Electroplating photoresist resin for lead frame, carrier plate, PCB and RDL packaging and preparation method and application thereof

Abstract

The invention relates to the field of electroplating photoresist, and particularly discloses electroplating photoresist resin for lead frame, carrier plate, PCB (printed circuit board) and RDL (redistribution layer) packaging as well as a preparation method and application of the electroplating photoresist resin. The electroplating photoresist resin for packaging the lead frame, the carrier plate, the PCB and the RDL is prepared from the following raw materials in parts by weight: 90 to 110 parts of acrylate monomer; 8 to 12 parts of acrylate mono-terminated isocyanate; 1.8 to 2.2 parts of an initiator; 0.08 to 0.12 part of a polymerization inhibitor; 0.08 to 0.12 part of a catalyst; 25 to 35 parts of a solvent; and carrying out electroplating coating on the photoresist wet film under the conditions that the photoresist wet film is irradiated by a photosensitive light source, the voltage of a rectifier is 60-150V, the electroplating time is 10-30s and the ratio of the line width to the line distance is 1: 1, so as to obtain an electroplated photoresist wet film with the thickness of 3-25 microns and the porosity of less than 0.5%. The prepared electroplating photoresist resin electroplating photoresist wet film solves the problems that an existing photosensitive dry film is limited in resolution ratio, poor in uniformity and poor in adaptability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electroplating photoresist, in particular to an electroplating photoresist resin for lead frame, carrier plate, PCB and RDL packaging and a preparation method and application thereof. BACKGROUND

[0002] As a key material for pattern transfer in the photoetching process, the performance of the photoresist directly affects the manufacturing precision of microelectronic devices such as semiconductors and display panels. As one of the core categories of photoresists, the photosensitive dry film is mainly used in the pattern transfer process in the manufacturing of lead frames, carrier plates, RDLs and PCBs, and plays a decisive role in circuit precision and yield. With the continuous development of microelectronic device manufacturing technology, the performance requirements for photoresists are also becoming higher and higher, and the improvement of the performance of photoresists can further improve the manufacturing precision of related microelectronic devices, thereby promoting the development of the semiconductor, display panel and other industries.

[0003] In the prior art, a photosensitive dry film with a three-layer composite structure is generally used, the uppermost layer is a 12-25 μm thick PE protective film for isolating oxygen, the middle layer is a 15-60 μm thick acrylate photosensitive resin containing a photoinitiator and an additive, and the bottom layer is a 16-100 μm thick PET carrier film. Its production process includes five major processes of resin synthesis, precision coating, 80-120℃ hot air drying, polyethylene film compounding and roll packaging. When applied, it needs to go through 6 processing procedures of film coating, film pressing, exposure, development, etching and film removal. However, the photosensitive dry film has the following core defects: first, there is a resolution limit, when the light penetrates through the resin layer with a thickness of more than 15 μm, scattering phenomenon exceeding 12° occurs, resulting in exposure distortion of the side wall, so that the actual minimum line width is still as high as 25 μm, and there is a technical barrier; second, the uniformity is defective, the tension fluctuation in the coating process reaches ±5%, causing the film thickness tolerance to reach ±3 μm, and the yield in the manufacturing of 10 μm level circuit drops to below 40%; finally, the substrate adaptability is poor, the bending stiffness of the PE protective film / PET carrier film exceeds 5Gpa, and it cannot be attached to irregular substrates with a curvature radius of less than 5 mm, completely blocking its application in the field of three-dimensional packaging.

[0004] The above problems result in limited circuit precision, reduced yield and narrow application range, which cannot meet the current demand for high-precision and high-adaptability photoresists in microelectronic device manufacturing. Therefore, researchers have turned their attention to other categories of photoresists in order to improve the performance advantages of photoresists and broaden the application range. SUMMARY

[0005] In order to solve the above technical problems, the present application provides an electroplating photoresist resin for lead frame, carrier plate, PCB and RDL packaging and a preparation method and application thereof.

[0006] In a first aspect, the present application provides a kind of electroplating photoresist resin for lead frame, carrier plate, PCB and RDL package, by weight parts, the raw materials used include the following components: Acrylate monomer 90-110 parts; Acrylate single-end blocked isocyanate 8-12 parts; Initiator 1.8-2.2 parts; Polymerization inhibitor 0.08-0.12 parts; Catalyst 0.08-0.12 parts; Solvent 25-35 parts; The acrylate monomer includes at least three of methyl methacrylate, 3-(2-hydroxyethyl) 2-adamantyl methacrylate, methyl cyclopentyl acrylate, 3-phenoxy benzyl acrylate, 2-isopropyl-2-adamantanol acrylate, butyl acrylate, methacrylic acid, methyl acrylate, styrene, hydroxyethyl acrylate, glycerol 1,3-diglycerol diacrylate, dimethylaminoethyl methacrylate, N-isobutoxy methyl acrylamide, isobornyl acrylate, isobornyl methacrylate, isooctyl acrylate, hexafluorobutyl acrylate, and hydroxyethyl acrylate.

[0007] Optionally, the preparation method of the acrylate single-end blocked isocyanate includes the following steps: blending and dispersing acrylate and diisocyanate in acetone at a molar ratio of 1:1.1, adding a catalyst and introducing inert gas into the reaction system, and obtaining acrylate single-end blocked isocyanate by reaction. The catalyst includes organotin catalyst or amine catalyst.

[0008] Preferably, in the preparation method of the acrylate single-end blocked isocyanate, the acrylate used includes any one of hydroxyethyl acrylate, hydroxyethyl methacrylate and pentaerythritol triacrylate, and the diisocyanate includes any one of isophorone diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate and toluene diisocyanate.

[0009] Preferably, in the preparation method of the acrylate single-end blocked isocyanate, the acrylate used is pentaerythritol triacrylate.

[0010] Preferably, by weight parts, the raw materials used further include 0.8-1.2 parts of modified nano silicon particles.

[0011] Preferably, the modifier used to prepare the modified nano silicon particles includes one or more of γ-methacryloyloxypropyltrimethoxysilane, γ-glycidyl ether propyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, and nitrogen-aminoethyl-3-aminopropylmethyldimethoxysilane.

[0012] By adopting the technical scheme, the application realizes single end-capped isocyanate, the remaining active -NCO group at the other end reacts with the functional group in the acrylic ester prepolymer, realizes grafting, retains the double bond in the acrylic ester single end-capped isocyanate, and grafts with the modified nano silicon particles with good hydrophobicity, forms the electroplating photoresist resin with good hydrophobicity, etching resistance and photosensitivity, effectively improves the photoresist performance, and helps to improve the microelectronic device manufacturing precision.

[0013] The solvent includes any one of ethyl heptanoate, propylene glycol methyl ether acetate, isopropyl alcohol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and 1,3-dioxolane, in the specific embodiment of the application, isopropyl alcohol is selected, the initiator includes any one of azobisisobutyronitrile, potassium persulfate, benzoyl peroxide and ammonium sulfate, in the specific embodiment of the application, azobisisobutyronitrile is selected, the polymerization inhibitor includes any one of p-hydroxyanisole, hydroquinone, 2.6-di-tert-butyl-p-cresol and phenothiazine, in the specific embodiment of the application, p-hydroxyanisole is selected, the catalyst includes any one of dibutyltin dilaurate, triethylamine and 1,4-diazabicyclo[2.2.2]octane, in the specific embodiment of the application, 1,4-diazabicyclo[2.2.2]octane is selected, the substances used in the application are only illustrative, and a person skilled in the art can adjust and replace according to the actual situation, which cannot limit the protection scope of the application.

[0014] In the second aspect, the application provides a preparation method of an electroplating photoresist resin for lead frame, carrier plate, PCB and RDL packaging, including the following steps: The acrylic ester monomer, the initiator and the solvent are blended at a temperature of 60-80℃, after heat preservation for 150-200min, the acrylic ester single end-capped isocyanate, the polymerization inhibitor and the catalyst are added, the reaction is carried out for 210-260min, then the temperature is lowered, and the electroplating photoresist resin is obtained.

[0015] Preferably, the acrylic ester monomer, the initiator and the solvent are blended at a temperature of 60-80℃, and the modified nano silicon particles are also blended, the preparation method of the modified nano silicon particles is as follows: The pH of the nano silicon particle dispersion liquid with a concentration of 10-30wt% is adjusted to 4-5, the modifier is added, and stirring is carried out at a temperature of 60-80℃ for 6-8h, then filtration and drying are carried out, and the modified nano silicon particles are obtained.

[0016] Preferably, the weight ratio of the modifier to the nano silicon particles is (1-10):(90-99).

[0017] By adopting the technical scheme, the Si-O-Si covalent bond is formed by condensation of the modifier and the nano silicon particles, meanwhile, the methyl acryloyloxy group (-OCOC(CH3)=CH2) in the modifier can be subjected to free radical polymerization with the unsaturated resin in the system, so as to realize strong combination of the organic-inorganic interface, and the modified nano silicon particles are uniformly dispersed in the organic phase, and the agglomeration phenomenon is weak, and the hydrophobic group thereof can reduce the moisture absorption of the material, so that the electroplating photoresist resin has good water resistance.

[0018] After the modified nano silicon particles are prepared, the acrylate monomer, the modified nano silicon particles, the initiator and the solvent are pre-blended and pre-polymerized at a specific temperature, then the acrylate single-ended isocyanate, the polymerization inhibitor and the catalyst are added for reaction, so that the electroplating photoresist resin with good hydrophobic ability, etching resistance and photosensitivity can be prepared.

[0019] In the preparation of the modified nano silicon particles, any one of methyl isobutyl ketone, isopropyl alcohol, dipropylene glycol butyl ether, formic acid, glacial acetic acid and lactic acid is used to adjust the pH in the system, and in the specific embodiment of the present application, the glacial acetic acid is selected, which is only used as an example, and the person skilled in the art can adjust and replace according to the actual situation, and the protection scope of the present application cannot be limited by this. In a third aspect, the present application provides an electroplating photoresist wet film for lead frame, carrier plate, PCB and RDL packaging, which is prepared by the following method: the electroplating photoresist resin is subjected to electroplating film forming under the conditions that the photo source is irradiated, the rectifier voltage is 60-150V, the electroplating time is 10-30s, and the line width to line spacing ratio is 1:1, to obtain the electroplating photoresist wet film with a thickness of 3-25μm, and when the electroplating film forming is performed, the wavelength of the photo source used is 248nm / 365nm / 405nm / 436nm, and the light intensity is 50-2000mJ / cm 2 .

[0020] Preferably, the porosity of the electroplating photoresist wet film is <0.5%.

[0021] By adopting the technical scheme, the present application obtains a wet film of electroplating photoresist without the protection of PE protective film / PET carrier film under certain conditions, has low bending stiffness, can be attached to a special-shaped substrate with a curvature radius of less than 5 mm, and has good substrate adaptability; the material consumables are less than 50% of the thickness of a traditional dry film, the thin film structure greatly reduces the light scattering effect, and the resolution is more than 3 times higher than that of a traditional process; the etching resistance of the electrodeposited film layer is significantly improved due to a triple mechanism, the resin particles are deposited on the substrate at a speed of 5 m / s under the driving of an electric field, a compact packing with a porosity of less than 0.5% is formed (the porosity of a traditional coated film is more than 2%), the resin dense structure is greatly increased; the charged resin and the metal substrate form an ionic bond-covalent bond composite interface due to the chemical bonding effect, the adhesion is more stable; the double bond conversion rate is more than 95% during ultraviolet curing, so that the crosslinking density is greater; the above mechanisms work together to make the acid etching resistance time break through 30 min, and reach 3 times the protection strength of a traditional dry film; the electric field directional adsorption and the closed-loop recycling system make the utilization rate of the electroplating photoresist resin reach 99% (the traditional coating is only 58%), the raw material loss is reduced by more than 40%, and the manufacturing cost per square meter is directly reduced by 35%; the non-pressurized deposition (pressure < 0.1 N / cm 2 ) reduces the broken piece rate from 18% to 0.3%, and promotes the electronic circuit yield to break through 99%; the resin can be deposited on a special-shaped surface with a curvature radius of greater than or equal to 0.5 mm and a three-dimensional structure with an aspect ratio of 5:1 at one time, solves the rigidity dependence of the traditional process on a planar substrate, and expands to new fields such as aerospace curved surface sensors.

[0022] In summary, the present application has the following beneficial technical effects: 1. The present application utilizes the reaction of diisocyanate and acrylic ester with hydroxyl and double bond to realize single end-capped isocyanate, the remaining active -NCO group at the other end reacts with the functional groups in the acrylic ester prepolymer to realize grafting, the double bond in the single end-capped isocyanate is retained, and the modified nano-silicon particles with good hydrophobicity are grafted to form an electroplating photoresist resin with good hydrophobicity, etching resistance and photosensitivity, solving the resolution limitation problem of the existing photoresist and improving the circuit precision; the condensation of the modifier and the nano-silicon particles forms a Si-O-Si covalent bond, the modified nano-silicon particles are uniformly dispersed in the organic phase, agglomeration is reduced, the hydrophobic group reduces the moisture absorption of the material, and the electroplating photoresist resin has good water resistance, solving the uniformity defect problem of the existing photoresist and improving the circuit manufacturing yield; 2. The electroplated photoresist wet film prepared in this application solves the problem of poor substrate adaptability of existing photoresist materials. The resolution is more than three times higher than that of traditional processes. The significantly improved etching resistance of the electrodeposited film stems from a triple mechanism: resin particles are deposited on the substrate at a speed of 5 m / s driven by an electric field, forming a dense packing with a porosity of less than 0.5% (compared to over 2% porosity in traditional coatings), greatly increasing the resin's dense structure; due to the chemical bonding effect, charged resin and the metal substrate form an ionic-covalent composite interface, resulting in more stable adhesion; and the double bond conversion rate reaches over 95% during UV curing, leading to a higher crosslinking density. The synergistic effect of these mechanisms enables acid etching resistance time to exceed 30 minutes, achieving three times the protective strength of traditional dry films; the electric field-directed adsorption and closed-loop recycling system enable a 99% utilization rate of the electroplated photoresist resin (compared to only 58% in traditional coatings), reducing material loss by more than 40% and directly reducing the manufacturing cost per square meter by 35%; and the non-pressurized deposition (pressure < 0.1 N / cm²) method... 2 This reduces the breakage rate from 18% to 0.3%, driving the yield of electronic circuits to exceed 99%. It can be completely deposited in one go on irregular surfaces with a curvature radius ≥0.5mm and three-dimensional structures with a depth-to-width ratio of 5:1, solving the rigid dependence of traditional processes on planar substrates and expanding into new fields such as aerospace curved surface sensors. Attached Figure Description

[0023] Figure 1 This is a measurement diagram of the line lithography fineness of the electroplated photoresist wet film obtained in Application Example 3 of this application. Detailed Implementation

[0024] The substrate used in this application has an irregular surface with a curvature radius of ≥0.5mm and a three-dimensional structure with a depth-to-width ratio of 5:1.

[0025] The present application will be further described in detail below with reference to preparation examples, embodiments, application examples and comparative examples.

[0026] Preparation Example 1.1 A method for preparing acrylate mono-terminated isocyanates includes the following steps: Hydroxyethyl acrylate and isophorone diisocyanate were blended and dispersed in acetone at a molar ratio of 1:1.1, with the amount of acetone being 40 wt% of the total amount of hydroxyethyl acrylate and isophorone diisocyanate. 0.05 wt% of dibutyltin dilaurate was added, and nitrogen gas was introduced into the reaction system. The reaction was carried out at 45°C for 5 h to obtain acrylate monoterminated isocyanate.

[0027] Preparation Example 1.2 A method for preparing acrylate mono-terminated isocyanates includes the following steps: Hydroxyethyl methacrylate and isophorone diisocyanate were mixed and dispersed in acetone in a molar ratio of 1:1.1, the amount of acetone was 40wt% of the total amount of hydroxyethyl methacrylate and isophorone diisocyanate, 0.05wt% of dibutyltin dilaurate was added, nitrogen was introduced into the reaction system, and the reaction was carried out at a temperature of 45°C for 5h to obtain an acrylate mono-capped isocyanate.

[0028] Preparation Example 1.3 A method for preparing an acrylate mono-capped isocyanate, comprising the steps of: Pentaerythritol triacrylate and isophorone diisocyanate were mixed and dispersed in acetone in a molar ratio of 1:1.1, the amount of acetone was 40wt% of the total amount of pentaerythritol triacrylate and isophorone diisocyanate, 0.05wt% of dibutyltin dilaurate was added, nitrogen was introduced into the reaction system, and the reaction was carried out at a temperature of 45°C for 5h to obtain an acrylate mono-capped isocyanate.

[0029] Preparation Example 2.1 A method for preparing modified nano-silica particles, comprising the steps of: Acetic acid was added to a nano-silica particle dispersion liquid with a concentration of 10wt% to adjust the pH to 4-5, then γ-methacryloyloxypropyltrimethoxysilane was added and stirred at a temperature of 80°C for 6h, filtered, and dried to obtain modified nano-silica particles, the weight ratio of γ-methacryloyloxypropyltrimethoxysilane to nano-silica particles being 1:99.

[0030] Preparation Example 2.2 A method for preparing modified nano-silica particles, comprising the steps of: Acetic acid was added to a nano-silica particle dispersion liquid with a concentration of 30wt% to adjust the pH to 4-5, then γ-glycidoxypropyltrimethoxysilane was added and stirred at a temperature of 60°C for 8h, filtered, and dried to obtain modified nano-silica particles, the weight ratio of γ-glycidoxypropyltrimethoxysilane to nano-silica particles being 10:90.

[0031] Preparation Example 2.3 A method for preparing modified nano-silica particles, comprising the steps of: Acetic acid was added to a nano-silica particle dispersion liquid with a concentration of 20wt% to adjust the pH to 4-5, then γ-glycidoxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane were added and stirred at a temperature of 70°C for 7h, filtered, and dried to obtain modified nano-silica particles, the weight ratio of γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane to nano-silica particles being 1.5:1.5:97.

[0032] Example 1.1 A preparation method of a plating photoresin for lead frame, carrier board, PCB and RDL packaging, comprising the following steps: 110 g of acrylate monomer, 0.8 g of modified nano-silicon particles, 1.8 g of initiator azobisisobutyronitrile and 35 g of solvent isopropyl alcohol are blended at a temperature of 700℃, 12 g of acrylate single-terminated isocyanate, 0.12 g of polymerization inhibitor p-hydroxyanisole and 0.08 g of catalyst 1,4-diazabicyclo[2.2.2]octane are added after 150 min of heat preservation, the reaction is cooled down after 260 min, and the product is discharged to obtain the plating photoresin; wherein the 110 g of acrylate monomer is composed of 2:1:1.5:0.5 of methyl methacrylate, 3-(2-hydroxyethyl)adamantyl 2-methyl acrylate, 2-isopropyl-2-adamantanol acrylate and butyl acrylate; The modified nano-silicon particles are the modified nano-silicon particles prepared in Preparation Example 2.1. The acrylate single-terminated isocyanate is the acrylate single-terminated isocyanate prepared in Preparation Example 1.1.

[0033] Example 1.2 A preparation method of a plating photoresin for lead frame, carrier board, PCB and RDL packaging, comprising the following steps: 90 g of acrylate monomer, 1.2 g of modified nano-silicon particles, 2.2 g of initiator azobisisobutyronitrile and 25 g of solvent isopropyl alcohol are blended at a temperature of 80℃, 8 g of acrylate single-terminated isocyanate, 0.08 g of polymerization inhibitor p-hydroxyanisole and 0.12 g of catalyst 1,4-diazabicyclo[2.2.2]octane are added after 200 min of heat preservation, the reaction is cooled down after 210 min, and the product is discharged to obtain the plating photoresin; wherein the 90 g of acrylate monomer is composed of 2:1:1:0.5:0.5 of methylcyclopentyl acrylate, 3-phenoxybenzyl acrylate, 2-isopropyl-2-adamantanol acrylate, hexafluorobutyl acrylate and hydroxyethyl acrylate; The modified nano-silicon particles are the modified nano-silicon particles prepared in Preparation Example 2.2. The acrylate single-terminated isocyanate is the acrylate single-terminated isocyanate prepared in Preparation Example 1.2.

[0034] Example 1.3 A preparation method of a plating photoresin for lead frame, carrier board, PCB and RDL packaging, comprising the following steps: blending 100 g of acrylate monomer, 1 g of modified nano-silicon particles, 2 g of initiator azobisisobutyronitrile and 30 g of solvent isopropyl alcohol at a temperature of 120 DEG C, adding 10 g of acrylate single-terminated isocyanate, 0.1 g of polymerization inhibitor p-hydroxyanisole and 0.1 g of catalyst 1,4-diazabicyclo[2.2.2]octane after 175 min of heat preservation, cooling down after 235 min of reaction, and discharging to obtain the plating photoresin; wherein the 100 g of acrylate monomer is composed of 3-(2-hydroxyethyl) 2-methyladamantyl acrylate, 2-isopropyl-2-adamantanol acrylate, dimethylaminoethyl methacrylate, N-isobutoxy methyl acrylamide and hydroxyethyl acrylate in a ratio of 2:0.5:1:1:0.5; The modified nano-silicon particles are the modified nano-silicon particles prepared in Preparation Example 2.3. The acrylate single-terminated isocyanate is the acrylate single-terminated isocyanate prepared in Preparation Example 1.3.

[0035] Example 2.1 A preparation method of a plating photoresin for lead frame, carrier board, PCB and RDL packaging, which is different from Example 1.1 in that the modified nano-silicon particles prepared in Preparation Example 2.1 are removed, and the rest is the same as Example 1.1.

[0036] Example 2.2 A preparation method of a plating photoresin for lead frame, carrier board, PCB and RDL packaging, which is different from Example 1.1 in that the amount of the modified nano-silicon particles prepared in Preparation Example 2.1 is 0.5 g, and the rest is the same as Example 1.1.

[0037] Example 2.3 A preparation method of a plating photoresin for lead frame, carrier board, PCB and RDL packaging, which is different from Example 1.1 in that the amount of the modified nano-silicon particles prepared in Preparation Example 2.1 is 1.5 g, and the rest is the same as Example 1.1.

[0038] Comparative Example 1.1 Which is different from Example 1.1 in that the amount of acrylate monomer is 80 g, the amount of acrylate single-terminated isocyanate prepared in Preparation Example 1.1 is 15 g, and the rest is the same as Example 1.1.

[0039] Comparative Example 1.2 The difference from Example 1.1 is that the amount of acrylic ester monomer is 120 g, the amount of acrylic ester mono-capped isocyanate prepared in Preparation Example 1.1 is 5 g, and the rest is the same as Example 1.1.

[0040] Comparative Example 2.1 The difference from Example 1.1 is that the acrylic ester monomer is composed of 2-isopropyl-2-adamantanol acrylate and butyl acrylate in a weight ratio of 1:1, and the rest is the same as Example 1.1.

[0041] Comparative Example 2.2 The difference from Example 1.1 is that the acrylic ester monomer is 3-(2-hydroxyethyl) 2-methyladamantyl acrylate, and the rest is the same as Example 1.1.

[0042] Comparative Example 2.3 The difference from Example 1.1 is that the acrylic ester monomer is hydroxyethyl acrylate, and the rest is the same as Example 1.1.

[0043] Application Example 1 A wet film of electroplating photoresist for lead frame, carrier board, PCB and RDL packaging is prepared by the following method: The electroplating photoresist resin obtained in Example 1.1 is subjected to electroplating film formation on the surface of the substrate under the conditions of irradiation of a photosensitive light source, rectifier voltage of 60 V, electroplating time of 10 s, and line width to line spacing ratio of 1:1, and the wavelength of the photosensitive light source is 405 nm and the light intensity is 1000 mJ / cm 2 , to obtain an electroplating photoresist wet film with a thickness of 5 μm and a porosity of <0.5%.

[0044] Application Example 2 A wet film of electroplating photoresist for lead frame, carrier board, PCB and RDL packaging is prepared by the following method: The electroplating photoresist resin obtained in Example 1.2 is subjected to electroplating film formation on the surface of the substrate under the conditions of irradiation of a photosensitive light source, rectifier voltage of 150 V, electroplating time of 30 s, and line width to line spacing ratio of 1:1, and the wavelength of the photosensitive light source is 405 nm and the light intensity is 1000 mJ / cm 2 , to obtain an electroplating photoresist wet film with a thickness of 15 μm and a porosity of <0.5%.

[0045] Application Example 3 A wet film of electroplating photoresist for lead frame, carrier board, PCB and RDL packaging is prepared by the following method: The electroplating photoresist resin obtained in Example 1.1 was subjected to electroplating film formation on the surface of a substrate under the conditions of a photosensitive light source with a wavelength of 405 nm, an intensity of 1000 mJ / cm2, a rectifier voltage of 75 V, an electroplating time of 20 s, and a line width to line space ratio of 1:1, to obtain an electroplating photoresist wet film with a thickness of 10 μm and a porosity of <0.5%. 2 , obtained in Example 1.1 was replaced with the electroplating photoresist resin obtained in Example 1.3, and the rest was the same as in Application Example 3.

[0046] Application Example 4 An electroplating photoresist wet film for lead frame, carrier board, PCB and RDL packaging, which differs from Application Example 3 in that the electroplating photoresist resin obtained in Example 1.1 was replaced with the electroplating photoresist resin obtained in Example 1.3, and the rest was the same as in Application Example 3.

[0047] Application Example 5 An electroplating photoresist wet film for lead frame, carrier board, PCB and RDL packaging, which differs from Application Example 3 in that the electroplating photoresist resin obtained in Example 1.3 was replaced with the electroplating photoresist resin obtained in Example 2.1, and the rest was the same as in Application Example 3.

[0048] Application Example 6 An electroplating photoresist wet film for lead frame, carrier board, PCB and RDL packaging, which differs from Application Example 3 in that the electroplating photoresist resin obtained in Example 1.3 was replaced with the electroplating photoresist resin obtained in Example 2.2, and the rest was the same as in Application Example 3.

[0049] Application Example 7 An electroplating photoresist wet film for lead frame, carrier board, PCB and RDL packaging, which differs from Application Example 3 in that the electroplating photoresist resin obtained in Example 1.3 was replaced with the electroplating photoresist resin obtained in Example 2.3, and the rest was the same as in Application Example 3.

[0050] Comparative Application Example 1 An electroplating photoresist wet film for lead frame, carrier board, PCB and RDL packaging, which differs from Application Example 1 in that the electroplating photoresist resin obtained in Example 1.1 was replaced with the electroplating photoresist resin obtained in Comparative Example 1.1, and the rest was the same as in Application Example 1.

[0051] Comparative Application Example 2 An electroplating photoresist wet film for lead frame, carrier board, PCB and RDL packaging, which differs from Application Example 1 in that the electroplating photoresist resin obtained in Example 1.1 was replaced with the electroplating photoresist resin obtained in Comparative Example 1.2, and the rest was the same as in Application Example 1.

[0052] Comparative Application Example 3 A wet film of electroplating photoresist for lead frame, carrier board, PCB and RDL packaging, which is different from application example 1 in that the electroplating photoresist resin obtained in example 1.1 is replaced by the electroplating photoresist resin obtained in comparative example 2.1, and the rest is the same as application example 1.

[0053] Comparative application example 4 A wet film of electroplating photoresist for lead frame, carrier board, PCB and RDL packaging, which is different from application example 1 in that the electroplating photoresist resin obtained in example 1.1 is replaced by the electroplating photoresist resin obtained in comparative example 2.2, and the rest is the same as application example 1.

[0054] Comparative application example 5 A wet film of electroplating photoresist for lead frame, carrier board, PCB and RDL packaging, which is different from application example 1 in that the electroplating photoresist resin obtained in example 1.1 is replaced by the electroplating photoresist resin obtained in comparative example 2.3, and the rest is the same as application example 1.

[0055] Performance detection The line photoetching fineness (line width error value detected by FIB sample cutting and SEM electron microscope scanning), film thickness uniformity (film thickness error value detected by laser film thickness meter and white light interferometer), hydrophobic ability (weight change rate calculated by immersion method), and acid etching resistance (resistance to etching time detected after 10 min etching in etching solution at a temperature of 55±5℃ after development) of the wet film of electroplating photoresist obtained in application examples and comparative application examples were detected.

[0056] Table 1 data recording table Group Line width error value / μm Film thickness error value / μm Weight change rate % Etching resistance time / min Example 1 ±0.15 ±0.3 0.37 32 Example 2 ±0.16 ±0.3 0.32 43 Example 3 ±0.11 ±0.2 0.30 37 Example 4 ±0.09 ±0.3 0.22 40 Example 5 ±0.08 ±0.2 0.97 30 Example 6 ±0.06 ±0.3 0.85 32 Example 7 ±0.22 ±0.5 0.20 41 Comparative Example 1 ±0.83 ±0.7 0.39 28 Comparative Example 2 ±0.76 ±0.9 0.36 26 Comparative Example 3 ±0.63 ±0.8 0.43 24 Comparative Example 4 ±0.78 ±1.0 0.41 22 Comparative Example 5 ±0.83 ±1.0 0.47 19 According to the data in table 1, the application realizes single end-capped isocyanate, the remaining active -NCO group at the other end reacts with the functional groups in the acrylic ester prepolymer to realize grafting, the double bond in the single end-capped isocyanate of acrylic ester is preserved, and then the modified nano-silicon particles with good hydrophobicity are grafted to form an electroplating photoresist resin with good hydrophobicity, etching resistance and photosensitivity, which effectively improves the performance of the photoresist and helps to improve the manufacturing precision of microelectronic devices.

[0057] The application is electroplated and photoetched under certain conditions to obtain an electroplated photoetching glue wet film without PE protective film / PET carrier film protection, low bending stiffness, capable of adhering to a special-shaped substrate with a curvature radius of less than 5 mm, good substrate adaptability; the material consumables are less than 50% of the thickness of the traditional dry film, the thin film structure greatly reduces the light scattering effect, the resolution is more than 3 times higher than that of the traditional process; the etching resistance of the electrodeposited film layer is significantly improved due to three mechanisms, the resin particles are deposited on the substrate at a speed of 5 m / s driven by the electric field, forming a close-packed structure with a porosity of less than 0.5% (the porosity of the traditional coated film is more than 2%), greatly increasing the dense structure of the resin; due to the chemical bonding effect, the charged resin and the metal substrate form an ionic bond-covalent bond composite interface, which is more stable; the double bond conversion rate is more than 95% during ultraviolet curing, so that the crosslinking density is larger; the above mechanisms work together to make the acid etching resistance time break through 30 min, reaching 3 times the protection strength of the traditional dry film; the electric field directional adsorption and closed-loop recycling system make the utilization rate of the electroplated photoetching glue resin reach 99% (the traditional coating is only 58%), the raw material loss is reduced by more than 40%, and the direct manufacturing cost per square meter is reduced by 35%; the non-pressurized deposition (pressure <0.1 N / cm 2 ) reduces the broken piece rate from 18% to 0.3%, and promotes the electronic circuit yield to break through 99%; it can be deposited on the special-shaped surface with a curvature radius of ≥0.5 mm and a three-dimensional structure with a depth-width ratio of 5:1 at one time, solving the rigidity dependence of the traditional process on the plane substrate and expanding to new fields such as aerospace curved surface sensors.

[0058] The embodiments of the specific embodiment are the preferred embodiments of the application, and are not limited to the protection scope of the application, so that: any equivalent changes made according to the structure, shape, principle of the application should be covered within the protection scope of the application.

Claims

1. An electroplating photoresist resin for lead frame, carrier board, PCB and RDL packaging, characterized by, The raw materials used include the following components by weight parts: acrylate monomer 90-110 parts; acrylate monoterminated isocyanate 8-12 parts; initiator 1.8-2.2 parts; polymerization inhibitor 0.08-0.12 parts; catalyst 0.08-0.12 parts; solvent 25-35 parts; The acrylate monomer includes at least three of methyl methacrylate, 3-(2-hydroxyethyl) 2-methyladamantyl acrylate, methylcyclopentyl acrylate, 3-phenoxybenzyl acrylate, 2-isopropyl-2-adamantanol acrylate, butyl acrylate, methacrylic acid, methyl acrylate, styrene, hydroxyethyl acrylate, glycerol 1,3-diglycerol diacrylate, dimethylaminoethyl methacrylate, N-isobutoxy methyl acrylamide, isobornyl acrylate, isobornyl methacrylate, isooctyl acrylate, hexafluorobutyl acrylate, and hydroxyethyl acrylate.

2. The electroplating photoresist resin for lead frame, carrier, PCB and RDL packaging according to claim 1, characterized in that, In the preparation method of the acrylate monoterminated isocyanate, the acrylate used includes any one of hydroxyethyl acrylate, hydroxyethyl methacrylate, and pentaerythritol triacrylate, and the diisocyanate includes any one of isophorone diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, and toluene diisocyanate.

3. The electroplating photoresist resin for lead frame, carrier, PCB and RDL packaging according to claim 2, characterized in that, In the preparation method of the acrylate monoterminated isocyanate, the acrylate used is pentaerythritol triacrylate.

4. The electroplating photoresist resin for lead frame, carrier, PCB and RDL packaging according to claim 1, characterized in that, The raw materials used also include 0.8-1.2 parts of modified nano silicon particles by weight parts.

5. The electroplating photoresist resin for lead frame, carrier board, PCB and RDL packaging according to claim 4, characterized in that, The modifier used in the preparation of the modified nano silicon particles includes one or more of γ-methacryloyloxypropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, and nitrogen-aminoethyl-3-aminopropylmethyldimethoxysilane.

6. A method of preparing the electroplating photoresist resin for RDL packaging according to claim 1, characterized by, The steps include: The acrylate monomer, initiator, and solvent are copolymerized at a temperature of 60-80°C, and after 150-200 min of incubation, the acrylate monoterminated isocyanate, polymerization inhibitor, and catalyst are added, and after 210-260 min of reaction, the temperature is lowered, the product is discharged, and the electroplating photoresist resin is obtained.

7. The method of claim 6, wherein the electroplating photoresist resin is prepared for lead frame, carrier board, PCB and RDL packaging. When the acrylate monomer, initiator, and solvent are blended at a temperature of 60-80°C, the modified nano silicon particles are also added for blending, and the preparation method of the modified nano silicon particles is as follows: The pH of a nano silicon particle dispersion liquid with a concentration of 10-30 wt% is adjusted to 4-5, and after the addition of a modifier, the mixture is stirred and reacted at a temperature of 60-80°C for 6-8 h, filtered, and dried to obtain the modified nano silicon particles.

8. The method of claim 7, wherein the electroplating photoresist resin is prepared for lead frame, carrier board, PCB and RDL packaging. The weight ratio of the modifier to the nano silicon particles is (1-10):(90-99).

9. A plating photoresist wet film for leadframe, carrier board, PCB and RDL packaging, characterized in that, The electroplating photoresist resin of any one of claims 1-5 is subjected to electroplating film forming under the conditions of a photosensitive light source, a rectifier voltage of 60-150 V, an electroplating time of 10-30 s, and a line width to line space ratio of 1:1 to obtain an electroplating photoresist wet film having a thickness of 3-25 μm, wherein the wavelength of the photosensitive light source used in the electroplating film forming is 248 nm / 365 nm / 405 nm / 436 nm, and the light intensity is 50-2000 mJ / cm 2 .

10. A photoresist wet film for electroplating of leadframe, carrier board, PCB and RDL packaging according to claim 9, wherein, The porosity of the wet film of the electroplating photoresist is <0.5%.

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