Photosensitive resin composition and use thereof

Abstract

The application discloses a photosensitive resin composition and application thereof, and belongs to the technical field of photoresists. The composition comprises a first component; the first component is a polymer soluble in an alkaline aqueous solution, and a main chain skeleton of the polymer is an acrylate polymer; in terms of mass percentage, monomers for preparing the first component contain 30-40% of acrylate monomer A and 40-50% of acrylate monomer B, and the balance is monomer C; the acrylate monomer A is a monomer with a cyclic structure group, the acrylate monomer B is a monomer with a long-chain aliphatic group, and the monomer C is a monomer with a phenolic hydroxyl group and / or a carboxyl group. The photosensitive resin composition has good resolution, etching resistance and excellent adhesion stability, has a negative characteristic, and can be developed by using an alkaline aqueous solution. The photosensitive resin composition can be used for preparing an RDL wiring layer and can reserve a larger number of lines.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of photoresist technology, in particular, to a photosensitive resin composition and application thereof. BACKGROUND

[0002] Photoetching is a technology that, with the help of photoresist (also known as photoetching glue), under the irradiation of a specific light source, the pattern on a mask is transferred to a substrate through steps such as development and etching. This technology can be used to draw micro-nano patterns and has a wide range of applications in integrated circuits, optoelectronic devices, and micro / nano mechanical system circuit preparation.

[0003] Photoetching technology includes three elements: light source, photoresist, and photoetching process. Among them, photoresist is the most critical functional material in the photoetching process. After exposure, some components in the exposed area of the photoresist undergo chemical reactions, causing the solubility of the exposed area to change in the developing solution. After development in the developing solution, a specific photoetching pattern is obtained.

[0004] Photoresist is generally composed of four parts: film-forming resin, photosensitive substance, solvent, and appropriate additives. Among them, the film-forming resin is the main component of the photoresist and plays a supporting role in the entire photoresist, making the photoresist have etching resistance and having an important influence on the performance of the photoresist. According to the change in the solubility of the photoresist film in the developing solution before and after exposure, the photoresist can be divided into positive photoresist and negative photoresist. Among them, negative photoresist refers to the exposure area that, after being irradiated by ultraviolet light or radiation, undergoes crosslinking and is insoluble in the developing solution, while the non-exposed area is not crosslinked and is soluble in the developing solution. Through the difference in solubility of the resin before and after exposure, the desired pattern is formed.

[0005] The film-forming resin in negative photoresist plays a decisive role in various properties of the etching layer and can be divided into alkali-soluble copolymers and alkali-soluble photosensitive copolymers. Alkali-soluble copolymers are mainly obtained by free radical copolymerization of vinyl-based monomers containing carboxyl groups. Alkali-soluble photosensitive copolymers are mainly divided into two types: one is the grafting of double bond functional monomers onto free radical copolymers; the other is the modification of various epoxy resins using acrylic monomers, acid anhydrides, or isocyanate compounds.

[0006] In the production process of the negative photoresist, the adhesion and the binding force of the film forming resin itself cannot reach the ideal state, so some single functional or multi-functional crosslinking agent and photosensitive substance with a large number of unsaturated bonds are often used in combination with the resin. However, in the application of low film thickness photoresist, due to the large use of crosslinking agent and photosensitizer, the exposure size of the pattern area is obviously affected, the development time cannot be guaranteed within a reasonable specification range, and the pattern morphology cannot be maintained. In addition, the performance defects of the resin cannot be completely compensated by the additive. Therefore, the improvement of the performance of the film forming resin itself is the key to improve the performance of the negative photoresist.

[0007] In view of this, the present application is proposed. SUMMARY

[0008] One of the purposes of the present application is to provide a photosensitive resin composition with good resolution, etching resistance and excellent adhesion stability, negative characteristics, and development with an alkaline aqueous solution.

[0009] The second purpose of the present application is to provide an application of the photosensitive resin composition.

[0010] The present application can be implemented as follows:

[0011] In a first aspect, the present application provides a photosensitive resin composition, comprising a first component;

[0012] The first component is a polymer soluble in an alkaline aqueous solution, and the main chain skeleton of the polymer is an acrylate polymer.

[0013] The monomers for preparing the first component contain 30-40% of acrylate monomer A and 40-50% of acrylate monomer B, and the balance is monomer C, in terms of mass percentage.

[0014] Among them, the acrylate monomer A is a monomer with a cyclic structure group, the acrylate monomer B is a monomer with a long-chain aliphatic group, and the monomer C is a monomer with a phenolic hydroxyl group and / or a carboxyl group.

[0015] In an optional embodiment, the acrylate monomer A includes at least one of isobornyl acrylate, isobornyl methacrylate, adamantane-1-yl acrylate, adamantane-1-yl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, bicyclopentyl acrylate and bicyclopentyl methacrylate.

[0016] In an optional embodiment, the acrylate monomer B includes at least one of 4-hydroxybutyl acrylate, ethyl-2-methyl-1,3-dioxolanyl acrylate, cyclohexane dicarboximide acrylate, 1,9-nonanediol diacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

[0017] In an optional embodiment, the monomer C is an acrylate monomer or a phenolic hydroxyl monomer.

[0018] In an optional embodiment, the monomer C includes at least one of 4-vinylphenol, 4-isopropenylphenol, acrylic acid, methacrylic acid, and 4-hydroxy-2-methyl acrylanilide.

[0019] In an optional embodiment, the first component has a weight average molecular weight of 5,000 to 20,000.

[0020] In an optional embodiment, the photosensitive resin composition further includes a second component and a third component;

[0021] The second component is a photopolymerization initiator, and the third component is a compound having a polymerizable functional group.

[0022] In an optional embodiment, the photosensitive resin composition includes 100 parts of the first component, 1 to 20 parts of the second component, and 1 to 60 parts of the third component by mass fraction.

[0023] In an optional embodiment, the second component includes at least one of methyl benzoylformate, benzoin dimethyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropanone, and (2,4,6-trimethylbenzoyl)-diphenyl phosphine oxide; preferably, the second component is (2,4,6-trimethylbenzoyl)-diphenyl phosphine oxide.

[0024] In an optional embodiment, the third component is a substance capable of converting a linear or lightly branched macromolecule into a three-dimensional network structure; preferably, the third component includes at least one of diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and pentaerythritol tetraacrylate.

[0025] In an optional embodiment, the photosensitive resin composition further includes a fourth component, a fifth component, and at least one of the third component;

[0026] The fourth component is a solvent, the fifth component is an antioxidant, and the sixth component is a polymerization inhibitor.

[0027] In an alternative embodiment, the photosensitive resin composition further comprises 80-120 parts of a fourth component, 0.1-1 part of a fifth component, and 0.1-0.5 part of a sixth component, in the same mass fraction as the first component.

[0028] In an alternative embodiment, the solvent is an organic solvent; preferably, the organic solvent comprises at least one of propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, methyl 3-methoxypropionate, methanol, ethyl acetate, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, 1-methoxy-2-propanol, 1-methoxy-2-acetoxypropane, and propylene glycol 1-monomethyl ether 2-acetate;

[0029] And / or, the antioxidant comprises at least one of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-p-cresol, and N-phenyl-α-naphthylamine;

[0030] And / or, the polymerization inhibitor comprises a polyphenol and / or a substituted phenol; or, the polymerization inhibitor is p-hydroxyanisole.

[0031] In a second aspect, the present application provides the use of the photosensitive resin composition according to any one of the preceding embodiments, for example, for preparing an RDL wiring layer.

[0032] The beneficial effects of the present application include:

[0033] The acrylate monomer A in the present application is used to improve the structural stability of the resin, the acrylate monomer B is used to improve the adhesion of the resin, and the monomer C is used to improve the solubility of the resin in alkaline aqueous solution. After the above-mentioned monomers are combined, a film-forming resin with high adhesion and high bonding force can be synthesized.

[0034] By using the first component with the acrylate monomer A, the acrylate monomer B, and the monomer C as the key component of the photosensitive resin composition, the photosensitive resin composition has good resolution, etching resistance, and excellent adhesion stability. DETAILED DESCRIPTION

[0035] In order to make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. If the specific conditions are not specified in the embodiments, the conventional conditions or the conditions suggested by the manufacturers are adopted. If the manufacturers of the reagents or instruments are not specified, the conventional products that can be purchased in the market are adopted.

[0036] The photosensitive resin composition and the application thereof provided in the present application will be described in detail below.

[0037] The present application provides a photosensitive resin composition, which comprises a first component.

[0038] The first component is a polymer soluble in an alkaline aqueous solution, and the main chain skeleton of the polymer is an acrylate polymer.

[0039] The monomers for preparing the first component contain 30-40% of acrylate monomer A and 40-50% of acrylate monomer B, and the balance is monomer C, in terms of mass percentage.

[0040] For example, the amount of the acrylate monomer A in the monomers for preparing the first component can be 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% or 40%, or any other value within the range of 30-40%.

[0041] The amount of the acrylate monomer B can be 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49% or 50%, or any other value within the range of 40-50%.

[0042] The acrylate monomer A is a monomer containing a cyclic structure group, the acrylate monomer B is a monomer containing a long-chain aliphatic group, and the monomer C is a monomer containing a phenolic hydroxyl group and / or a carboxyl group.

[0043] Specifically, the cyclic structure group contained in the acrylate monomer A is at least one, for example, 1, 2, 3, 4 or more. Similarly, the long-chain aliphatic group contained in the acrylate monomer B is at least one, for example, 1, 2, 3, 4 or more. The monomer C can contain only a phenolic hydroxyl group, only a carboxyl group, or both a phenolic hydroxyl group and a carboxyl group.

[0044] For reference, the acrylate monomer A can exemplarily include at least one of isobornyl acrylate, isobornyl methacrylate, adamant-1-yl acrylate, adamant-1-yl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, dicyclopentenyl acrylate and dicyclopentenyl methacrylate.

[0045] The acrylic monomer B exemplarily can include at least one of 4-hydroxybutyl acrylate, ethyl-2-methyl-1,3-dioxolyl acrylate, cyclohexane dicarboximide acrylate, 1,9-nonanediol diacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.

[0046] The monomer C is an acrylic monomer or a phenolic monomer, which exemplarily can include at least one of 4-vinylphenol, 4-isopropenylphenol, acrylic acid, methacrylic acid and 4-hydroxy-2-methyl acryl aniline.

[0047] The acrylic monomer A is used to improve the structural stability of the resin, the acrylic monomer B is used to improve the adhesion of the resin (which can also be understood as the adhesion to the substrate), and the monomer C is used to improve the solubility of the resin in an alkaline aqueous solution. After the above-mentioned monomers are combined, a film-forming resin with high adhesion and high binding force can be synthesized.

[0048] By using the first component with the acrylic monomer A, the acrylic monomer B and the monomer C as the key component of the photosensitive resin composition, the photosensitive resin composition can have good resolution, etching resistance and excellent adhesion stability.

[0049] Preferably, in the present application, the weight average molecular weight of the first component is 5000-20000. The weight average molecular weight can be determined by gel permeation chromatography by standard styrene standard curve conversion.

[0050] Setting the weight average molecular weight of the first component in the above-mentioned molecular weight range can have more excellent performance. If the weight average molecular weight of the first component is less than 5000, it is easy to cause the size of the photosensitive resin composition after final exposure to be small, the binding force between the substrate to be weak, the alkali solubility to be too strong, and the morphology to be poor; if the weight average molecular weight of the first component is greater than 20000, it is easy to cause the size of the photosensitive resin composition after final exposure to be too large, the binding force between the substrate to be too strong, the alkali solubility to be weak, and the morphology to be poor.

[0051] The first component can be obtained by one-pot copolymerization of the preset acrylic monomers.

[0052] Further, the photosensitive resin composition provided by the present application further comprises a second component and a third component.

[0053] The second component is a photopolymerization initiator, which is a kind of compound that can absorb a certain wavelength of energy in the light region to generate free radicals, cations and the like, thereby initiating monomer polymerization, cross-linking and curing.

[0054] By way of reference, the second component can exemplarily include at least one of methyl benzoylformate, benzoin methyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropanone, and (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide. Preferably, the second component is (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide.

[0055] The third component is a compound having a polymerizable functional group, and can specifically be a compound capable of converting a linear or lightly branched macromolecule into a three-dimensional network structure, so as to improve the heat resistance, wear resistance, and solvent resistance of the resin.

[0056] By way of reference, the third component can exemplarily include at least one of diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and pentaerythritol tetraacrylate.

[0057] The photosensitive resin composition includes 100 parts of the first component, 1-20 parts of the second component, and 1-60 parts of the third component by mass fraction.

[0058] By way of reference, the amount of the second component contained in the photosensitive resin composition can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, or 20 parts, or the like, or any other value within the range of 1-20 parts, on the premise that the first component is 100 parts.

[0059] Similarly, the amount of the third component can be 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, or 60 parts, or the like, or any other value within the range of 1-60 parts.

[0060] Further, the photosensitive resin composition provided by the present application further includes at least one of a fourth component, a fifth component, and the third component.

[0061] The fourth component is a solvent, and is preferably an organic solvent.

[0062] By way of reference, the organic solvent can exemplarily include at least one of propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, methyl 3-methoxypropionate, methanol, ethyl acetate, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, 1-methoxy-2-propanol, 1-methoxy-2-acetoxypropane, and propylene glycol 1-monomethyl ether 2-acetate.

[0063] The fifth component is an anti-aging agent to retard aging of the composition.

[0064] By way of reference, the anti-aging agent can exemplarily include at least one of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-p-cresol, and N-phenyl-α-naphthylamine.

[0065] The sixth component is a polymerization inhibitor to terminate polymerization.

[0066] By way of reference, the polymerization inhibitor can also employ a polyphenol and / or a substituted phenol. A compound of a type suitable for a vinyl-type monomer polymerization system, such as p-hydroxyanisole, can also be used.

[0067] The photosensitive resin composition includes 80 to 120 parts of the fourth component, 0.1 to 1 part of the fifth component, and 0.1 to 0.5 part of the sixth component, in the same mass parts as the first component.

[0068] By way of reference, the photosensitive resin composition can include the fourth component in an amount of 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, 115 parts, or 120 parts, or any other value within the range of 80 to 120 parts, on the premise that the first component is 100 parts.

[0069] Similarly, the fifth component can be in an amount of 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, or 1 part, or any other value within the range of 0.1 to 1 part.

[0070] The sixth component can be in an amount of 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, 0.35 part, 0.4 part, 0.45 part, or 0.5 part, or any other value within the range of 0.1 to 0.5 part.

[0071] The photosensitive resin composition according to the present application can be prepared by mixing the components.

[0072] The photosensitive resin composition obtained above has a negative characteristic, can be developed with an aqueous alkaline solution, and the unexposed part is easily soluble in the aqueous alkaline solution, while the exposed part is insoluble in the aqueous alkaline solution, and the dissolution rate ratio of the unexposed part to the exposed part is excellent.

[0073] In addition, the application further provides the use of the photosensitive resin composition, for example, for preparing an RDL wiring layer, which can retain more lines.

[0074] The features and performances of the application are further described in detail below in combination with examples.

[0075] Example 1

[0076] (1) A four-necked flask equipped with a condenser, a thermometer and a stirrer was charged with a mixture of 10 g of 4-vinylphenol (monomer C), 30 g of isobornyl methacrylate (acrylate monomer A), 10 g of isobornyl acrylate (acrylate monomer A), 50 g of hydroxyethyl methacrylate (acrylate monomer B), 0.2 g of n-dodecanethiol, 4 g of azobisisobutyronitrile and 150 g of methanol.

[0077] (2) The mixture was heated in a thermostatic oil bath, the oil bath temperature was set to 80°C, and the heating was started to be timed when the internal temperature reached the boiling state of the solution.

[0078] (3) The heating was continued for 4 h, and then a solution of 1 g of azobisisobutyronitrile and 35 g of methanol was added to the reaction solution, and the heating was continued for 8 h.

[0079] (4) The reaction was terminated, and the temperature was lowered to ≤40°C, and then the product was discharged.

[0080] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water, and dispersed by stirring, and then separated into layers, and the upper clear liquid was removed, and the operation was repeated three times, and then placed in a vacuum drying oven at 45°C for 48 h to obtain a white powder of the polymer, and the molecular weight of the polymer was determined.

[0081] Example 2

[0082] (1) A four-necked flask equipped with a condenser, a thermometer and a stirrer was charged with a mixture of 15 g of 4-vinylphenol (monomer C), 30 g of isobornyl methacrylate (acrylate monomer A), 5 g of isobornyl acrylate (acrylate monomer A), 50 g of hydroxyethyl methacrylate (acrylate monomer B), 0.2 g of n-dodecanethiol, 4 g of azobisisobutyronitrile and 150 g of methanol.

[0083] (2) The above mixture is heated using a constant temperature oil bath, the oil bath temperature is set to 80°C, and heating is continued until the internal temperature reaches the boiling point of the solution, and timing is started.

[0084] (3) The reaction is heated for 4 hours, and a solution composed of 1 g of azobisisobutyronitrile and 35 g of methanol is added to the reaction solution, and the reaction is continued for 8 hours.

[0085] (4) The reaction is terminated, and the temperature is lowered to ≤40°C, and the product is discharged.

[0086] (5) The resin is dissolved in tetrahydrofuran, and is added dropwise to pure water, and is dispersed by stirring, and after standing and separating, the supernatant is removed, and the operation is repeated three times, and is placed in a vacuum drying oven at 45°C for 48 hours, and a white powder of the polymer is obtained, and the molecular weight of the polymer is measured.

[0087] Example 3

[0088] (1) A four-necked flask equipped with a condenser, a thermometer, and a stirrer is charged with a mixture composed of 10 g of 4-vinylphenol (monomer C), 20 g of methacrylic acid (monomer C), 30 g of isobornyl methacrylate (acrylate monomer A), 40 g of hydroxyethyl methacrylate (acrylate monomer B), 0.2 g of n-dodecanethiol, 4 g of azobisisobutyronitrile, and 150 g of methanol.

[0089] (2) The above mixture is heated using a constant temperature oil bath, the oil bath temperature is set to 80°C, and heating is continued until the internal temperature reaches the boiling point of the solution, and timing is started.

[0090] (3) The reaction is heated for 4 hours, and a solution composed of 1 g of azobisisobutyronitrile and 35 g of methanol is added to the reaction solution, and the reaction is continued for 8 hours.

[0091] (4) The reaction is terminated, and the temperature is lowered to ≤40°C, and the product is discharged.

[0092] (5) The resin is dissolved in tetrahydrofuran, and is added dropwise to pure water, and is dispersed by stirring, and after standing and separating, the supernatant is removed, and the operation is repeated three times, and is placed in a vacuum drying oven at 45°C for 48 hours, and a white powder of the polymer is obtained, and the molecular weight of the polymer is measured.

[0093] Example 4

[0094] (1), into a four-necked flask equipped with a condenser, a thermometer, and a stirrer, was added a mixture of 10 g of 4-vinylphenol (monomer C), 15 g of methacrylic acid (monomer C), 20 g of isobornyl methacrylate (acrylate monomer A), 15 g of isobornyl acrylate (acrylate monomer A), 20 g of hydroxyethyl methacrylate (acrylate monomer B), 20 g of 4-hydroxybutyl acrylate (acrylate monomer B), 0.2 g of n-dodecanethiol, 4 g of azobisisobutyronitrile, and 150 g of methanol.

[0095] (2) The above mixture was heated using a constant-temperature oil bath, the oil bath temperature was set to 80°C, and heating was continued until the internal temperature reached the boiling point of the solution, and the timing was started.

[0096] (3) The reaction was continued for 4 hours, a solution prepared by dissolving 1 g of azobisisobutyronitrile in 35 g of methanol was added to the reaction solution, and the reaction was continued for 8 hours.

[0097] (4) The reaction was terminated, and the temperature was lowered to ≤40°C, and the product was discharged.

[0098] (5) The resin was dissolved in tetrahydrofuran, and the solution was added dropwise to pure water, and the mixture was stirred to disperse the solution, and the upper clear liquid was removed after the mixture was left to stand and separate into layers, and the operation was repeated three times, and the product was left in a vacuum drying oven at 45°C for 48 hours to obtain a white powder, and the molecular weight of the polymer was measured.

[0099] Example 5

[0100] (1), into a four-necked flask equipped with a condenser, a thermometer, and a stirrer, was added a mixture of 10 g of 4-vinylphenol (monomer C), 15 g of methacrylic acid (monomer C), 20 g of isobornyl methacrylate (acrylate monomer A), 15 g of isobornyl acrylate (acrylate monomer A), 20 g of hydroxyethyl methacrylate (acrylate monomer B), 20 g of 4-hydroxybutyl acrylate (acrylate monomer B), 0.2 g of n-dodecanethiol, 4 g of azobisisobutyronitrile, and 150 g of methanol.

[0101] (2) The above mixture was heated using a constant-temperature oil bath, the oil bath temperature was set to 80°C, and heating was continued until the internal temperature reached the boiling point of the solution, and the timing was started.

[0102] (3) The reaction was continued for 4 hours, a solution prepared by dissolving 1 g of azobisisobutyronitrile in 35 g of methanol was added to the reaction solution, and the reaction was continued for 8 hours.

[0103] (4) The reaction was terminated, and the temperature was lowered to ≤40°C, and the product was discharged.

[0104] (5) The resin is dissolved in tetrahydrofuran, and then added dropwise into pure water with sufficient stirring and dispersion. After standing and separating into layers, the supernatant is removed, and the operation is repeated three times. Then, the mixture is placed in a vacuum drying oven at 45°C for 48 hours to obtain a white powder of the polymer. The molecular weight of the polymer is measured.

[0105] Example 6

[0106] (1) A four-necked flask equipped with a condenser, a thermometer, and a stirrer is charged with a mixture of 10 g of 4-vinylphenol (monomer C), 15 g of methacrylic acid (monomer C), 30 g of isobornyl methacrylate (acrylate monomer A), 45 g of hydroxyethyl methacrylate (acrylate monomer B), 0.2 g of n-dodecanethiol, 4 g of azobisisobutyronitrile, and 150 g of methanol.

[0107] (2) The above mixture is heated using a thermostatic oil bath, and the oil bath temperature is set to 80°C. The heating is continued until the internal temperature reaches the boiling point of the solution, and the timing is started.

[0108] (3) The heating is continued for 4 hours, and a solution composed of 1 g of azobisisobutyronitrile and 35 g of methanol is added to the reaction solution. The heating is continued for 8 hours.

[0109] (4) The reaction is terminated, and the temperature is lowered to ≤40°C, and the product is discharged.

[0110] (5) The resin is dissolved in tetrahydrofuran, and then added dropwise into pure water with sufficient stirring and dispersion. After standing and separating into layers, the supernatant is removed, and the operation is repeated three times. Then, the mixture is placed in a vacuum drying oven at 45°C for 48 hours to obtain a white powder of the polymer. The molecular weight of the polymer is measured.

[0111] Example 7

[0112] (1) A four-necked flask equipped with a condenser, a thermometer, and a stirrer is charged with a mixture of 10 g of 4-vinylphenol (monomer C), 10 g of methacrylic acid (monomer C), 30 g of isobornyl methacrylate (acrylate monomer A), 30 g of hydroxyethyl methacrylate (acrylate monomer B), 20 g of 4-hydroxybutyl acrylate (acrylate monomer B), 0.2 g of n-dodecanethiol, 4 g of azobisisobutyronitrile, and 150 g of methanol.

[0113] (2) The above mixture is heated using a thermostatic oil bath, and the oil bath temperature is set to 80°C. The heating is continued until the internal temperature reaches the boiling point of the solution, and the timing is started.

[0114] (3) The heating is continued for 4 hours, and a solution composed of 1 g of azobisisobutyronitrile and 35 g of methanol is added to the reaction solution. The heating is continued for 8 hours.

[0115] (4) The reaction is terminated, and the temperature is lowered to ≤40°C, and the product is discharged.

[0116] (5) The resin is dissolved in tetrahydrofuran, added dropwise into pure water, dispersed by stirring, and separated by layering. The supernatant is removed, and the operation is repeated three times. The product is placed in a vacuum drying oven at 45°C for 48 hours to obtain a white powder. The molecular weight of the polymer is determined.

[0117] Example 8

[0118] (1) A four-necked flask equipped with a condenser, a thermometer, and a stirrer is charged with a mixture of 20 g of methacrylic acid (monomer C), 20 g of isobornyl methacrylate (acrylate monomer A), 10 g of isobornyl acrylate (acrylate monomer A), 50 g of hydroxyethyl methacrylate (acrylate monomer B), 0.2 g of n-dodecanethiol, 4 g of azobisisobutyronitrile, and 150 g of methanol.

[0119] (2) The mixture is heated using a constant-temperature oil bath, and the oil bath temperature is set to 80°C. The heating is started when the internal temperature reaches the boiling point of the solution.

[0120] (3) The heating is continued for 4 hours. A solution of 1 g of azobisisobutyronitrile and 35 g of methanol is added to the reaction solution, and the heating is continued for 8 hours.

[0121] (4) The reaction is terminated, and the temperature is lowered to ≤40°C to discharge the product.

[0122] (5) The resin is dissolved in tetrahydrofuran, added dropwise into pure water, dispersed by stirring, and separated by layering. The supernatant is removed, and the operation is repeated three times. The product is placed in a vacuum drying oven at 45°C for 48 hours to obtain a white powder. The molecular weight of the polymer is determined.

[0123] Example 9

[0124] (1) A four-necked flask equipped with a condenser, a thermometer, and a stirrer is charged with a mixture of 10 g of 4-vinylphenol (monomer C), 10 g of methacrylic acid (monomer C), 20 g of isobornyl methacrylate (acrylate monomer A), 20 g of isobornyl acrylate (acrylate monomer A), 15 g of hydroxyethyl methacrylate (acrylate monomer B), 25 g of 4-hydroxybutyl acrylate (acrylate monomer B), 0.2 g of n-dodecanethiol, 4 g of azobisisobutyronitrile, and 150 g of methanol.

[0125] (2) The mixture is heated using a constant-temperature oil bath, and the oil bath temperature is set to 80°C. The heating is started when the internal temperature reaches the boiling point of the solution.

[0126] (3) Heating for 4 hours, and then adding a solution of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continuing heating for 8 hours.

[0127] (4) Terminating the reaction, and starting to cool down to ≤ 40°C to discharge.

[0128] (5) Dissolving the resin in tetrahydrofuran, and then adding pure water dropwise to disperse by stirring, and then removing the supernatant after standing and separating, and repeating three times, and then placing in a vacuum drying oven at 45°C to dry for 48 hours to obtain a white powder polymer, and then measuring the molecular weight of the polymer.

[0129] Example 10

[0130] (1) Adding a mixed solution of 15 g of 4-vinylphenol (monomer C), 15 g of methacrylic acid (monomer C), 10 g of isobornyl methacrylate (acrylate monomer A), 30 g of isobornyl acrylate (acrylate monomer A), 25 g of hydroxyethyl methacrylate (acrylate monomer B), 5 g of 4-hydroxybutyl acrylate (acrylate monomer B), 0.2 g of n-dodecanethiol, 4 g of azobisisobutyronitrile, and 150 g of methanol to a four-necked flask equipped with a condenser, a thermometer, and a stirrer.

[0131] (2) Heating the above mixed solution using a constant temperature oil bath, and setting the oil bath temperature to 80°C, and then heating to the internal temperature reaching the boiling state of the solution to start timing.

[0132] (3) Heating for 4 hours, and then adding a solution of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continuing heating for 8 hours.

[0133] (4) Terminating the reaction, and starting to cool down to ≤ 40°C to discharge.

[0134] (5) Dissolving the resin in tetrahydrofuran, and then adding pure water dropwise to disperse by stirring, and then removing the supernatant after standing and separating, and repeating three times, and then placing in a vacuum drying oven at 45°C to dry for 48 hours to obtain a white powder polymer, and then measuring the molecular weight of the polymer.

[0135] Comparative Example 1

[0136] (1) Adding a mixed solution of 20 g of isobornyl methacrylate (acrylate monomer A), 20 g of adamantan-1-yl methacrylate (acrylate monomer A), 30 g of cyclopentyl acrylate (acrylate monomer A), 30 g of isobornyl acrylate (acrylate monomer A), 0.2 g of n-dodecanethiol, 4 g of azobisisobutyronitrile, and 150 g of methanol to a four-necked flask equipped with a condenser, a thermometer, and a stirrer.

[0137] (2) The above mixture is heated using a constant temperature oil bath, the oil bath temperature is set to 80°C, and heating is continued until the internal temperature reaches the boiling state of the solution, and timing is started.

[0138] (3) The reaction is heated for 4 hours, a solution composed of 1 g of azobisisobutyronitrile and 35 g of methanol is added to the reaction solution, and the reaction is continued to be heated for 8 hours.

[0139] (4) The reaction is terminated, and the temperature is lowered to ≤40°C, and the product is discharged.

[0140] (5) The resin is dissolved in tetrahydrofuran, and pure water is added dropwise, and the mixture is stirred and dispersed, and after standing and separating into layers, the supernatant is removed, and the operation is repeated three times, and the product is placed in a vacuum drying oven at 45°C and dried for 48 hours, and a white powder of the polymer is obtained, and the molecular weight of the polymer is measured.

[0141] That is, the monomers of the first component of the comparative example contain only the acrylic ester monomer A, and do not contain the acrylic ester monomer B and the monomer C.

[0142] Comparative Example 2

[0143] (1) A four-necked flask equipped with a condenser, a thermometer, and a stirrer is charged with a mixture composed of 45 g of hydroxyethyl methacrylate (acrylic ester monomer B), 20 g of 4-hydroxybutyl acrylate (acrylic ester monomer B), 35 g of hydroxypropyl acrylate (acrylic ester monomer B), 0.2 g of n-dodecanethiol, 4 g of azobisisobutyronitrile, and 150 g of methanol.

[0144] (2) The above mixture is heated using a constant temperature oil bath, the oil bath temperature is set to 80°C, and heating is continued until the internal temperature reaches the boiling state of the solution, and timing is started.

[0145] (3) The reaction is heated for 4 hours, a solution composed of 1 g of azobisisobutyronitrile and 35 g of methanol is added to the reaction solution, and the reaction is continued to be heated for 8 hours.

[0146] (4) The reaction is terminated, and the temperature is lowered to ≤40°C, and the product is discharged.

[0147] (5) The resin is dissolved in tetrahydrofuran, and pure water is added dropwise, and the mixture is stirred and dispersed, and after standing and separating into layers, the supernatant is removed, and the operation is repeated three times, and the product is placed in a vacuum drying oven at 45°C and dried for 48 hours, and a white powder of the polymer is obtained, and the molecular weight of the polymer is measured.

[0148] That is, the monomers of the first component of the comparative example contain only the acrylic ester monomer B, and do not contain the acrylic ester monomer A and the monomer C.

[0149] Comparative Example 3

[0150] (1), into a four-necked flask equipped with a condenser, a thermometer, and a stirrer, was added a mixture of 45 g of methacrylic acid (monomer C), 20 g of acrylic acid (monomer C), 35 g of 4-vinylphenol (monomer C), 0.2 g of n-dodecanethiol, 4 g of azobisisobutyronitrile, and 150 g of methanol.

[0151] (2), the above mixture was heated using a thermostat oil bath, the oil bath temperature was set to 80°C, and heating was continued until the internal temperature reached the boiling state of the solution, and the timing was started.

[0152] (3), the reaction was continued for 4 hours, a solution composed of 1 g of azobisisobutyronitrile and 35 g of methanol was added to the reaction solution, and the reaction was continued for 8 hours.

[0153] (4), the reaction was terminated, and the temperature was lowered to ≤40°C, and the product was discharged.

[0154] (5), the resin was dissolved in tetrahydrofuran, and pure water was added dropwise, and the mixture was stirred and dispersed, and after the mixture was left to stand and separated into layers, the supernatant was removed, and the operation was repeated three times, and the product was left in a vacuum drying oven at 45°C for 48 hours, and a white powdery polymer was obtained, and the molecular weight of the polymer was measured.

[0155] That is, the monomers of the first component of the comparative example contained only monomer C, and did not contain the acrylate monomer A and the acrylate monomer B.

[0156] Comparative Example 4

[0157] (1), into a four-necked flask equipped with a condenser, a thermometer, and a stirrer, was added a mixture of 45 g of methacrylic acid (monomer C), 20 g of acrylic acid (monomer C), 35 g of 4-vinylphenol (monomer C), 20 g of methacrylic acid hydroxyethyl ester (acrylate monomer B), 0.2 g of n-dodecanethiol, 4 g of azobisisobutyronitrile, and 150 g of methanol.

[0158] (2), the above mixture was heated using a thermostat oil bath, the oil bath temperature was set to 80°C, and heating was continued until the internal temperature reached the boiling state of the solution, and the timing was started.

[0159] (3), the reaction was continued for 4 hours, a solution composed of 1 g of azobisisobutyronitrile and 35 g of methanol was added to the reaction solution, and the reaction was continued for 8 hours.

[0160] (4), the reaction was terminated, and the temperature was lowered to ≤40°C, and the product was discharged.

[0161] (5), the resin was dissolved in tetrahydrofuran, and pure water was added dropwise, and the mixture was stirred and dispersed, and after the mixture was left to stand and separated into layers, the supernatant was removed, and the operation was repeated three times, and the product was left in a vacuum drying oven at 45°C for 48 hours, and a white powdery polymer was obtained, and the molecular weight of the polymer was measured.

[0162] That is, the monomers of the first component of the comparative example contain only the acrylic ester monomer B and the monomer C, and do not contain the acrylic ester monomer A.

[0163] Comparative Example 5

[0164] (1) A four-necked flask equipped with a condenser, a thermometer, and a stirrer was charged with a mixture of 25 g of methacrylic acid (monomer C), 20 g of acrylic acid (monomer C), 35 g of 4-vinylphenol (monomer C), 20 g of isobornyl methacrylate (acrylic ester monomer A), 0.2 g of n-dodecanethiol, 4 g of azobisisobutyronitrile, and 150 g of methanol.

[0165] (2) The above mixture was heated using a constant-temperature oil bath, the oil bath temperature was set to 80°C, and heating was performed until the internal temperature reached the boiling state of the solution, and then the timing was started.

[0166] (3) The reaction was heated for 4 h, and a solution composed of 1 g of azobisisobutyronitrile and 35 g of methanol was added to the reaction solution, and the reaction was further heated for 8 h.

[0167] (4) The reaction was terminated, and the temperature was lowered to ≤40°C, and then the product was discharged.

[0168] (5) The resin was dissolved in tetrahydrofuran, and the solution was added dropwise to pure water, and dispersed by stirring. After the layers were separated, the upper clear liquid was removed, and the operation was repeated three times. The product was then placed in a vacuum drying oven at 45°C and dried for 48 h, and a white powdery polymer was obtained. The molecular weight of the polymer was measured.

[0169] That is, the monomers of the first component of the comparative example contain only the acrylic ester monomer A and the monomer C, and do not contain the acrylic ester monomer B.

[0170] Comparative Example 6

[0171] (1) A four-necked flask equipped with a condenser, a thermometer, and a stirrer was charged with a mixture of 30 g of isobornyl methacrylate (acrylic ester monomer A), 30 g of adamantan-1-yl methacrylate (acrylic ester monomer A), 40 g of hydroxyethyl methacrylate (acrylic ester monomer B), 0.2 g of n-dodecanethiol, 4 g of azobisisobutyronitrile, and 150 g of methanol.

[0172] (2) The above mixture was heated using a constant-temperature oil bath, the oil bath temperature was set to 80°C, and heating was performed until the internal temperature reached the boiling state of the solution, and then the timing was started.

[0173] (3) The reaction was heated for 4 h, and a solution composed of 1 g of azobisisobutyronitrile and 35 g of methanol was added to the reaction solution, and the reaction was further heated for 8 h.

[0174] (4) The reaction was terminated, and the temperature was lowered to ≤40°C, and then the product was discharged.

[0175] (5) The resin was dissolved in tetrahydrofuran, and the solution was added dropwise to pure water with stirring, and dispersed. After the upper layer was removed by standing, the operation was repeated three times. The resultant was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powder. The molecular weight of the polymer was measured.

[0176] That is, the monomers of the first component of the comparative example contained only the acrylic ester monomer A and the acrylic ester monomer B, and did not contain the monomer C.

[0177] Examples 1 to 10 and Comparative Examples 1 to 6

[0178] The photosensitive compositions of Examples 1 to 10 and Comparative Examples 1 to 6 were prepared by using the components and amounts shown in Table 1. The amounts in Table 1 are parts by weight of each component with respect to 100 parts by weight of the first component. The components required for the amounts in Table 1 were weighed according to the standard, and then added to a standard glass bottle. The bottle was tightly capped, and then placed on a uniform mixer to mix overnight (at least 8 hours or more) at room temperature.

[0179] The components used were as follows:

[0180] Second component (photoinitiator):

[0181] b1: (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide;

[0182] b2: methyl benzoylformate;

[0183] b1 and b2 were used together, and each of b1 and b2 accounted for 50 wt% of the second component.

[0184] Third component (polymerizable monomer):

[0185] c1: pentaerythritol tetraacrylate;

[0186] c2: diethylene glycol dimethacrylate;

[0187] c1 and c2 were used together, and each of c1 and c2 accounted for 50 wt% of the second component.

[0188] Fourth component (organic solvent):

[0189] d1: propylene glycol methyl ether acetate;

[0190] d2: diethylene glycol dimethyl ether;

[0191] d1 and d2 were used together, and d1 accounted for 70 wt% of the fourth component, and d2 accounted for 30 wt% of the fourth component.

[0192] Fifth component (age resistor):

[0193] e1: 2,2'-methylenebis(4-methyl-6-tert-butylphenol).

[0194] The sixth component (a polymerization inhibitor):

[0195] f1: p-hydroxyanisole.

[0196] After the uniform coating, the coating machine is used for coating, and after baking, pattern exposure is performed. After exposure, it is placed in the developing solution for development, and then the resolution and line retention are observed. The results are shown in Table 2.

[0197] Table 1

[0198]

[0199]

[0200] Table 1 (continued)

[0201]

[0202] Table 2 results

[0203]

[0204]

[0205] As can be seen from Table 2, the photosensitive resin compositions provided by Examples 1-10 all have excellent developing windows, indicating that the contrast of the alkali solubility difference between the unexposed area and the exposed area is excellent.

[0206] Compared with the examples, Comparative Examples 1 and 3 show excellent alkali solubility, but show poor adhesion to the substrate and fewer line retention numbers; Comparative Examples 2, 4, 5 and 6 show acceptable adhesion to the substrate, but show poor alkali solubility.

[0207] In summary, the photosensitive resin composition provided by the present application has a cyclic and long-chain acrylic monomer structure introduced into the first component, so that the photosensitive resin composition has good resolution, etching resistance and excellent adhesion stability. The photosensitive resin composition has negative characteristics, can be developed with an alkaline aqueous solution, the unexposed part to ultraviolet light is easily soluble in the alkaline aqueous solution, while the part exposed to ultraviolet light is insoluble in the alkaline aqueous solution, and the dissolution speed ratio of the unexposed part to the exposed part is excellent.

[0208] The above merely describes the preferred embodiments of the present application, and is not used to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A photosensitive resin composition, characterized in that, The photosensitive resin composition comprises, by weight, 100 parts of a first component, 1 part of a second component, 20 parts of a third component, 100 parts of a fourth component, 0.1 parts of a fifth component, and 0.2 parts of a sixth component; The monomers used to prepare the first component contain 30% acrylate monomer A and 50% acrylate monomer B by mass percentage, with the remainder being monomer C. The acrylate monomer A is isoborneol methacrylate, or the acrylate monomer A is isoborneol acrylate and isoborneol methacrylate in a mass ratio of 10:

20. The acrylate monomer B is hydroxyethyl methacrylate, or the acrylate monomer B is 4-hydroxybutyl acrylate and hydroxyethyl methacrylate in a mass ratio of 20:

30. The monomer C is methacrylic acid, or the monomer C is 4-vinylphenol and methacrylic acid in a mass ratio of 10:10; The second component consists of 50 wt% (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide and 50 wt% methyl benzoylformate; The third component consists of 50 wt% pentaerythritol tetraacrylate and 50 wt% diethylene glycol dimethacrylate; The fourth component consists of 70 wt% propylene glycol methyl ether acetate and 30 wt% diethylene glycol dimethyl ether; The fifth component is 2,2'-methylenebis(4-methyl-6-tert-butylphenol); The sixth component is p-hydroxyanisole.

2. The application of the photosensitive resin composition as described in claim 1, characterized in that, The photosensitive resin composition is used to prepare the RDL wiring layer.

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