, m = 4-7, n = 4-7;

[0009] R is

[0010] The aliphatic polyester type polyurethane acrylate of the present invention is a tetrafunctional (C=C double bond) aliphatic PUA resin, the end group of which is hydroxyethyl acrylate group, the degree of polymerization (m and n) is 4-7, and it does not contain benzene ring benzyl structure. -NOC and -OH form a hydrogen bond structure, which significantly improves the rigidity of the aliphatic PUA resin and avoids yellowing. The ester group provides excellent toughness and very weak water absorption. The ester bond is stable and non-rotatable, making the aliphatic PUA resin have strong anti-deformation ability. The combined action of the hydrogen bond and the ester group forms an aliphatic PUA resin with excellent toughness, and the anti-fracture and anti-deformation abilities are excellent. The six-membered ring has a large space occupancy, which can reduce the volume shrinkage rate after curing and improve the anti-deformation ability of the aliphatic PUA resin.

[0011] Preferably, the preparation method of the aliphatic polyester type polyurethane acrylate comprises the following steps: dropping an organic solution of HDI trimer curing agent into an organic solution of polycaprolactone polyol for the first addition reaction, and then dropping hydroxyethyl acrylate for the second addition reaction to obtain the aliphatic polyester type polyurethane acrylate.

[0012] More preferably, the preparation method of the aliphatic polyester type polyurethane acrylate is specifically as follows:

[0013] S1. Stir polycaprolactone diol (number average molecular weight is 1000) and N,N-dimethylformamide to completely dissolve the polycaprolactone polyol to obtain an organic solution of polycaprolactone polyol; wherein, the mass ratio of polycaprolactone polyol to N,N-dimethylformamide is 1:5.

[0014] S1. Dissolve the HDI trimer curing agent in 1,4-dioxane to obtain an organic solution of the HDI trimer curing agent; wherein, the mass ratio of the HDI trimer curing agent to 1,4-dioxane is 1:5.

[0015] S3. At 70 °C, an organic solution of HDI trimer curing agent is dropped into an organic solution of polycaprolactone polyol. After the dropping is completed, the mixture is stirred at a constant temperature for 1 h, and the infrared spectrum of the reaction system is measured. The reaction continues until the broad diffused peak of the hydroxyl group near 3300 cm -1 disappears, obtaining the first reaction solution; wherein, the molar ratio of polycaprolactone polyol to HDI trimer is 1:2.

[0016] S4. Hydroxyethyl acrylate is dropped into the first reaction solution. After the dropping is completed, the reaction proceeds for 13 h, and the infrared spectrum of the system is measured. The reaction continues until the stretching vibration peak of the hydroxyl group at 3513 cm -1 and the stretching vibration peak of -NOC at 2230 cm -1 disappear. After the reaction ends, it is cooled to below 50 °C, and the solvent (N,N-dimethylformamide and 1,4-dioxane) is removed by vacuum distillation at 80 °C, obtaining an aliphatic polyester type polyurethane acrylate (tetrafunctional, without residual -NOC and -OH); wherein the molar ratio of polycaprolactone polyol to hydroxyethyl acrylate is 1:4.

[0017] Preferably, the structural formula of the epoxy acrylate resin is shown in Formula B:

[0018]

[0019] In the said Formula B, m = 200 - 300, n = 200 - 300.

[0020] More preferably, the preparation method of the epoxy acrylate resin includes: dissolving epoxy resin in propylene glycol monomethyl ether acetate to obtain an epoxy resin solution, slowly dropping a mixed solution of acrylic acid, hydroquinone, tetrabutylammonium bromide, chromium acetylacetonate and propylene glycol monomethyl ether acetate into the epoxy resin solution, carrying out the first-step reaction at 90 °C, then adding 7.1 g of maleic acid to the reaction solution, adding 7.1 g of propylene glycol monomethyl ether acetate additionally, and carrying out the second-step reaction at 90 °C. After cooling, the epoxy acrylate resin is obtained.

[0021] Preferably, the monomer compound is selected from at least one of acrylate compounds, epoxy vinyl ether compounds, styrene compounds, methylstyrene compounds, diazonaphthoquinone compounds, lactone compounds, acrylamide compounds, and phenolic compounds.

[0022] The monomer compound is selected from at least one of 1,6 - hexanediol bis(meth)acrylate, dipropylene glycol / tripropylene glycol bis(meth)acrylate, diethylene glycol / triethylene glycol bis(meth)acrylate, ethoxylated bisphenol A bis(meth)acrylate, neopentyl glycol diethoxy / propoxy bis(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexaacrylate.

[0023] Preferably, the initiator is selected from at least one of halogenated hydrocarbon derivatives, compounds with a triazole skeleton, compounds with a diazole skeleton, compounds with an imidazole skeleton, phosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α - hydroxy ketone compounds, and α - amino ketone compounds.

[0024] Preferably, the initiator is a photoinitiator.

[0025] More preferably, the initiator is selected from at least one of IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 of BASF Corporation, and N - 1919 of ADEKA Corporation.

[0026] Preferably, the cross - linker is selected from at least one of hydroxymethyl compounds, melamine compounds, vinyl ether compounds, benzophenone compounds, and acrylate compounds.

[0027] Preferably, the surfactant is selected from at least one of fluorine - based surfactants, non - ionic surfactants, cationic surfactants, anionic surfactants, and polysiloxane surfactants.

[0028] More preferably, the fluorine - based surfactant is selected from at least one of F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F781F of the Megafac series products of Edison DIC Corporation, FC430, FC431, FC171 of the Fluorad series products of 3M Corporation, and SC - 382, SC - 101, SC - 103, SC - 104, SC - 105, SC1068, SC - 381 of the Surflon series products of Asahi Glass Co., Ltd.

[0029] More preferably, the nonionic surfactant is selected from at least one of glycerol, trimethylolpropane, trimethylolethane, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester.

[0030] Further preferably, the nonionic surfactant is selected from at least one of Pluronic L10, Pluronic L31, Pluronic L61, Pluronic L62, Pluronic 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304, Tetronic 701, Tetronic 704, Tetronic 901, Tetronic 904, Tetronic 150R1, and Solsperse 2000 manufactured by BASF Corporation.

[0031] More preferably, the cationic surfactant is selected from at least one of Efka-745, KP341, Perfluor No.75, Perfluor No.90, and Perfluor No.95.

[0032] More preferably, the anionic surfactant is selected from W004, W005, and W017 of Yushang Company.

[0033] Preferably, by mass, the raw material components further include 400 - 800 parts of an organic solvent.

[0034] The solvent used in the photosensitive resin composition is not particularly limited as long as it can disperse or dissolve the components of the photosensitive resin composition without reacting with these components, and has moderate volatility and an appropriate drying rate, and can provide a uniform and smooth coating film after volatilization. Solvents generally used in this technical field can be used.

[0035] More preferably, the organic solvent is selected from at least one of alcohols, ethers, glycol ethers, diol ether esters, diol ethers, aromatic hydrocarbons, ketones, alkoxy esters, etc.

[0036] Further preferably, the organic solvent is selected from diol ether esters and alkoxy esters.

[0037] Further preferably, the diol ether esters are selected from at least one of propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, and propylene glycol monopropyl ether propionate.

[0038] Further preferably, the alkoxy esters are selected from at least one of propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, propyl propoxyacetate, propyl acetate, 3-methoxybutyl acetate, and 3-methoxybutyl ethoxyacetate.

[0039] The second aspect of the present invention provides an application of the photosensitive resin composition described in the first aspect in semiconductor preparation, display panel manufacturing, or printed circuit boards.

[0040] The third aspect of the present invention provides a photosensitive film obtained by curing the photosensitive resin composition described in the first aspect.

[0041] Preferably, the method for preparing the photosensitive film includes: coating the photosensitive resin composition onto a substrate, followed by drying, exposure, and development for patterning to obtain the photosensitive film.

[0042] More preferably, the coating method is selected from spraying, flow coating, roll coating, wire bar coating, or screen printing. More preferably, the drying is carried out at 60°C to 100°C.

[0043] The fourth aspect of the present invention provides a circuit board including the photosensitive film described in the third aspect.

[0044] The beneficial effects of the present invention are as follows:

[0045] The present invention provides a photosensitive resin composition and its application. By introducing an aliphatic polyester-based polyurethane acrylate into an epoxy acrylate-based photosensitive resin composition, the elastic recovery rate of the photoresist can be increased, and the yield of the manufacturing process can be improved. The photosensitive resin composition of the present invention can form a photocured pattern with excellent elastic recovery rate and high-resolution pattern developability after curing, and has great application potential in the formation of spacer patterns and the manufacturing of image display devices. In addition, the photoresist prepared from the photosensitive resin composition of the present invention has an excellent maximum depression amount, which means that the photoresist can be used under a wider range of wafer materials and surface conditions and can form a good film on different material surfaces. Description of the Drawings

[0046] Figure 1 It is the surface morphology of the cured film. Detailed Embodiments

[0047] The content of the present invention will be further described in detail through specific examples below. The raw materials used in the following examples, unless otherwise specified, can be obtained from conventional commercial channels or prepared and separated by simple synthesis; the processes used, unless otherwise specified, are all conventional processes in the art.

[0048] The PUA resin used in the following examples refers to the aliphatic polyester type polyurethane acrylate of patent document CN202410205347.3. The preparation method of the aliphatic polyester type polyurethane acrylate is as follows: an organic solution of HDI trimer curing agent is dropped into an organic solution of polycaprolactone polyol for the first addition reaction, and then hydroxyethyl acrylate is dropped for the second addition reaction to obtain the PUA resin. The temperatures of the first addition reaction and the second addition reaction are independently 70 - 100 °C, and the times are independently 1 - 3 h. Specifically refer to Example 1 of the specification of patent document CN202410205347.3.

[0049] The structural formula of the epoxy acrylate resin used in the following examples and comparative examples is shown in Formula B:

[0050]

[0051] The specific preparation method of the epoxy acrylate resin is as follows: 72 g of o-cresol novolac epoxy resin (EOCN) (molecular weight 400 - 460 g / mol) is dissolved in 72 g of propylene glycol monomethyl ether acetate to obtain an epoxy resin solution. A mixed solution of 20.5 g of acrylic acid, 0.4 g of hydroquinone, 0.4 g of tetrabutylammonium bromide, 0.2 g of chromium acetylacetonate and propylene glycol monomethyl ether acetate is slowly dropped into the epoxy resin solution (the dropping time is 4 h), and the first step reaction is carried out by stirring at 90 °C for 19 h. Then 7.1 g of maleic acid is added to the reaction solution, 7.1 g of propylene glycol monomethyl ether acetate is added, and the second step reaction is carried out by maintaining the temperature at 90 °C and stirring for 17 h. After cooling, the epoxy acrylate resin is obtained.

[0052] The monomer compound used in the following examples and comparative examples is dipentaerythritol hexaacrylate (DPHA); the photoinitiator is BSFOXE-02; the photocrosslinking agent is Sartomer SR9051; the surfactant is DICF-554; the solvent is a compound solvent of butyl 3-methoxyacetate (MBA) and propylene glycol monomethyl ether acetate (PGMEA) (w / w = 3:7).

[0053] The following Table 1 shows the compositions of the photosensitive resins in the examples and comparative examples, and the physical properties of each example and comparative example are detected after curing and film forming through experimental examples to verify the effects of the present invention.

[0054] Table 1: Compositions of the photosensitive resins in the examples and comparative examples

[0055]

[0056]

[0057] Note: The numbers in parentheses indicate the mass parts in the overall formulation; among them, A1(40) represents 10 parts of PUA resin and 30 parts of epoxy acrylate resin; A2(40) represents 15 parts of PUA resin and 25 parts of epoxy acrylate resin; A3(40) represents 20 parts of PUA resin and 20 parts of epoxy acrylate resin; A4(40) represents 40 parts of epoxy acrylate resin; A4(20) represents 20 parts of epoxy acrylate resin; A4(30) represents 30 parts of epoxy acrylate resin.

[0058] The preparation methods of the compositions of Examples 1-3 and Comparative Examples 1-3 are as follows: First, dissolve the photoinitiator in the solvent, then sequentially add the PUA resin, epoxy acrylate resin, photopolymerizable monomer, and photo-crosslinking agent, and finally add the surfactant, and stir evenly by magnetic stirring.

[0059] Experimental analysis

[0060] 1. Preparation of photoresist

[0061] Coating: Using a spin coater, set the rotation speed at 320 rpm and the acceleration at 160 rpm, and select sodium glass with a thickness of 0.3 mm for liquid crystal displays. Take 3 mL of the photosensitive resin compositions of Examples 1-3 and Comparative Examples 1-3 and coat them on the sodium glass respectively. After coating, a 3.5-μm-thick film is obtained.

[0062] Pre-baking: Place the glass on a hot plate device, set the temperature at 90 °C, and bake for 120 seconds.

[0063] Exposure: Use a SUSS MA8 proximity exposure machine, filter the light source band with an i-Line filter, and the exposure dose is 50 mJ / cm 2 .

[0064] Development: Use a developer potassium hydroxide (KOH) with a mass percentage of 0.045% for immersion development for 1 minute, and then perform air drying with compressed air to form the required pattern.

[0065] Baking: Heat the developed patterned film at 230 °C in an oven for 30 minutes to complete curing and obtain the photoresist.

[0066] 2. Test method

[0067] Surface topography test: Use a scanning electron microscope to test the surface topography of the cured film made of the photosensitive resin composition in Example 1. The specific topography is as Figure 1 shown.

[0068] The test method for elastic recovery rate is as follows: Use a nanoindentation instrument HM2000, manufactured by FISCHER in Germany. Use a 50um * 50um indenter to measure the maximum indentation depth (H max ) and the permanent deformation (H p ) of the photoresists in Examples 1-3 and Comparative Examples 1-3 under 80 mN, and calculate the corresponding elastic recovery rate (ER).

[0069] The test method for pattern resolution is as follows: After the photosensitive resin compositions in Examples 1-3 and Comparative Examples 1-3 are coated, pre-baked, exposed, developed, and baked, use a scanning electron microscope to observe the dimensions (critical dimension, unit: micrometer) of the top and bottom of the pattern, as well as the corresponding Taper angle (unit: degree).

[0070] 3. The test results are shown in Table 2 as follows:

[0071] Table 2

[0072]

[0073] From the performance test results in Table 2, it can be seen that Examples 1-3 can all obtain good maximum indentation depth and elastic recovery rate. At the same time, the dimensions and Taper angles of Examples 1-3 meet the requirements of Ultra Fine PS, that is, it may meet the needs of manufacturing smaller-sized PS photoresists, indicating that introducing aliphatic polyester-based polyurethane acrylate into the epoxy acrylate-based photosensitive resin composition can improve the elastic recovery rate of the photoresist without affecting the resolution.

[0074] In addition, the maximum indentation depth of the photoresists in Examples 1-3 is better than that of the comparative examples. A larger maximum indentation depth means that the photoresist can be used under a wider range of wafer materials and surface conditions. Different wafer materials (such as silicon, silicon carbide, sapphire, etc.) have different hardnesses and surface characteristics, and the photoresist needs to be able to form a good thin film on the surfaces of these different materials. At the same time, there may be some impurities, particles, or micro-scratches on the wafer surface. A larger maximum indentation depth can enable the photoresist to better overcome these surface defects during the coating process, improve the adhesion and coverage of the photoresist to the wafer surface, thereby expanding the application range of the photoresist.

[0075] The above is the preferred embodiment of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements are also regarded as the protection scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that, The raw material components include the following parts by mass: 30 to 50 parts of resin, 30 to 50 parts of monomer compound, 1 to 10 parts of initiator, 0.1 to 5 parts of crosslinking agent, and 0.01 to 1 part of surfactant; the resin includes aliphatic polyester type polyurethane acrylate and epoxy acrylate resin; the mass ratio of the aliphatic polyester type polyurethane acrylate to the epoxy acrylate resin is (1 to 5):

3.

2. The photosensitive resin composition according to claim 1, wherein The structural formula of the aliphatic polyester type polyurethane acrylate is as shown in Formula A: In the said Formula A, m = 4 to 7, n = 4 to 7; R is 3. The photosensitive resin composition according to claim 1, wherein The structural formula of the epoxy acrylate resin is as shown in Formula B: In the said Formula B, m = 200 - 300, n = 200 - 300.

4. The photosensitive resin composition according to claim 1, characterized in that, The monomer compound is selected from at least one of acrylate compounds, epoxy vinyl ether compounds, styrene compounds, methyl styrene compounds, diazonaphthoquinone compounds, lactone compounds, acrylamide compounds, and phenolic compounds.

5. The photosensitive resin composition according to claim 1, wherein The initiator is selected from at least one of halogenated hydrocarbon derivatives, compounds with a triazole skeleton, compounds with a diazole skeleton, compounds with an imidazole skeleton, phosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxy ketone compounds, and α-amino ketone compounds; And / or, the crosslinking agent is selected from at least one of hydroxymethyl compounds, melamine compounds, vinyl ether compounds, benzophenone compounds, and acrylate compounds.

6. The photosensitive resin composition according to claim 1, wherein The surfactant is selected from at least one of fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and polysiloxane surfactants.

7. The photosensitive resin composition according to claim 1, wherein By mass, the raw material components further include 400 to 800 parts of organic solvent.

8. Use of the photosensitive resin composition according to any one of claims 1 - 7 in semiconductor preparation, display panel manufacturing, or printed circuit boards.

9. A photosensitive film, characterized in that, Cured from the photosensitive resin composition according to any one of claims 1 - 7.

10. A circuit board, characterized in that, Including the photosensitive film according to claim 9.

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