UV (ultraviolet) light-cured alkali-developable resin composition and application thereof

Abstract

The invention relates to the technical field of electronic materials, in particular to a UV light-cured alkali developing resin composition and application. The preparation method comprises the following steps: firstly, taking a polyepoxy compound, unsaturated monocarboxylic acid, unsaturated monocarboxylic acid anhydride and dicarboxylic acid anhydride as raw materials to prepare unsaturated group-containing alkali developable resin with excellent developability and excellent heat resistance and dielectric property of a cured product, and on the basis of the resin, adding a specific photopolymerization initiator to prepare the unsaturated group-containing alkali developable resin. The photocuring alkali developing resin composition is synthesized; the photopolymerization initiator having an oxime bond according to the present invention has excellent solubility in a specific solvent, can reduce inactivation of the photopolymerization initiator having an oxime bond, and can prevent recrystallization. Therefore, the resin researched and developed by the invention is high in dispersion efficiency, good in viscosity reduction, good in stability and good in color developing property when being used as a dispersion medium in red paste; the synthesis process is green and environment-friendly, a free radical copolymerization method is adopted in the synthesis process, the cost is low, and the production process is stable and free of pollution.

Description

Technical Field

[0001] The present invention relates to the technical field of electronic materials, in particular to a UV light-curable alkali-developable resin composition and its application. Background Art

[0002] Photoresist, also known as photoresist, refers to a thin film material whose solubility changes when exposed to ultraviolet light, electron beams, ion beams, X-rays, or other radiation. Photoresist is the material with the highest technical barriers among electronic chemicals, characterized by high purity requirements, complex production processes, and a long technical accumulation period.

[0003] Photoresist is composed of a film-forming resin (polymerizing agent), a photoinitiator, a solvent, and additives. The film-forming resin is used to bind the various materials in the photoresist together, forming the photoresist's backbone and determining its fundamental properties, such as hardness, flexibility, and adhesion. Photoinitiators, including photosensitizers and photoacid generators, are key components of photoresist and play a decisive role in its sensitivity and resolution.

[0004] Resin is the skeleton of photoresist and also the most core component, so photoresist resin is crucial to the performance of photoresist.

[0005] The structural design of the resin involves the type and ratio of monomers, which directly determines the achievable linewidth (CD) of the photoresist at a specific wavelength. It also influences the Alkali Dissolution Rate (ADR) characteristics, thereby determining factors such as the exposure energy (EOP). Furthermore, the resin's molecular weight and PDI (Potentiation Index) also affect the photoresist's film thickness, etch resistance, and adhesion. In other words, the quality of the resin determines the quality of the photolithographic "image," and the stability of the resin quality determines the consistency of each image.

[0006] The industrialization of semiconductor photoresist resins faces numerous challenges, the first of which is synthesis technology. Photoresist resin synthesis techniques can be categorized into free radical polymerization, anionic polymerization, and living radical polymerization. Currently, free radical polymerization is the most commonly used. This technique easily controls the resin's molecular weight and is readily commercializable. However, its drawback is that the PDI (polydispersity index) is difficult to control, resulting in the inability to achieve certain photolithography performance requirements. Other challenges include amplification stability and metal ion removal, stable raw material and resin supply, lengthy customer certification and procurement processes, and the need to achieve economies of scale for customized products.

[0007] Alkali-developable ultraviolet (UV)-curing resins offer advantages such as high resolution, rapid photosensitivity, and excellent corrosion resistance, making them key materials for color photoresists, insulating organic films, and printed circuit boards (PCBs). Japan currently dominates this research field, while my country imports over 90% of its high-performance resins. Therefore, the development and manufacture of high-performance, highly efficient, and environmentally friendly alkali-developable UV-curing resins is of great significance.

[0008] Photocurable alkali-developable resin compositions are subject to numerous requirements, including curing with low exposure, excellent alkali developability, high heat resistance of the cured product, excellent substrate adhesion, and excellent dielectric properties. Conventional resin materials are obtained by further reacting an intermediate obtained by reacting a cresol novolac-type epoxy resin, acrylic acid, and methacrylic anhydride with tetrahydrophthalic anhydride. While acid-side chain epoxy acrylates offer high curability upon light irradiation and excellent developability, the resulting cured products lack sufficient heat resistance and dielectric properties, making it difficult to achieve excellent developability or high-definition pattern linearity, thus failing to meet increasingly stringent requirements. Summary of the Invention

[0009] In order to solve the problems mentioned above in the background art, the present invention has developed a photocurable alkali-developable resin composition and its application, which has excellent developability, and heat resistance and dielectric properties of the cured product.

[0010] To achieve the above object, the present invention provides the following technical solutions: The present invention provides a UV light-curable alkali-developable resin composition, comprising: an alkali-developable resin containing an unsaturated group, a photopolymerization initiator, a heat-curing component, and a filler; The alkali-developable resin containing unsaturated groups is obtained by reacting a polyepoxide, an unsaturated monocarboxylic acid, an unsaturated monocarboxylic anhydride, and a dicarboxylic anhydride as raw materials; the alkali-developable resin containing unsaturated groups has an acid value of 75 to 85, a viscosity of 1.1 to 1.3, a solid content of 40 to 45, a weight average molecular weight of 8000 to 8600, and a PDI of 2.0 to 2.6; The photopolymerization initiator has a structure shown in the following formula 1: Formula 1; The filler is glass powder and / or talc powder modified by a silane coupling agent, and has a particle size of 50-200 nm.

[0011] Furthermore, in the preparation of the alkali-developable resin containing unsaturated groups, the polyepoxy compound is a well-known hydroxyl-containing resin, specifically one or more of: o-cresol epoxy resin, bisphenol epoxy resin, phenylene ether epoxy resin, naphthylene ether epoxy resin, biphenyl epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol novolac epoxy resin, naphthol novolac epoxy resin, naphthol-phenol co-decanoic novolac epoxy resin, naphthol-cresol co-decanoic novolac epoxy resin, phenol aralkyl epoxy resin, naphthol aralkyl epoxy resin, and dicyclopentadiene-phenol.

[0012] Preferably, the polyepoxide is o-cresol epoxy resin, cresol novolac epoxy resin, or bisphenol novolac epoxy resin.

[0013] The unsaturated monocarboxylic acid is acrylic acid; or other well-known unsaturated monocarboxylic acids.

[0014] The unsaturated monocarboxylic anhydride is methacrylic anhydride; or other well-known saturated monocarboxylic anhydrides.

[0015] The dicarboxylic anhydride is tetrahydrophthalic anhydride; or other well-known dicarboxylic anhydrides.

[0016] Furthermore, the composition comprises, by weight: 90-100 parts of an alkali-developable resin containing an unsaturated group, 1-5 parts of a photopolymerization initiator, 1-5 parts of a thermosetting component, and 20-30 parts of a filler.

[0017] Furthermore, the preparation of the filler comprises the following steps: ball-milling glass powder and / or talc powder, then uniformly mixing with PGDA, adding a silane coupling agent having a methacryloyl group, mixing and uniformly dispersing the mixture, and filtering, washing with water, and vacuum drying to obtain a modified filler; Furthermore, the thermosetting component is a multifunctional epoxy resin, and the specific multifunctional epoxy resin is bisphenol epoxy resin, bisphenol A epoxy resin and other well-known epoxy resins.

[0018] Furthermore, the UV light-curable alkali-developable resin composition also includes an organic solvent, which is not particularly limited and can dissolve various components such as the aforementioned unsaturated group-containing alkali-developable resin, photopolymerization initiator, thermosetting component, filler, etc., and can be dried under dry conditions without causing adverse effects on the dried coating film.

[0019] Specifically, the organic solvent can be ketones (methyl ethyl ketone, acetone, cyclohexanone, methyl isobutyl ketone, etc.), cellosolve, butyl cellosolve, ethers (glycol ethers); acetates (ethyl acetate, butyl acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, etc.), alcohols (ethanol, propanol, ethylene glycol, propylene glycol, methoxypropanol, etc.).

[0020] The present invention also provides a method for preparing the UV light-curable alkali-developable resin composition as described above, comprising the following steps: mixing 90-100 parts of the alkali-developable resin containing an unsaturated group as described above, 1-5 parts of a photopolymerization initiator, 1-5 parts of a thermosetting component, and 20-30 parts of a filler, and grinding the mixture in a ball mill to obtain a UV light-curable alkali-developable resin composition.

[0021] The present invention also provides a cured product obtained by curing the UV light-curable alkali-developable resin composition.

[0022] The present invention also provides a use of the UV light-curable alkali-developable resin composition in a semiconductor photoresist resin material.

[0023] Compared with the prior art, the present invention has the following beneficial effects: This invention synthesizes an alkali-developable resin containing unsaturated groups. The main raw materials include: a polyepoxide, an unsaturated monocarboxylic acid, an unsaturated monocarboxylic anhydride, and a dicarboxylic anhydride. The resulting alkali-developable resin containing double bond groups has a specific hydroxyl value and acid value, and a specific molecular weight range. The resin with a specific acid value and hydroxyl value exhibits excellent developability, and the cured product has excellent heat resistance and dielectric properties.

[0024] The present invention synthesizes a UV-curable, alkali-developable resin composition based on the above resin by adding a specific photopolymerization initiator. The synthesis process of the present invention is environmentally friendly and uses a free radical copolymerization method, which is low-cost and has a stable and pollution-free production process.

[0025] The invention introduces a carboxyl group into the molecular structure of the photopolymerization initiator to improve its water solubility; it can effectively solve the problem of excessive development and biting caused by the existing oxime ester photoinitiator due to its high sensitivity, and reduce pollution during use.

[0026] The photopolymerization initiator having an oxime bond of the present invention has excellent solubility in specific solvents (aqueous solvents), can reduce deactivation of the photopolymerization initiator having an oxime bond, and can also prevent recrystallization. The present invention preferably uses the photopolymerization initiator having an oxime bond to synthesize a UV-curable, alkali-developable resin composition. This is environmentally friendly and reduces the use of organic solvents.

[0027] The filler of the present invention is modified with a silane coupling agent to impart photoreactive (or thermoreactive) functional groups to its surface. The reaction of the filler with a carboxyl-containing resin or a thermosetting resin further enhances heat resistance. The addition of a thermosetting component further enhances heat resistance. DETAILED DESCRIPTION

[0028] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention. Example 1

[0029] Alkali-developable resin containing unsaturated groups Add 120g of dipropylene glycol monomethyl ether acetate and 400g of o-cresol epoxy resin, mix and dissolve, then add 0.5g of p-methoxyphenol, raise the temperature to 70-75°C, add 40g of acrylic acid, stir at 100rpm for 10min, then add 120g of methacrylic anhydride and 40g of acrylic acid, stir at 100rpm for 10min, raise the temperature to 100-105°C, and react for 3-3.5h.

[0030] Add 220 g of diethylene glycol monoethyl ether acetate, 165 g of tetrahydrophthalic anhydride, and 0.5 g of p-methoxyphenol, and react at 105-110°C for 2 hours to obtain an alkali-developable resin containing unsaturated groups, which has an acid value of 75-85, a viscosity of 1.1-1.3, a solid content of 40-45, a weight-average molecular weight of 8000-8600, and a PDI of 2.0-2.6. Example 2

[0031] 95 g of the unsaturated group-containing alkali-developable resin prepared in Example 1, 3 g of a photopolymerization initiator, 3 g of a thermosetting component, and 25 g of a filler were mixed and ground in a ball mill to obtain a UV-curable alkali-developable resin composition.

[0032] The photopolymerization initiator has a structure shown in the following formula 1: Formula 1; The heat curing component is a bisphenol epoxy resin; The filler is prepared by ball-milling 1000g of glass powder, then uniformly mixing it with PGDA, adding 20g of a silane coupling agent having a methacryloyl group, mixing and uniformly dispersing it, and filtering, washing with water, and vacuum drying to obtain a modified filler with a particle size of 50-200nm. Example 3

[0033] 100 g of the unsaturated group-containing alkali-developable resin prepared in Example 1, 5 g of the photopolymerization initiator of Formula 1, 4 g of a bisphenol-type epoxy resin, and 30 g of a filler were mixed and ground in a ball mill to obtain a UV-curable alkali-developable resin composition.

[0034] The filler is prepared by ball-milling 600 g of glass powder and 400 g of talc powder, then uniformly mixing with PGDA, adding 20 g of a silane coupling agent having a methacryloyl group, mixing and uniformly dispersing the mixture, and filtering, washing with water, and vacuum drying to obtain a modified filler with a particle size of 50-200 nm. Example 4

[0035] 90 g of the unsaturated group-containing alkali-developable resin prepared in Example 1, 1 g of the photopolymerization initiator of Formula 1, 2 g of a bisphenol-type epoxy resin, and 25 g of a filler were mixed and ground in a ball mill to obtain a UV-curable alkali-developable resin composition.

[0036] The filler is prepared by ball-milling 1000g of glass powder, then uniformly mixing it with PGDA, adding 20g of a silane coupling agent having a methacryloyl group, mixing and uniformly dispersing it, and filtering, washing with water, and vacuum drying to obtain a modified filler with a particle size of 50-200nm. Example 5

[0037] 100 g of the unsaturated group-containing alkali-developable resin prepared in Example 1, 2 g of the photopolymerization initiator of Formula 1, 1 g of a bisphenol-type epoxy resin, and 20 g of a filler were mixed and ground in a ball mill to obtain a UV-curable alkali-developable resin composition.

[0038] The filler is prepared by ball-milling 1000g of glass powder, then uniformly mixing it with PGDA, adding 20g of a silane coupling agent having a methacryloyl group, mixing and uniformly dispersing it, and filtering, washing with water, and vacuum drying to obtain a modified filler with a particle size of 50-200nm.

[0039] The UV-curable alkali-developable resin compositions prepared in Examples 2-5 were applied to a substrate using an applicator and dried at 80°C for 30 minutes, 1 hour, and 1.5 hours. After UV irradiation, the cured product was heated at 90-100°C for 1 hour, and the cured product was peeled from the substrate to obtain a cured product. The developed product was then evaluated for its developability, heat resistance, and dielectric properties.

[0040] Developability A 1% sodium carbonate aqueous solution was used at 2.0 kgf / cm 2 The film was developed with a spray pressure of 1000 nm for 60 seconds, and the presence or absence of a coating film after development was observed and evaluated according to the following criteria.

[0041] ○: The coating film was completely removed after development, and complete development was possible.

[0042] ×: A small amount of the coating film remains after development and is not removed, indicating incomplete development.

[0043] In terms of the clarity of the formed image, the cured products prepared from the UV light-curable alkali-developable resin compositions prepared in Examples 2 to 5 of the present invention have good linearity and less development residue, among which Example 2 is the best.

[0044] Heat resistance A 6 mm x 35 mm test piece was cut out from the cured product and evaluated using a viscoelasticity measuring apparatus (frequency 1 Hz, heating rate 3°C / min) at the temperature where the elastic modulus changed the most (the tan δ change rate was the largest) as the glass transition temperature.

[0045] Dielectric properties The dielectric constant of the cured product (1) at 1 GHz was measured by a volumetric method using an impedance material analyzer "HP4291B" manufactured by Agilent Technologies Japan, Ltd. after being absolutely dried and stored in a room at 25°C and 60% humidity for 24 hours.

[0046] Table 1 performance Example 2 Example 3 Example 4 Example 5 Developability ○ ○ ○ ○ Heat resistance (℃) 186 177 181 179 Dielectric constant 2.2 2.5 2.4 2.35 The above results indicate that the UV-curable alkali-developable resin composition of the present invention has excellent developability, good linearity, and little development residue, and also has excellent heat resistance and dielectric properties.

[0047] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0048] It should be noted that the above content merely illustrates the technical idea of ​​the present invention and cannot be used to limit the scope of protection of the present invention. For ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications all fall within the scope of protection of the claims of the present invention.

Claims

1. A UV light-curable alkali-developable resin composition, characterized in that: include: Alkali-developable resin containing unsaturated groups, photopolymerization initiator, thermosetting component, filler; The alkali-developable resin containing an unsaturated group is obtained by reacting a polyepoxy compound, an unsaturated monocarboxylic acid, an unsaturated monocarboxylic anhydride and a dicarboxylic anhydride as raw materials; The photopolymerization initiator has a structure shown in the following formula 1: Formula 1; The filler is glass powder and / or talc powder modified by a silane coupling agent, and has a particle size of 50-200 nm.

2. A UV light-curable alkali-developable resin composition according to claim 1, characterized in that: The composition comprises, by weight, 90-100 parts of an alkali-developable resin containing an unsaturated group, 1-5 parts of a photopolymerization initiator, 1-5 parts of a heat-curing component, and 20-30 parts of a filler.

3. A UV light-curable alkali-developable resin composition according to claim 2, characterized in that: The preparation of the filler comprises the following steps: ball-milling glass powder and / or talc powder, then uniformly mixing with PGDA, adding a silane coupling agent having a methacryloyl group, mixing and uniformly dispersing the mixture, and filtering, washing with water, and vacuum drying to obtain the modified filler.

4. The UV light-curable alkali-developable resin composition according to claim 1, wherein The alkali-developable resin containing unsaturated groups has an acid value of 75-85, a viscosity of 1.1-1.3, a solid content of 40-45, a weight-average molecular weight of 8000-8600, and a PDI of 2.0-2.

6.

5. The UV light-curable alkali-developable resin composition according to claim 1, characterized in that: The heat curing component is a multifunctional epoxy resin.

6. A method for preparing the UV-curable alkali-developable resin composition according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: mixing 90-100 parts of the unsaturated group-containing alkali-developable resin according to any one of claims 1 to 5, 1-5 parts of a photopolymerization initiator, 1-5 parts of a thermosetting component, and 20-30 parts of a filler, and grinding the mixture in a ball mill to obtain a UV light-curable alkali-developable resin composition.

7. A solidified product, characterized in that: The resin composition is obtained by curing the UV-curable alkali-developable resin composition according to any one of claims 1 to 5.

8. Use of the UV light-curable alkali-developable resin composition according to any one of claims 1 to 5 in semiconductor photoresist resin materials.

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