An alkali-soluble resin, a method for producing the same, and a photosensitive dry film resist

Abstract

The application discloses an alkali-soluble resin and a preparation method thereof, and a photosensitive dry film resist, and belongs to the technical field of photosensitive dry film resist. The structural formula of the alkali-soluble resin is shown as formula I. In the alkali-soluble resin, polymaleic anhydride is modified into polymaleimide, and a fluorine-containing group is introduced on the N atom of the polymaleimide; the two groups synergistically act, can effectively improve the plating resistance of the photosensitive dry film of the corresponding alkali-soluble resin, and reduce the plating penetration or film throwing phenomenon of the photosensitive dry film resist product in the use process. The fluorine-substituted maleimide polymer can also improve the leveling property of the photosensitive dry film resist in the coating process, reduce the volume shrinkage rate of the dry film, and further improve the finished product yield of the photosensitive dry film.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of photosensitive dry film resist, and particularly relates to an alkali-soluble resin, a preparation method thereof and a photosensitive dry film resist. BACKGROUND

[0002] In the process of manufacturing printed circuit board, semiconductor package and lead frame, dry film resist has been widely used. In the process of manufacturing, dry film resist is pasted on copper substrate, then a mask with a pattern is used to cover the dry film resist for pattern exposure. Then, the unexposed area is cleaned by using weak alkaline aqueous solution, and then etching or plating treatment is performed to form the required pattern. Finally, the part of the dry film exposed to the light is removed by using alkaline stripping solution, so as to realize pattern transfer.

[0003] There are two main methods for manufacturing printed circuit board, i.e. mask method and pattern plating method. The mask method is to protect the copper through hole for mounting joint by using a protective layer, and then to form a circuit by etching and stripping. Nowadays, with the miniaturization of electronic equipment, high precision and lamination of PCB are required, and high resolution and high adhesion of dry film resist are required. Therefore, fine pitch pattern manufacturing is required in the process, and the pattern plating method becomes very important. Copper is plated on the copper substrate, and then tinned solder is plated for protection. Then, the circuit is formed by stripping and etching. In the process of plating copper, oil removing agent and tin brightener are used for surface treatment of the copper substrate. At the same time, the oil removing agent and tin brightener also attack the dry film resist. If the dry film resist has weak resistance to plating, the side wall of the dry film resist will be deformed and not uniform, and the bottom will be turned up, which will cause plating penetration during plating, resulting in poor circuit pattern.

[0004] As a core component of photosensitive dry film resist (about 40%-70% of the mass of the dry film), alkali-soluble resin has a great influence on the development, adhesion and plating resistance of the photosensitive dry film resist. However, there are few alkali-soluble resins with good plating resistance, and some alkali-soluble resins with good plating resistance have poor compatibility with other components, which will affect the development, adhesion and other properties of the photosensitive dry film resist. Therefore, it is an urgent technical problem to develop an alkali-soluble resin with good comprehensive performance. SUMMARY

[0005] In view of this, the purpose of the present application is to provide an alkali-soluble resin, a preparation method thereof and a photosensitive dry film resist.

[0006] In the first aspect, the present application provides an alkali-soluble resin, the structural formula of which is shown as formula I:

[0007]

[0008] Wherein, R1 is hydrogen atom or methyl; R2 is C0-C6 methylene; R3 is hydrogen or methyl; R4 is C1-C10 linear alkyl, branched alkyl, aromatic group; R5 is mono-fluorine or poly-fluorine substituted C1-C10 alkyl or aromatic group; R6 is hydrogen or methyl; a, b, c, d respectively represent the mass percentage of each polymer monomer, 15%≤a≤25%; 45%≤b≤55%; 15%≤c≤25%; 5%≤d≤15%, a+b+c+d=100%.

[0009] In a second aspect, the present application provides a preparation method of alkali-soluble resin, the synthetic route is as follows:

[0010]

[0011] The method comprises the following steps:

[0012] (1) monomer 1, monomer 2, monomer 3, monomer 4, the first part initiator and solvent are mixed to obtain solution A; the second part initiator is mixed with the solvent to obtain solution B; the solvent is added to the reactor and heated to the reaction temperature, then solution A is continuously fed into the reactor, after feeding, the reaction is set time, then solution B is added dropwise to the reaction solution, after dropwise addition, the temperature is increased to continue the reaction, to obtain a reaction solution containing primary alkali-soluble resin A;

[0013] (2) under ice bath condition, the solution containing NH2-R5 is added dropwise to the reaction solution containing primary alkali-soluble resin A, after dropwise addition, the temperature is increased to room temperature for reaction, to obtain a reaction solution containing intermediate alkali-soluble resin B;

[0014] (3) sodium acetate and acetic anhydride are added to the reaction solution containing intermediate alkali-soluble resin B, the temperature is increased to the set temperature for reaction, after reaction, separation and purification are carried out to obtain alkali-soluble resin.

[0015] In a third aspect, the present application provides a preparation method of alkali-soluble resin, the synthetic route is as follows:

[0016]

[0017] The method comprises the following steps:

[0018] (1) under ice bath condition, the solution containing NH2-R5 is added dropwise to the solution containing monomer 4, after dropwise addition, the temperature is increased to room temperature for first-stage reaction, after reaction, separation and purification are carried out to obtain intermediate 1; intermediate 1, sodium acetate and acetic anhydride are mixed, the temperature is increased to the set temperature for second-stage reaction, after separation and purification, monomer 5 is obtained;

[0019] (2) monomer 1, monomer 2, monomer 3, monomer 5, the first part of initiator and solvent are mixed to obtain solution A; the second part of initiator and solvent are mixed to obtain solution B; solvent is added into a reactor and heated to a reaction temperature, then solution A is continuously fed into the reactor, after solution A is completely fed, solution B is added dropwise into the reaction liquid after setting time, after heating to the set temperature, the reaction continues, after the reaction is completed, separation and purification are carried out to obtain the alkali-soluble resin.

[0020] In a fourth aspect, the present application provides a photosensitive dry film resist comprising the alkali-soluble resin described above.

[0021] In a fifth aspect, the present application provides an application of the photosensitive dry film resist in a printed circuit board, a lead frame or a semiconductor packaging substrate.

[0022] Compared with the prior art, one or more of the above technical solutions can achieve at least one of the following beneficial effects:

[0023] In the present application, the alkali-soluble resin contains a maleimide monomer, which can improve the rigidity and thermal stability of the entire molecular chain, thereby improving the heat resistance and mechanical strength of the entire alkali-soluble resin, i.e., the hardness, volume shrinkage, scratch resistance and wear resistance of the photosensitive dry film are improved, and the introduction of the imide ring can also endow the final photosensitive dry film with certain swelling resistance and strong acid and alkali resistance.

[0024] In the alkali-soluble resin of the present application, the polymaleic anhydride is modified into polymaleimide, and a fluorine-containing group is introduced into the N atom of the polymaleimide, which synergistically acts to effectively improve the plating resistance of the photosensitive dry film of the corresponding alkali-soluble resin, reducing the phenomenon of plating penetration or film shedding of the photosensitive dry film resist during use. The use of fluorine-substituted maleimide polymers can also improve the leveling property of the photosensitive dry film resist during coating, reduce the volume shrinkage rate of the dry film, and thus improve the yield of the photosensitive dry film. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 The Fourier transform infrared spectrograms of the primary alkali-soluble resin A and the alkali-soluble resin A1 prepared in Example 1 of the present application.

[0026] Figure 2 The nuclear magnetic resonance hydrogen spectrum of monomer 5 prepared in Example 4 of the present application.

[0027] Figure 3 The nuclear magnetic resonance carbon spectrum of monomer 5 prepared in Example 4 of the present application.

[0028] Figure 4 The Fourier transform infrared spectrograms of monomer 5 and the alkali-soluble resin A4 prepared in Example 4 of the present application. Detailed Implementation

[0029] To facilitate understanding of the present invention, the present invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of protection of the present invention is not limited to the following specific embodiments.

[0030] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the scope of the invention.

[0031] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.

[0032] As mentioned above, in a first aspect, the present invention provides an alkali-soluble resin with the structural formula shown in Formula I:

[0033]

[0034] Wherein, R1 is a hydrogen atom or a methyl group; R2 is a C0-C6 methylene group; R3 is hydrogen or a methyl group; R4 is a C1-C10 straight-chain alkyl group, a branched alkyl group, or an aromatic group; R5 is a monofluorinated or polyfluorinated substituted C1-C10 alkyl group or an aromatic group; R6 is hydrogen or a methyl group; a, b, c, and d represent the mass percentage content of the corresponding monomers, 15%≤a≤25%; 45%≤b≤55%; 15%≤c≤25%; 5%≤d≤15%, and a+b+c+d=100%.

[0035] Preferably, the alkali-soluble resin has a weight-average molecular weight of 40,000 to 100,000 g / mol and a molecular weight distribution of 1.2 to 4.0.

[0036] Preferably, R5 is a polyfluorinated C1-C10 alkyl group.

[0037] Preferably, the alkali-soluble resin is one or more of formulas (1) to (5):

[0038] .

[0039] Secondly, the present invention provides a method for preparing an alkali-soluble resin, the synthetic route of which is as follows:

[0040]

[0041] Includes the following steps:

[0042] (1) mixing monomer 1, monomer 2, monomer 3, monomer 4, the first part of initiator and solvent to obtain solution A; mixing the second part of initiator and solvent to obtain solution B; adding solvent into the reactor and heating to the reaction temperature, then continuously feeding solution A into the reactor, after feeding, setting the reaction time, then adding solution B into the reaction liquid drop by drop, after adding, heating to continue the reaction to obtain the reaction liquid containing primary base-soluble resin A;

[0043] (2) adding the solution containing NH2-R5 into the reaction liquid containing primary base-soluble resin A under ice bath condition, after adding, heating to room temperature to react, obtaining the reaction liquid containing intermediate base-soluble resin B;

[0044] (3) adding sodium acetate and acetic anhydride into the reaction liquid containing intermediate base-soluble resin B, heating to the set temperature to react, after reaction, separating and purifying to obtain base-soluble resin.

[0045] In the preparation method of the present application, maleic anhydride is introduced into the monomers of primary base-soluble resin A as a monomer, then N atom and fluorine-containing group are introduced through the reaction of anhydride and NH2-R5, and after ring closing, fluorine-containing polymaleinimide is obtained. Through experimental research, it is found that compared with the method of directly polymerizing fluorine-containing maleinimide (monomer 5) with monomer 1, monomer 2 and monomer 3, the comprehensive performance of the base-soluble resin prepared by the method will be further improved; this may be because the introduction of fluorine atom will enhance the polymerization activity of fluorine-containing maleinimide, so that the electron deficiency degree of the olefin of fluorine-containing maleinimide is intensified, while the olefin on monomer 3 is electron-rich structure, so that in the polymerization process, fluorine-containing maleinimide and monomer 3 will occur alternating polymerization, thereby affecting the performance of base-soluble resin such as plating resistance and adhesion.

[0046] Preferably, in step (1), the monomer 1 is one or more of acrylic acid, methacrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 3-methylbut-3-enoic acid and 4-methyl-4-pentenoic acid.

[0047] Preferably, in step (1), the monomer 2 is one or more of methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, t-butyl acrylate, butyl methacrylate, t-butyl methacrylate, n-octyl acrylate, isooctyl acrylate, n-octyl methacrylate, isooctyl methacrylate, benzyl acrylate and benzyl methacrylate.

[0048] Preferably, in step (1), the monomer 4 is one or both of maleic anhydride and citraconic anhydride.

[0049] Preferably, in step (1), the mass ratio of monomer 1, monomer 2 and monomer 3 is (15-25):(45-55):(15-25); including but not limited to: 15:55:25, 20:40:20, 25:45:15, 18:52:18, 22:48:17, 25:55:25, 15:45:15, 19:47:22, etc.

[0050] Preferably, in step (1) and step (2), the molar ratio of monomer 4 to NH2-R5 in step (2) is 1:(1.00-1.05); the mass ratio of monomer 3 to the total mass of monomer 4 and NH2-R5 is (15-25):(5.5-16.9), including but not limited to: 15:5.5, 20:5.5, 25:5.5, 15:11.2, 20:11.2, 25:11.2, 15:16.9, 20:16.9, 25:16.9, etc.

[0051] By controlling the mass percentage of each monomer, the alkali-soluble resin can have good photosensitivity, resolution, adhesion and other properties while effectively improving its anti-plating performance.

[0052] Preferably, in step (1), the first part of the initiator is 0.1-2% of the total mass of monomer 1, monomer 2, monomer 3 and monomer 4, including but not limited to: 0.1%, 0.5%, 1%, 1.5%, 2%, etc.; the second part of the initiator is 0.1-2% of the total mass of monomer 1, monomer 2, monomer 3 and monomer 4, including but not limited to: 0.1%, 0.5%, 1%, 1.5%, 2%, etc.

[0053] Preferably, in step (1), the first part of the initiator and the second part of the initiator are each independently one or more of azobisisobutyronitrile, azobisisoheptyl nitrile, dibenzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide.

[0054] Preferably, in step (1), the solvent is one or more of dichloromethane, trichloromethane, acetone, butanone, toluene, ethyl acetate, acetonitrile, dimethylbenzene, tetrahydrofuran, cyclohexanone, N’N-dimethylformamide, 1,4-dioxane, propylene glycol methyl ether acetate.

[0055] Preferably, in step (1), the reaction temperature is 60-80℃, including but not limited to: 60℃, 65℃, 70℃, 75℃, 80℃, etc.; solution A is controlled to be completed within 1-3h, including but not limited to: 1h, 1.5h, 2h, 2.5h, 3h, etc.; the setting time is 3-5h, including but not limited to: 3h, 3.5h, 4h, 4.5h, 5h, etc.; solution B is controlled to be completed within 15-45min (including but not limited to: 15min, 25min, 35min, 45min, etc.), and the temperature is raised to 70-90℃ (including but not limited to: 70℃, 75℃, 80℃, 85℃, 90℃, etc.) for continued reaction for 4-6h, including but not limited to: 4h, 4.5h, 5h, 5.5h, 6h, etc.

[0056] Preferably, in step (2), NH2-R5 is one or more of 4-fluoroaniline, 3-fluoroaniline, 2,2-difluoroethylamine, 2,2,2-trifluoroethylamine, 2,2,3,3,3-pentafluoropropylamine, 2,2,3,3,4,4,4-heptafluorobutylamine, 1H,1H-perfluoroheptylamine, p-trifluoromethylaniline, m-trifluoromethylaniline, 3-fluoro-4-trifluoromethylaniline.

[0057] Preferably, in step (2), the solvent used for the solution containing NH2-R5 is one or more of dichloromethane, trichloromethane, acetone, butanone, toluene, ethyl acetate, acetonitrile, dimethylbenzene, tetrahydrofuran, cyclohexanone, N'N-dimethylformamide, 1,4-dioxane, propylene glycol methyl ether acetate.

[0058] Preferably, in step (2), the reaction time is 12-24h, including but not limited to: 12h, 13h, 5h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, etc.

[0059] Preferably, in step (3), the amount of sodium acetate added is 1-14% of the mass of the intermediate base-soluble resin B in step (2), including but not limited to: 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, etc.; the amount of acetic anhydride added is 0.5-5 times the mass of the intermediate base-soluble resin B in step (2), including but not limited to: 0.5 times, 1 times, 1.5 times, 2 times, 2.5 times, 3 times, 3.5 times, 4 times, 4.5 times, 5 times, etc.

[0060] Preferably, in step (3), the temperature is set to 80-120℃, including but not limited to: 80℃, 90℃, 100℃, 110℃, 120℃, etc.; the reaction time is 12-24h, including but not limited to: 12h, 13h, 5h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, etc.

[0061] In a third aspect, the present application provides a preparation method of the alkali-soluble resin, and the synthesis route is as follows:

[0062]

[0063] including the following steps:

[0064] (1) under ice bath conditions, a solution containing monomer 4 is added dropwise with a solution containing NH2-R5, after the dropwise addition is completed, the temperature is raised to room temperature for the first stage reaction, after the reaction is completed, the intermediate 1 is obtained after separation and purification; intermediate 1, sodium acetate and acetic anhydride are mixed, and then heated to a set temperature for the second stage reaction, and then separated and purified to obtain monomer 5;

[0065] (2) monomer 1, monomer 2, monomer 3, monomer 5, the first part of the initiator and the solvent are mixed to obtain solution A; the second part of the initiator and the solvent are mixed to obtain solution B; the solvent is added to the reactor and heated to the reaction temperature, then solution A is continuously fed into the reactor, after solution A is completely fed, solution B is added dropwise to the reaction solution after the reaction is set for a certain time, then heated to a set temperature for continuous reaction, after the reaction is completed, the alkali-soluble resin is obtained after separation and purification.

[0066] Preferably, in step (1), the monomer 4 is one or both of maleic anhydride and citraconic anhydride.

[0067] Preferably, in step (1), the NH2-R5 is one or more of 4-fluoroaniline, 3-fluoroaniline, 2,2-difluoroethylamine, 2,2,2-trifluoroethylamine, 2,2,3,3,3-pentafluoropropylamine, 2,2,3,3,4,4,4-heptafluorobutylamine, 1H,1H-perfluoroheptylamine, p-trifluoromethylaniline, m-trifluoromethylaniline, 3-fluoro-4-trifluoromethylaniline.

[0068] Preferably, in step (1), the molar ratio of monomer 4 to NH2-R5 is 1: (1.00-1.05); the amount of sodium acetate added is 50-80% of the mass of intermediate 1, including but not limited to: 50%, 55%, 60%, 65%, 70%, 75%, 80%, etc.; the amount of acetic anhydride added is 10-20 times the mass of intermediate 1, including but not limited to: 10 times, 11 times, 12 times, 13 times, 14 times, 15 times, 16 times, 17 times, 18 times, 19 times, 20 times, etc.

[0069] Preferably, in step (1), the first-stage reaction time is 8-16 h, including but not limited to: 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 5 h, 14 h, 15 h, 16 h, etc.; the set temperature is 80-120°C, including but not limited to: 80°C, 90°C, 100°C, 110°C, 120°C, etc.; the second-stage reaction time is 6-12 h, including but not limited to: 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, etc.

[0070] Preferably, in step (2), the monomer 1 is one or more of acrylic acid, methacrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 3-methylbut-3-enoic acid, and 4-methyl-4-pentenoic acid.

[0071] Preferably, in step (2), the monomer 2 is one or more of methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, tert-butyl acrylate, butyl methacrylate, tert-butyl methacrylate, n-octyl acrylate, isooctyl acrylate, n-octyl methacrylate, isooctyl methacrylate, benzyl acrylate, and benzyl methacrylate.

[0072] Preferably, in step (2), the mass ratio of monomer 1, monomer 2, monomer 3, and monomer 5 is 15-25:45-55:15-25:5-15, including but not limited to: 15:55:20:10, 20:50:15:15, 25:45:25:5, 22:48:22:8, 19:52:20:9, 18:49:22:11, etc.; the first portion of initiator is 0.1-2% of the total mass of monomer 1, monomer 2, monomer 3, and monomer 5, including but not limited to: 0.1%, 0.5%, 1%, 1.5%, 2%, etc.; the second portion of initiator is 0.1-2% of the total mass of monomer 1, monomer 2, monomer 3, and monomer 5, including but not limited to: 0.1%, 0.5%, 1%, 1.5%, 2%, etc.

[0073] Preferably, in step (2), the first portion of initiator and the second portion of initiator are each independently one or more of azobisisobutyronitrile, azobisisoheptyl nitrile, dibenzoyl peroxide, tert-butyl peroxybenzoate, and di-tert-butyl peroxide.

[0074] Preferably, in step (2), the reaction temperature is 60-80℃, including but not limited to: 60℃, 65℃, 70℃, 75℃, 80℃, etc.; solution A is controlled to be completed within 1-3h, including but not limited to: 1h, 1.5h, 2h, 2.5h, 3h, etc.; the setting time is 3-5h, including but not limited to: 3h, 3.5h, 4h, 4.5h, 5h, etc.; solution B is controlled to be completed within 15-45min (including but not limited to: 15min, 25min, 35min, 45min, etc.), the setting temperature is 70-90℃ (including but not limited to: 70℃, 75℃, 80℃, 85℃, 90℃, etc.), and the continuous reaction time is 4-6h, including but not limited to: 4h, 4.5h, 5h, 5.5h, 6h, etc.

[0075] In a fourth aspect, the present application provides a photosensitive dry film resist, comprising the aforementioned alkali-soluble resin.

[0076] Preferably, the photosensitive dry film resist comprises, in terms of mass fraction:

[0077] The alkali-soluble resin is 42-65 parts, including but not limited to: 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, etc.

[0078] The photopolymerization monomer is 21-48 parts, including but not limited to: 21 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts, etc.

[0079] The photoinitiator is 0.1-5 parts, including but not limited to: 0.1 parts, 0.5 parts, 1 parts, 2 parts, 3 parts, 4 parts, 5 parts, etc.

[0080] The auxiliary agent is 0.1-5 parts, including but not limited to: 0.1 parts, 0.5 parts, 1 parts, 2 parts, 3 parts, 4 parts, 5 parts, etc.

[0081] Preferably, the photopolymerization monomer is one or more of 1,6-hexanediol acrylate, tripropyleneglycol diacrylate, ethoxylated bisphenol A diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, glyceryl triacrylate propoxylate, ethoxylated trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate.

[0082] Preferably, the photoinitiator is one or more of anthraquinone, benzophenone, benzoin, acridine, oxime ester, and hexaarylbiimidazole photoinitiators.

[0083] Preferably, the adjuvant includes one or more of a leveling agent, a defoaming agent, a dye, an adhesion additive, a color changing agent, a fluorescent agent, a polymerization inhibitor, an antioxidant, a plasticizer, a dispersant.

[0084] In a fifth aspect, the present application provides a photosensitive dry film resist for use in a printed circuit board, a lead frame or a semiconductor package substrate.

[0085] Example 1

[0086] The structural formula of the alkali-soluble resin A1 in this example is as follows:

[0087]

[0088] wherein: a, b, c and d represent the mass percentage content of the corresponding polymerized monomers, wherein a = 20%, b = 50%, c = 20%, d = 10%.

[0089] The specific synthesis route is as follows:

[0090]

[0091] The specific preparation method comprises the following steps:

[0092] S1: 20 g of methacrylic acid, 50 g of methyl methacrylate, 20 g of styrene, 5.48 g of maleic anhydride, 0.5 g of AIBN and 80 g of butanone are mixed to obtain solution A; 0.5 g of AIBN is mixed with 22 g of butanone to obtain solution B; 20 g of butanone is added to a reactor and heated to 70°C, then solution A is continuously fed into the reactor, and the time is controlled for 2 h; after solution A is completely fed, the reaction is continued for 4 h, then solution B is added dropwise to the reaction solution, and the time is controlled for 30 min; after the dropwise addition is completed, the temperature is raised to 80°C and the reaction is continued for 4 h to obtain a reaction solution containing a primary alkali-soluble resin A;

[0093] S2: Under the condition of ice bath at 0°C, 50.00 g of a butanone solution containing 5.64 g of 2,2,2-trifluoroethylamine is added dropwise to the reaction solution containing the primary alkali-soluble resin A obtained in step S1, and after the dropwise addition is completed, the temperature is raised to room temperature and the reaction is continued for 18 h to obtain a reaction solution containing an intermediate alkali-soluble resin B;

[0094] S3: 7.33 g of sodium acetate and 164.16 g of acetic anhydride are added to the reaction solution containing the intermediate alkali-soluble resin B in step S2, and the temperature is raised to 100°C and the reaction is continued for 18 h; after the reaction is completed, separation and purification are carried out to obtain the alkali-soluble resin A1.

[0095] The weight average molecular weight of the alkali-soluble resin A1 prepared in this example is 61500 g / mol, and the molecular weight distribution is 1.68.

[0096] The primary alkali-soluble resin A and the alkali-soluble resin A1 prepared in this example were subjected to Fourier transform infrared spectroscopy test, and the results can be seen in Figure 1 . It can be seen that in the curve of the primary alkali-soluble resin A, the wide peak at 3277 cm -1 is the stretching vibration peak of O-H on polymethacrylic acid, the peaks at 1857 cm -1 and 1785 cm -1 are the stretching vibration peaks of C=O on polymaleic anhydride, the peak at 1732 cm -1 is the stretching vibration peak of C=O on polymethacrylic acid and polymethyl methacrylate, the peaks at 1273-1148 cm -1 are the stretching vibration peaks of C-O on polymethacrylic acid and polymethyl methacrylate, and the stretching vibration peaks of C-O-C on polymaleic anhydride and polymethyl methacrylate, the peaks at 759 cm -1 and 706 cm -1 are the bending vibration peaks of C-H on polystyrene, indicating that the primary alkali-soluble resin A is successfully prepared; in the curve of the alkali-soluble resin A1, the peaks at 1857 cm -1 and 1785 cm -1 on polymaleic anhydride disappear, the stretching vibration peak of C=O on polymaleimide moves to 1724 cm -1 and combines with the stretching vibration peak of C=O on polymethacrylic acid and polymethyl methacrylate, multiple C-F stretching vibration peaks appear at 1400-1100 cm -1 , proving that the alkali-soluble resin A1 is successfully prepared.

[0097] Example 2

[0098] The structural formula of the alkali-soluble resin A2 in this example is:

[0099]

[0100] wherein a, b, c and d represent the mass percentage content of the corresponding polymerized monomers, wherein a = 20%, b = 55%, c = 20%, and d = 5%.

[0101] The synthesis route is basically the same as in Example 1; the specific steps are as follows:

[0102] S1: 20 g of methacrylic acid, 55 g of methyl methacrylate, 20 g of styrene, 2.74 g of maleic anhydride, 0.5 g of AIBN and 80 g of butanone were mixed to obtain solution A; 0.5 g of AIBN and 22 g of butanone were mixed to obtain solution B; 20 g of butanone was added to a reactor, and the temperature was raised to 70°C, then solution A was continuously fed into the reactor, and the time was controlled for 2 h; after solution A was completely fed, the reaction was continued for 4 h, then solution B was added dropwise to the reaction solution, and the time was controlled for 30 min, after the dropwise addition was completed, the temperature was raised to 80°C, and the reaction was continued for 4 h to obtain a reaction solution containing primary base-soluble resin A;

[0103] S2: 50.00 g of a butanone solution containing 2.82 g of 2,2,2-trifluoroethylamine was added dropwise to the reaction solution of the primary base-soluble resin A under ice bath at 0°C, and the temperature was raised to room temperature for reaction for 18 h to obtain a reaction solution containing intermediate base-soluble resin B;

[0104] S3: 3.66 g of sodium acetate and 82.08 g of acetic anhydride were added to the reaction solution of the intermediate base-soluble resin B, and the temperature was raised to 100°C for reaction for 18 h; after the reaction was completed, separation and purification were performed to obtain base-soluble resin A2.

[0105] The weight average molecular weight of the base-soluble resin A2 prepared in this example was 67200 g / mol, and the molecular weight distribution was 1.65.

[0106] Example 3

[0107] The structural formula of the base-soluble resin A3 in this example is:

[0108]

[0109] Wherein: a, b, c and d represent the mass percentage content of the corresponding polymerized monomers, wherein a = 20%, b = 45%, c = 20%, and d = 15%.

[0110] The synthesis route is basically the same as that of Example 1; the specific steps are as follows:

[0111] S1: 20 g of methacrylic acid, 55 g of methyl methacrylate, 20 g of styrene, 2.74 g of maleic anhydride, 0.5 g of AIBN and 80 g of butanone were mixed to obtain solution A; 0.5 g of AIBN and 22 g of butanone were mixed to obtain solution B; 20 g of butanone was added to a reactor, and the temperature was raised to 70°C, then solution A was continuously fed into the reactor, and the time was controlled for 2 h; after solution A was completely fed, the reaction was continued for 4 h, then solution B was added dropwise to the reaction solution, and the time was controlled for 30 min, after the dropwise addition was completed, the temperature was raised to 80°C, and the reaction was continued for 4 h to obtain a reaction solution containing primary base-soluble resin A;

[0112] S2: Under the condition of ice bath 0℃, 50.00 g of butanone solution containing 8.46 g of 2, 2, 2-trifluoroethylamine was added dropwise into the reaction solution of primary base-soluble resin A, and after the dropwise addition was completed, the reaction was carried out at room temperature for 18 h to obtain a reaction solution containing intermediate base-soluble resin B;

[0113] S3: 10.99 g of sodium acetate and 246.25 g of acetic anhydride were added into the reaction solution of intermediate base-soluble resin B, and the temperature was raised to 100℃ for reaction for 18 h; after the reaction was completed, separation and purification were carried out to obtain base-soluble resin A3.

[0114] The weight average molecular weight of the base-soluble resin A3 prepared in this example was 58400 g / mol, and the molecular weight distribution was 1.81.

[0115] Example 4

[0116] The structural formula of the base-soluble resin A4 in this example is as follows:

[0117]

[0118] Wherein: a, b, c and d represent the mass percentage content of the corresponding polymerized monomers, wherein a = 20%, b = 50%, c = 20%, d = 10%.

[0119] The specific synthesis route is as follows:

[0120]

[0121] The method comprises the following steps:

[0122] S1: Under the condition of ice bath 0℃, 50.00 g of butanone solution containing 8.46 g of 2, 2, 2-trifluoroethylamine was added dropwise into the reaction solution of primary base-soluble resin A, and after the dropwise addition was completed, the reaction was carried out at room temperature for 18 h to obtain a reaction solution containing intermediate base-soluble resin B;

[0123] S2: 20 g of methyl methacrylate, 50 g of methyl methacrylate, 20 g of styrene, 10 g of monomer 5, 0.5 g of AIBN and 80 g of butanone were mixed to obtain solution A; 0.5 g of AIBN was mixed with 22 g of butanone to obtain solution B; 20 g of butanone was added into a reactor, and the temperature was raised to 70℃, then solution A was continuously introduced into the reactor, and the time was controlled for 2 h; after the complete introduction of solution A, the reaction was continued for 4 h; solution B was added dropwise into the reaction solution, and the time was controlled for 30 min; after the dropwise addition was completed, the temperature was raised to 80℃, and the reaction was continued for 4 h; after the reaction was completed, a base-soluble resin A4 was obtained.

[0124] The weight average molecular weight of the alkali-soluble resin A4 prepared in this example was 75300 g / mol, and the molecular weight distribution was 2.02.

[0125] The monomer 5 prepared in this example was subjected to hydrogen nuclear magnetic resonance spectrum test, and the result can be seen from Figure 2 . 1 H NMR (400MHz, CDCl3) delta 6.85 (s, 2H), 4.14 (q, J = 8 Hz, 2H).

[0126] The monomer 5 prepared in this example was subjected to carbon nuclear magnetic resonance spectrum test, and the result can be seen from Figure 3 . 13 C NMR (100MHz, CDCl3) delta 168.83, 134.56, 122.98 (q, 1 J FC = 278 Hz), 38.66 (q, 2 J FC = 37 Hz).

[0127] The monomer 5, the alkali-soluble resin A4 prepared in this example were subjected to Fourier transform infrared spectrum test, and the result can be seen from Figure 4 . It can be seen that: in the curve of monomer 5, 3500~3000 cm -1 is the stretching vibration peak of C-H, 1719 cm -1 is the stretching vibration peak of C=O, 1612 cm -1 and 1584 cm -1 are the stretching vibration peaks of C=C, 1500~1100 cm -1 are the stretching vibration peaks of-CF3 and C-N, combined with the hydrogen nuclear magnetic resonance spectrum and the carbon nuclear magnetic resonance spectrum of monomer 5, it is indicated that the monomer 5 is successfully prepared; in the curve of the alkali-soluble resin A4, the wide peak at 3279 cm -1 is the stretching vibration peak of O-H on the polymethacrylic acid, the stretching vibration peak of C-H at 3100~2800 cm -1 is enhanced and widened, the stretching vibration peak of C=O at 1725 cm -1 is enhanced and widened, the peak at 1500~1100 cm -1 is enhanced and widened, which is caused by the stretching vibration of C-O on the newly added polymethacrylic acid and polymethyl methacrylate, and the stretching vibration of the aromatic ring on the polystyrene, 760 cm -1 and 705 cm -1The peak at 3060 cm-1 is the C-H bending vibration peak on polystyrene, which proves that the alkali-soluble resin A4 is successfully prepared.

[0128] Example 5

[0129] The structural formula of the alkali-soluble resin A5 prepared in this example is as follows:

[0130]

[0131] Wherein: a, b, c and d represent the mass percentage of the corresponding polymerized monomers, wherein a = 18%, b = 45%, c = 25%, d = 12%.

[0132] The specific synthesis route is as follows:

[0133]

[0134] The specific preparation method comprises the following steps:

[0135] S1: 18 g of 3-butenoic acid, 45 g of ethyl acrylate, 25 g of styrene, 6.57 g of maleic anhydride, 0.5 g of AIBN and 80 g of butanone are mixed to obtain solution A; 0.5 g of AIBN is mixed with 22 g of butanone to obtain solution B; 20 g of butanone is added to a reactor and heated to 70°C, then solution A is continuously introduced into the reactor, and the time is controlled for 2 h; after solution A is completely introduced, the reaction is continued for 4 h, then solution B is added dropwise to the reaction solution, and the time is controlled for 30 min; after the dropwise addition is completed, the temperature is raised to 80°C and the reaction is continued for 4 h to obtain a reaction solution containing the primary alkali-soluble resin A;

[0136] S2: Under the condition of ice bath at 0°C, 50.00 g of butanone solution containing 6.77 g of 2, 2, 2-trifluoroethylamine is added dropwise to the reaction solution containing the primary alkali-soluble resin A obtained in step S1, and after the dropwise addition is completed, the temperature is raised to room temperature and the reaction is continued for 18 h to obtain a reaction solution containing the intermediate alkali-soluble resin B;

[0137] S3: 8.79 g of sodium acetate and 197.00 g of acetic anhydride are added to the reaction solution containing the intermediate alkali-soluble resin B in step S2, and the temperature is raised to 100°C and the reaction is continued for 18 h; after the reaction is completed, separation and purification are carried out to obtain the alkali-soluble resin A5.

[0138] The weight average molecular weight of the alkali-soluble resin A5 prepared in this example is 60900 g / mol, and the molecular weight distribution is 1.88.

[0139] Example 6

[0140] The structural formula of the alkali-soluble resin A6 prepared in this example is as follows:

[0141]

[0142] wherein: a, b, c and d represent the mass percentage content of the corresponding polymerized monomers, wherein a = 25%, b = 52%, c = 15%, d = 8%. The specific synthesis route is as follows:

[0143]

[0144] The specific preparation method comprises the following steps:

[0145] S1: 25 g of acrylic acid, 52 g of butyl methacrylate, 15 g of styrene, 4.64 g of citraconic anhydride, 0.5 g of AIBN and 80 g of butanone were mixed to obtain solution A; 0.5 g of AIBN was mixed with 22 g of butanone to obtain solution B; 20 g of butanone was added to a reactor and heated to 70°C, then solution A was continuously introduced into the reactor, and the time was controlled for 2 h; after solution A was completely introduced, the reaction was continued for 4 h, then solution B was added dropwise to the reaction solution, and the time was controlled for 30 min; after the dropwise addition was completed, the temperature was increased to 80°C and the reaction was continued for 4 h to obtain a reaction solution containing a primary base-soluble resin A;

[0146] S2: Under the condition of ice bath 0°C, 50.00 g of butanone solution containing 4.19 g of 2,2,2-trifluoroethylamine was added dropwise to the reaction solution containing the primary base-soluble resin A obtained in step S1, and after the dropwise addition was completed, the temperature was increased to room temperature and the reaction was continued for 18 h to obtain a reaction solution containing an intermediate base-soluble resin B;

[0147] S3: 5.44 g of sodium acetate and 121.79 g of acetic anhydride were added to the reaction solution containing the intermediate base-soluble resin B in step S2, and the temperature was increased to 100°C and the reaction was continued for 18 h; after the reaction was completed, separation and purification were carried out to obtain a base-soluble resin A6.

[0148] The weight average molecular weight of the base-soluble resin A6 prepared in this example is 68100 g / mol, and the molecular weight distribution is 1.63.

[0149] Example 7

[0150] The structural formula of the base-soluble resin A7 in this example is:

[0151]

[0152] wherein: a, b, c and d represent the mass percentage content of the corresponding polymerized monomers, wherein a = 15%, b = 48%, c = 24%, d = 13%.

[0153] The specific synthesis route is as follows:

[0154]

[0155] The specific preparation method comprises the following steps:

[0156] S1: 18 g of 5-hexenoic acid, 45 g of isooctyl methacrylate, 25 g of styrene, 5.56 g of maleic anhydride, 0.5 g of AIBN and 80 g of butanone were mixed to obtain solution A; 0.5 g of AIBN and 22 g of butanone were mixed to obtain solution B; 20 g of butanone was added to a reactor and heated to 70°C, then solution A was continuously fed into the reactor for 2 h; after solution A was completely fed, the reaction was continued for 4 h, then solution B was added dropwise into the reaction solution for 30 min, after the dropwise addition was completed, the temperature was raised to 80°C and the reaction was continued for 4 h to obtain a reaction solution containing primary base-soluble resin A;

[0157] S2: 50.00 g of a butanone solution containing 8.63 g of 2,2,3,3,3-pentafluoropropylamine was added dropwise into the reaction solution containing primary base-soluble resin A obtained in step S1 under ice bath at 0°C, after the dropwise addition was completed, the temperature was raised to room temperature and the reaction was continued for 18 h to obtain a reaction solution containing intermediate base-soluble resin B;

[0158] S3: 7.45 g of sodium acetate and 166.83 g of acetic anhydride were added to the reaction solution containing intermediate base-soluble resin B in step S2, and the temperature was raised to 100°C and the reaction was continued for 18 h; after the reaction was completed, separation and purification were performed to obtain base-soluble resin A7.

[0159] The weight average molecular weight of the base-soluble resin A7 prepared in this example was 53700 g / mol, and the molecular weight distribution was 1.85.

[0160] Example 8

[0161] The structural formula of the base-soluble resin A8 in this example is:

[0162]

[0163] wherein: a, b, c and d represent the mass percentage content of the corresponding polymerized monomers, wherein a = 23%, b = 47%, c = 15%, d = 15%.

[0164] The specific synthesis route is as follows:

[0165]

[0166] The specific preparation method comprises the following steps:

[0167] S1: 23 g of methacrylic acid, 47 g of benzyl methacrylate, 15 g of styrene, 5.27 g of maleic anhydride, 0.5 g of AIBN and 80 g of butanone were mixed to obtain solution A; 0.5 g of AIBN and 22 g of butanone were mixed to obtain solution B; 20 g of butanone was added to a reactor and heated to 70°C, then solution A was continuously fed into the reactor for 2 h; after solution A was completely fed, the reaction was continued for 4 h, then solution B was added dropwise to the reaction solution for 30 min, after the dropwise addition was completed, the temperature was raised to 80°C and the reaction was continued for 4 h to obtain a reaction solution containing primary base-soluble resin A;

[0168] S2: 50.00 g of a butanone solution containing 10.91 g of 2,2,3,3,4,4,4-heptafluorobutylamine was added dropwise to the reaction solution containing primary base-soluble resin A obtained in step S1 under ice bath at 0°C, after the dropwise addition was completed, the temperature was raised to room temperature and the reaction was continued for 18 h to obtain a reaction solution containing intermediate base-soluble resin B;

[0169] S3: 7.05 g of sodium acetate and 158.01 g of acetic anhydride were added to the reaction solution containing intermediate base-soluble resin B in step S2, and the temperature was raised to 100°C and reacted for 18 h; after the reaction was completed, separation and purification were carried out to obtain base-soluble resin A8.

[0170] The weight average molecular weight of the base-soluble resin A8 prepared in this example is 69800 g / mol, and the molecular weight distribution is 1.69.

[0171] Comparative Example 1

[0172] The chemical formula of the base-soluble resin A9 prepared in this comparative example is as follows:

[0173]

[0174] wherein a1, a2, b, c and d represent the mass percentage content of the corresponding polymerized monomers, wherein a1 = 16.76%, a2 = 7.82%, b = 50%, c = 20%, d = 5.42%.

[0175] The synthesis route is as follows:

[0176]

[0177] comprising the following steps:

[0178] A solution A was prepared by mixing 16.76 g of methacrylic acid, 7.82 g of 2-(trifluoromethyl)acrylic acid, 50 g of methyl methacrylate, 20 g of styrene, 5.42 g of maleimide, 0.5 g of AIBN and 80 g of butanone; a solution B was prepared by mixing 0.5 g of AIBN and 22 g of butanone; 20 g of butanone was added to a reactor and heated to 70°C, then the solution A was continuously fed into the reactor, and the feeding time was controlled to be 2 h; after the solution A was completely fed, the reaction was continued for 4 h, then the solution B was added dropwise into the reaction solution, and the dropping time was controlled to be 30 min; after the dropping was completed, the temperature was increased to 80°C and the reaction was continued for 4 h to obtain the alkali-soluble resin A9.

[0179] The weight average molecular weight of the alkali-soluble resin A9 prepared in the present comparative example was 60300 g / mol, and the molecular weight distribution was 1.78.

[0180] Comparative Example 2

[0181] The chemical formula of the alkali-soluble resin A10 prepared in the present comparative example is as follows:

[0182]

[0183] wherein a, b, c and d represent the mass percentage content of the corresponding polymerized monomers, wherein a = 20%, b1 = 45.19%, b2 = 9.39%, c = 20%, d = 5.42%.

[0184] The synthetic route is as follows:

[0185]

[0186] comprising the following steps:

[0187] A solution A was prepared by mixing 20 g of methacrylic acid, 45.19 g of methyl methacrylate, 9.39 g of trifluoroethyl methacrylate, 20 g of styrene, 5.42 g of maleimide, 0.5 g of AIBN and 80 g of butanone; a solution B was prepared by mixing 0.5 g of AIBN and 22 g of butanone; 20 g of butanone was added to a reactor and heated to 70°C, then the solution A was continuously fed into the reactor, and the feeding time was controlled to be 2 h; after the solution A was completely fed, the reaction was continued for 4 h, then the solution B was added dropwise into the reaction solution, and the dropping time was controlled to be 30 min; after the dropping was completed, the temperature was increased to 80°C and the reaction was continued for 4 h to obtain the alkali-soluble resin A10.

[0188] The weight average molecular weight of the alkali-soluble resin A10 prepared in the present comparative example was 62100 g / mol, and the molecular weight distribution was 1.76.

[0189] Comparative Example 3

[0190] The chemical formula of the base-soluble resin A11 prepared in the present comparative example is as follows:

[0191]

[0192] wherein: a, b, c and d represent the mass percentage content of the corresponding polymerized monomers, wherein a = 20%, b = 50%, c1 = 14.96%, c2 = 9.62%, d = 5.42%.

[0193] The synthetic route is as follows:

[0194]

[0195] The steps include:

[0196] After mixing 20 g of methacrylic acid, 50 g of methyl methacrylate, 14.96 g of styrene, 9.62 g of p-trifluoromethyl styrene, 5.42 g of maleimide, 0.5 g of AIBN and 80 g of butanone, solution A is obtained; 0.5 g of AIBN is mixed with 22 g of butanone to obtain solution B; 20 g of butanone is added to the reactor and heated to 70°C, then solution A is continuously fed into the reactor, and the feeding time is controlled for 2 h; after the feeding of solution A is completed, the reaction is continued for 4 h, then solution B is added dropwise to the reaction solution, the dropping time is controlled for 30 min, after the dropping is completed, the temperature is raised to 80°C and the reaction is continued for 4 h to obtain the base-soluble resin A11.

[0197] The weight average molecular weight of the base-soluble resin A11 prepared in the present comparative example is 59400 g / mol, and the molecular weight distribution is 1.82.

[0198] Examples 9-16 and Comparative Examples 4-6

[0199] The composition of the photosensitive dry film resist of Examples 9-16 and Comparative Examples 4-6 can be seen in Table 1.

[0200] Table 1

[0201]

[0202] The photopolymerizable monomer B is composed of the following components: methoxypolyethylene glycol (350) monoacrylate 5 parts, 10 (ethoxyl) bisphenol A dimethacrylate 20 parts, 6 (propoxyl) bisphenol A dimethacrylate 5 parts, 3 (ethoxyl) trimethylolpropane triacrylate 10 parts, di (trimethylolpropane) tetraacrylate 4 parts.

[0203] The photoinitiator C is 2,2'-bis (o-chlorophenyl) -4,4', 5, 5'-tetraphenyl- bisimidazole (BCIM).

[0204] The auxiliary D consists of the following ingredients: leuco crystal violet 0.5 parts, malachite green 0.05 parts, p-toluenesulfonamide 0.8 parts, 2,6-di-tert-butyl-4-methylphenol 0.03 parts.

[0205] Alkali-soluble resin A:

[0206] A1 is the alkali-soluble resin of Example 1

[0207] A2 is the alkali-soluble resin of Example 2

[0208] A3 is the alkali-soluble resin of Example 3

[0209] A4 is the alkali-soluble resin of Example 4

[0210] A5 is the alkali-soluble resin of Example 5

[0211] A6 is the alkali-soluble resin of Example 6

[0212] A7 is the alkali-soluble resin of Example 7

[0213] A8 is the alkali-soluble resin of Example 8

[0214] A9 is the alkali-soluble resin of Comparative Example 1

[0215] A10 is the alkali-soluble resin of Comparative Example 2

[0216] A11 is the alkali-soluble resin of Comparative Example 3

[0217] The solvent consists of the following ingredients: acetone 8 parts, toluene 10 parts, methanol 5 parts.

[0218] The sample preparation method (including the preparation of the photosensitive dry film, film lamination, exposure, development), sample evaluation method, and evaluation results of Examples 9 to 16 and Comparative Examples 4 to 6 are described below.

[0219] (1) Sample preparation method

[0220]

Preparation of photosensitive dry film

[0221] The materials of Examples 1 to 8 and Comparative Examples 1 to 3 listed in Table 1 were mixed uniformly, respectively, to prepare a photosensitive resin composition. Subsequently, it was coated on the surface of a 15 μm thick PET support film using a coater (model: AB4220, manufactured by TQC, Netherlands). After baking at 80°C for 10 minutes, a photosensitive layer with a thickness of 38 μm was obtained. Finally, a PE film was covered on the surface of the photosensitive layer for protection, and the preparation of the photosensitive dry film was completed.

[0222]

Film lamination

[0223] A copper substrate on which a 35-μm-thick rolled 1.2-mm-thick copper foil was laminated was subjected to surface treatment such as polishing, micro-etching, water washing, and drying, and then preheated to 80°C. After the PE protective film on the surface of the photosensitive dry film obtained in the above examples and comparative examples was removed, the photosensitive resin composition was laminated on the copper substrate at a pressure roller temperature of 110°C, an air pressure of 0.35 MPa, and a lamination speed of 1.5 m / min to obtain a laminated sample.

[0224] [Exposure]

[0225] The laminated sample was left to stand for 20 min, and then exposed using an exposure machine (model: MAS 04L10 8, Chiptronics, main wavelength 405 nm). The photosensitivity was evaluated by the number of remaining segments of a Stouffer 41-stage exposure scale after exposure. The number of exposure segments was controlled to be 18 22.

[0226] [Development]

[0227] The sample after exposure was left to stand for 20 min or more, and then the PET support film was peeled off. The sample was developed using an alkali developing machine (manufactured by Guangzhou Julong Printing Plate Equipment Co., Ltd.). A 1 wt% Na2CO3 aqueous solution at 30°C was sprayed for a time twice the minimum development time. After development, the sample was washed with water and dried to obtain a substrate having a cured film for evaluation. The minimum development time was the shortest time required for the unexposed resist layer to be completely washed away in the development tank.

[0228] (2) Evaluation method

[0229] [Photosensitivity evaluation]

[0230] The photosensitivity was evaluated by the number of remaining segments of a Stouffer 41-stage exposure scale after exposure. The sample after the exposure process was left to stand for 20 min or more, and then the PET film layer was peeled off. A 1.0 wt% sodium carbonate aqueous solution at 30°C was sprayed to remove the unexposed resist layer. The development time was twice the minimum development time. After the above operation, a cured film obtained by curing the photosensitive resin composition was formed on the surface of the substrate. The photosensitivity of the photosensitive resin composition was evaluated by the exposure energy (mJ / cm 2 ) at which the number of remaining segments of the stage exposure scale obtained by the cured film was 20 segments. The smaller the value, the better the photosensitivity.

[0231] Judgment basis:

[0232] O: 70-90 mJ / cm 2 ;

[0233] Δ: 90-110 mJ / cm 2 ;

[0234] X: > 110 mJ / cm 2 .

[0235] Evaluation of resolution

[0236] On the above-mentioned post-laminating test substrate, exposure was performed using photomask data having a wiring pattern with a line width / interval width of n:n (unit: μm) at an energy such that the number of remaining stages after development of a Stouffer 41-stage exposure ruler reached 20. After the development process, the resist pattern was observed using an optical microscope, and the value of the minimum line width at which a complete cured resist line was formed was used as the value of the adhesion (μm) to evaluate the adhesion. The smaller this value, the better the resolution.

[0237] Evaluation of adhesion

[0238] On the above-mentioned post-laminating test substrate, exposure was performed using photomask data having a wiring pattern with a line width / interval width of n:400 (unit: μm) at an energy such that the number of remaining stages after development of a Stouffer 41-stage exposure ruler reached 20. After the development process, the resist pattern was observed using an optical microscope, and the value of the minimum line width at which a complete cured resist line was formed was used as the value of the adhesion (μm) to evaluate the adhesion. The smaller this value, the better the adhesion.

[0239] Evaluation of plating resistance

[0240] On the above-mentioned post-laminating test substrate, exposure was performed using photomask data having a wiring pattern with a line width / interval width of 1 / 1 ~ 6 / 6 (unit: mil) at an energy such that the number of remaining stages after development of a Stouffer 41-stage exposure ruler reached 20. After the development process, copper plating pretreatment was performed in the order of immersion in 10% degreasing solution for 10 min (40°C) → water washing for 1 min → microetching in 4% sodium thiosulfate solution for 1 min → 10% dilute sulfuric acid washing for 1 min, and then immersion in a copper plating solution was performed at room temperature at 3.0 A / dm 2 for 30 min. After that, tin plating pretreatment was performed in the order of water washing → delamination in 3.0% sodium hydroxide solution (55°C) → water washing → drying treatment. In addition, after the resist was peeled, whether or not copper plating had penetrated was observed from above using an optical microscope, a section was prepared, and whether or not plating had penetrated was confirmed using a scanning electron microscope (manufactured by Hitachi), model SU1000. 2

[0241] Criteria for judgment: ​

[0242] O: no plating penetration phenomenon;

[0243] Δ: slight plating penetration phenomenon;

[0244] X: serious plating penetration phenomenon.

[0245] [Assessment of plating contamination]

[0246] The dry film resist sample after exposure (20 segments of the stage exposure ruler remained) was immersed in a copper sulfate plating solution at a ratio of 0.8 m 2 / L at room temperature for 24 h, and the dry film resist was filtered out to obtain the sample to be tested. The organic carbon content (TOC) of the sample to be tested was measured by high-temperature catalytic combustion oxidation method, and the plating solution sample without resist was used as a blank sample. The greater the measured value of the organic carbon content (TOC), the greater the contamination of the plating solution.

[0247] Judgment basis:

[0248] O: TOC value < 500 ppm after deduction of blank;

[0249] Δ: 500 ppm ≤ TOC value ≤ 1000 ppm after deduction of blank;

[0250] X: TOC value > 1000 ppm after deduction of blank.

[0251] [Side edge appearance evaluation]

[0252] In the resist pattern used in the resolution evaluation described above, the best resolution part was made into a section, and observed with an SU1000 type scanning electron microscope (manufactured by Hitachi).

[0253] Judgment basis:

[0254] O: The cross section of the head of the dry film is rectangular;

[0255] Δ: The cross section of the head of the dry film is somewhat inverted trapezoidal;

[0256] X: The cross section of the head of the dry film is seriously inverted trapezoidal, or the bottom is hollowed out, or there is a significant crack in the side wall.

[0257] Evaluation results

[0258] The test results of Examples 9 to 16 and Comparative Examples 4 to 6 in evaluation items 1 to 4 are shown in Table 2.

[0259] Table 2

[0260]

[0261] As can be seen from the data in Table 2, the photosensitive dry film resist prepared in Example 9 has good photosensitivity, resolution, adhesion and plating resistance. The photosensitive resin composition prepared in Comparative Example 4 has poor resolution, adhesion and plating resistance, indicating that the fluorine-containing group is not suitable for grafting on the acrylic monomer. The photosensitive dry film resist prepared in Comparative Example 5 has insufficient adhesion and plating resistance, indicating that the fluorine-containing group is not suitable for grafting on the acrylate monomer. The photosensitive dry film resist prepared in Comparative Example 6 has insufficient resolution, adhesion and plating resistance, indicating that the fluorine-containing group is not suitable for grafting on the styrene monomer. The content of the polymaleimide in the alkali-soluble resin in the photosensitive dry film resist in Example 10 and Example 11 is too high or too low, which has a certain influence on the plating resistance. The preparation method of the alkali-soluble resin used in Example 12 is different, and the plating resistance is obviously decreased compared with Example 9, which may be because the fluorine-containing maleimide is prepared first, resulting in the occurrence of alternating polymerization of styrene and fluorine-containing maleimide in the subsequent polymerization process, affecting the plating resistance of the alkali-soluble resin. The photosensitive dry film resists in Example 13-16 use different types of alkali-soluble resins, but all have good comprehensive performance.

[0262] The above examples are only for illustrating the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and implement it, and cannot limit the protection scope of the present application. Any equivalent changes or modifications made according to the spirit and essence of the present application shall be covered within the protection scope of the present application.

Claims

1. An alkali-soluble resin, characterized in that, The structural formula is shown in Formula I: Wherein, R1 is a hydrogen atom or a methyl group; R2 is a C0-C6 methylene group; R3 is hydrogen or a methyl group; R4 is one of a C1-C10 straight-chain alkyl group, a branched alkyl group, or an aromatic group; R5 is a monofluorinated or polyfluorinated substituted C1-C10 alkyl group or an aromatic group; R6 is hydrogen or a methyl group; a, b, c, and d represent the mass percentage content of the corresponding monomers, 15%≤a≤25%; 45%≤b≤55%; 15%≤c≤25%; 5%≤d≤15%, and a+b+c+d=100%.

2. The alkali-soluble resin as described in claim 1, characterized in that, The alkali-soluble resin has a weight-average molecular weight of 40,000 to 100,000 g / mol and a molecular weight distribution of 1.2 to 4.

0. And / or: R5 is a polyfluorinated C1-C10 alkyl group.

3. The method for preparing the alkali-soluble resin according to claim 1 or 2, characterized in that, Its synthetic route is as follows: Includes the following steps: (1) After mixing monomer 1, monomer 2, monomer 3, monomer 4, the first part of the initiator and the solvent, solution A is obtained; after mixing the second part of the initiator and the solvent, solution B is obtained; the solvent is added to the reactor and the temperature is raised to the reaction temperature, and then solution A is continuously passed into the reactor. After the passage is completed, the reaction is set for a time, and then solution B is added dropwise to the reaction solution. After the dropwise addition is completed, the temperature is raised to continue the reaction, and a reaction solution containing primary alkali soluble resin A is obtained. (2) Under ice bath conditions, a solution containing NH2-R5 was added dropwise to the reaction solution containing primary base soluble resin A. After the addition was completed, the temperature was raised to room temperature to carry out the reaction, and a reaction solution containing intermediate base soluble resin B was obtained. (3) Add sodium acetate and acetic anhydride to the reaction solution containing intermediate base-soluble resin B, heat to the set temperature and carry out the reaction. After the reaction is complete, separate and purify to obtain base-soluble resin.

4. The method for preparing the alkali-soluble resin as described in claim 3, characterized in that, In step (1), monomer 1 is one or more of acrylic acid, methacrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 3-methylbut-3-enoic acid, and 4-methyl-4-pentenoic acid; And / or: the monomer 2 is one or more of methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, tert-butyl acrylate, butyl methacrylate, tert-butyl methacrylate, n-octyl acrylate, isooctyl acrylate, n-octyl methacrylate, isooctyl methacrylate, benzyl acrylate, and benzyl methacrylate; And / or: the monomer 4 is one or both of maleic anhydride and citrate anhydride; And / or: the mass ratio of monomer 1, monomer 2, and monomer 3 is (15~25):(45~55):(15~25); The molar ratio of monomer 4 to NH2-R5 in step (2) is 1:(1~1.05); the mass ratio of monomer 3 to the total mass of monomer 4 and NH2-R5 is (15~25):(5.5~16.9); And / or: the first part of the initiator is 0.1-2% of the total mass of monomer 1, monomer 2, monomer 3 and monomer 4; the second part of the initiator is 0.1-2% of the total mass of monomer 1, monomer 2, monomer 3 and monomer 4. And / or: The first part initiator and the second part initiator are each independently one or more of the following: azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, tert-butyl peroxide, and di-tert-butyl peroxide; And / or: In step (2), NH2-R5 is one or more of the following: 4-fluoroaniline, 3-fluoroaniline, 2,2-difluoroethylamine, 2,2,2-trifluoroethylamine, 2,2,3,3,3-pentafluoropropylamine, 2,2,3,3,4,4,4-heptafluorobutylamine, 1H,1H-perfluoroheptylamine, p-trifluoromethylaniline, m-trifluoromethylaniline, and 3-fluoro-4-trifluorotoluidine; And / or: In step (3), the amount of sodium acetate added is 1 to 14% of the mass of intermediate alkali soluble resin B in step (2); the amount of acetic anhydride added is 0.5 to 5 times the mass of intermediate alkali soluble resin B in step (2).

5. The method for preparing the alkali-soluble resin according to claim 3, characterized in that, In step (1), the reaction temperature is 60~80℃; the set time is 3~5h; the temperature is raised to 70~90℃ and the reaction continues for 4~6h; And / or: In step (2), the reaction time is 12~24h; And / or: In step (3), the temperature is set to 80~120℃ and the reaction time is 12~24h.

6. The method for preparing the alkali-soluble resin according to claim 1 or 2, characterized in that, The synthesis route is as follows: Includes the following steps: (1) Under ice bath conditions, a solution containing NH2-R5 was added dropwise to a solution containing monomer 4. After the addition was complete, the temperature was raised to room temperature to carry out the first stage reaction. After the reaction was complete, the intermediate 1 was obtained by separation and purification. Intermediate 1, sodium acetate and acetic anhydride were mixed and heated to the set temperature to carry out the second stage reaction. After separation and purification, monomer 5 was obtained. (2) After mixing monomer 1, monomer 2, monomer 3, monomer 5, the first part of the initiator and the solvent, solution A is obtained; after mixing the second part of the initiator and the solvent, solution B is obtained; the solvent is added to the reactor and the temperature is raised to the reaction temperature. Then, solution A is continuously introduced into the reactor. After solution A is completely introduced, after the reaction time is set, solution B is added dropwise to the reaction solution. After the addition is completed, the temperature is raised to the set temperature and the reaction continues. After the reaction is completed, the solution is separated and purified to obtain the alkali-soluble resin.

7. The method for preparing the alkali-soluble resin according to claim 6, characterized in that, In step (1), the molar ratio of monomer 4 to NH2-R5 is 1:(1.00~1.05); the amount of sodium acetate added is 50~80% of the mass of intermediate 1; the amount of acetic anhydride added is 10~20 times the mass of intermediate 1. And / or: In step (2), monomer 1, monomer 2, monomer 3 and monomer 5 are in a mass ratio of (15~25):(45~55):(15~25):(5~15); the first part of the initiator is 0.1~2% of the total mass of monomer 1, monomer 2, monomer 3 and monomer 5; the second part of the initiator is 0.1~2% of the total mass of monomer 1, monomer 2, monomer 3 and monomer 5.

8. A photosensitive dry film resist, characterized in that, Includes the alkali-soluble resin according to any one of claims 1 to 2; or the alkali-soluble resin prepared by any one of claims 3 to 7.

9. The photosensitive dry film resist as described in claim 8, characterized in that, According to the mass ratio, it includes: 42-65 parts of alkali-soluble resin, 21-48 parts of photopolymerizable monomer, 0.1-5 parts of photoinitiator, and 0.1-5 parts of additives.

10. The application of the photosensitive dry film resist as described in claim 8 or 9 in printed circuit boards, lead frames, or semiconductor packaging substrates.

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