Photosensitive resin composition, photosensitive dry film, cured film and circuit board

Abstract

The invention provides a photosensitive resin composition. The photosensitive resin composition comprises alkali-soluble resin, a photoinitiator, a thermal curing agent and a chemical nickel immersion gold resistant auxiliary agent, wherein the chemical nickel immersion gold resistant auxiliary agent is selected from one or more of silicate, a transition metal compound, a xanthic acid compound, a dithiocarbamate derivative, a cucurbituril compound, a polyether organic matter, a crown ether compound or ion exchange resin. According to the photosensitive resin composition and the preparation method thereof, the chemical nickel and gold immersion resistant auxiliary agent is added into the photosensitive resin composition, so that the chemical gold immersion resistance, the resolution, the flexibility and the deep curing property of the photosensitive resin composition in the chemical nickel and gold immersion treatment process can be effectively improved, and the comprehensive performance of a cured film can be improved.

Description

Technical Field

[0001] The present invention relates to the technical field of photosensitive materials, and in particular to a photosensitive resin composition, a photosensitive dry film, a cured film and a circuit board. Background Art

[0002] When installing electronic devices on printed circuit boards for electronic equipment, in order to prevent solder from falling on other areas, solder resist is often used to form a solder resist layer on the circuit board to cover it. The solder resist layer can also protect the circuit board in an environment with high temperature, humidity, pollutants or corrosive gases. At present, the mainstream solder resist is solder resist ink, which needs to be applied to the circuit board to solidify into a film when used. In addition, dry film solder resist has also been proposed; the solder resist is applied to the substrate to form a photosensitive dry film, so that the photosensitive dry film can be directly attached to the circuit board for use in the circuit board manufacturing process, and the photosensitive dry film can also omit the process of curing the film, and the solder resist layer formed by it is smoother.

[0003] As a surface treatment method for printed circuit boards, chemical nickel-gold treatment has many functions such as solderability, conduction, heat dissipation, and flat coating. It meets the requirements of multifunctional and excellent performance of surface treatment for the high-density development of printed circuit boards, and has been widely used in the manufacturing process of printed circuit boards. However, there are many problems in the process of chemical nickel-gold treatment, such as: it may cause the solder mask to turn white and peel off, which may lead to short circuit or even open circuit in high temperature and humid environment. Among them, there are many reasons why chemical nickel-gold treatment causes the solder mask to peel off, including the formula of the solder mask, the characteristics of the nickel-gold solution, the curing temperature and time of the solder mask, the nickel-gold treatment temperature and time, etc. Among them, improving the formula of the solder mask to improve its resistance to chemical gold is one of the lowest cost and most effective methods.

[0004] In the face of the problem of poor resistance to gold plating in the solder resist in the prior art, many approaches are adopted to solve the above problem. First, by improving the deep curing property of the solder resist film, its resistance to gold plating can be improved to a certain extent. Among them, reducing the content of inorganic fillers, especially the filler content of the solder resist film close to the side of the circuit board in the thickness direction, is one of the means to improve deep curing. However, when the filler content is low, it may make it difficult for the solder resist film to achieve a specific appearance and mechanical properties; and inorganic fillers have a certain influence on the heat resistance of the solder resist film. Generally, the nickel-gold deposition process requires certain temperature conditions. If the heat resistance is insufficient due to insufficient fillers, it is more unfavorable to improve the resistance to gold plating of the solder resist film; when the solder resist film adopts a double-layer or multi-layer structure, by reducing the filler of the layer close to the circuit board, the amount of light reaching the bottom layer (the layer close to the circuit board) can be increased, thereby improving the deep curing property and then improving the resistance to gold plating. However, it is necessary to consider the problem of interlayer peeling affecting reliability, and the preparation process of the multi-layer structure is also relatively complicated and difficult to industrialize. Second, the heat resistance of the solder mask can be increased by increasing the content of specific fillers, that is, the resistance to gold oxidation by increasing the resistance of the solder mask to the temperature conditions during the nickel-gold deposition process, but too much filler affects the flexibility of the solder mask. Third, the formula of the nickel-gold deposition solution can be improved to reduce its aggressiveness to the solder mask, which can reduce the solder mask peeling phenomenon, but the formula of the nickel-gold deposition solution is complex, and it is very difficult to develop a nickel-gold deposition solution that has a fast nickel-gold deposition speed, good effect, less attack on the solder mask, and mild nickel-gold deposition conditions. Fourth, the resistance to gold oxidation can be improved by increasing the thickness of the solder mask layer, but it is bound to affect the cost, production efficiency, and flexibility, which is not in line with the trend of thinning circuit boards. Fifth, the process can be improved by increasing the heat curing time and temperature and reducing the nickel-gold deposition time and temperature to reduce the attack of nickel-gold deposition on the solder mask, but the former may cause the solder mask to age, discolor and turn yellow, and have poor flexibility, and the latter is not conducive to the effect of nickel-gold deposition.

[0005] In summary, the photosensitive resin composition in the prior art has a technical problem of poor resistance to chemical gold during the chemical nickel-gold deposition process, and it is urgently needed to provide a photosensitive resin composition to improve the above problem. Summary of the invention

[0006] The main purpose of the present invention is to provide a photosensitive resin composition, a photosensitive dry film, a cured film and a circuit board to solve the technical problems in the prior art that the photosensitive resin composition has poor resistance to gold or poor resolution or poor flexibility during chemical nickel-gold treatment.

[0007] The invention provides a photosensitive resin composition, which comprises: an alkali-soluble resin, a photoinitiator, a thermal curing agent and a chemical nickel-gold resistant additive; wherein the chemical nickel-gold resistant additive is selected from one or more of silicates, transition metal compounds, xanthate compounds, dithiocarbamate derivatives, cucurbitacin compounds, polyether organics, crown ether compounds or ion exchange resins.

[0008] Further, the photosensitive resin composition also includes: a photopolymerizable monomer and an optional filler; preferably, the components of the photosensitive resin composition include, by weight: 100 parts of an alkali-soluble resin, 0.1 to 50 parts of a photopolymerizable monomer, 0.1 to 5 parts of a photoinitiator, 5 to 20 parts of a thermal curing agent, 0.01 to 30 parts of a chemically resistant nickel-gold precipitate additive, and 0 to 150 parts of a filler; preferably, the chemically resistant nickel-gold precipitate additive is selected from one or more of silicates, transition metal compounds, xanthate compounds, dithiocarbamate derivatives, cucurbitacin compounds, or crown ether compounds, and the components of the photosensitive resin composition include, by weight: 100 parts of an alkali-soluble resin, 0.1 to 50 parts of a photopolymerizable monomer, 0.1 to 5 parts of a photoinitiator, 5 to 20 parts of a A thermal curing agent, 0.01 to 5 parts of a chemical resistant nickel-gold immersion aid, and 0 to 150 parts of a filler; or, the chemical resistant nickel-gold immersion aid is selected from a polyether organic matter, and the components of the photosensitive resin composition include, by mass, 100 parts of an alkali-soluble resin, 0.1 to 50 parts of a photopolymerizable monomer, 0.1 to 5 parts of a photoinitiator, 5 to 20 parts of a thermal curing agent, 0.01 to 15 parts of a chemical resistant nickel-gold immersion aid, and 0 to 150 parts of a filler; or, the chemical resistant nickel-gold immersion aid is selected from an ion exchange resin, and the components of the photosensitive resin composition include, by mass, 100 parts of an alkali-soluble resin, 0.1 to 50 parts of a photopolymerizable monomer, 0.1 to 5 parts of a photoinitiator, 5 to 20 parts of a thermal curing agent, 1 to 30 parts of a chemical resistant nickel-gold immersion aid, and 0 to 150 parts of a filler.

[0009] Further, the chemical resistant nickel-gold precipitating additive is a compound of silicate and ion exchange resin, and the components of the photosensitive resin composition include, by weight: 100 parts of alkali-soluble resin, 0.1-50 parts of photopolymerizable monomers, 0.1-5 parts of photoinitiators, 5-20 parts of thermal curing agents, 0.02-30 parts of chemical resistant nickel-gold precipitating additives, and 0-150 parts of fillers; wherein the silicate and the ion exchange resin are each independently selected from 0.01-15 parts; preferably, the weight ratio of the silicate to the ion exchange resin is (1-5):1; more preferably, the weight ratio of the silicate to the ion exchange resin is (1.5-2.5):1; or, the chemical resistant The nickel-gold additive is a compound of a transition metal compound and an ion exchange resin, and the components of the photosensitive resin composition include, by weight: 100 parts of an alkali-soluble resin, 0.1 to 50 parts of a photopolymerizable monomer, 0.1 to 5 parts of a photoinitiator, 5 to 20 parts of a thermal curing agent, 0.02 to 30 parts of a chemically resistant nickel-gold additive, and 0 to 150 parts of a filler; wherein the transition metal compound and the ion exchange resin are each independently selected from 0.01 to 15 parts; preferably, the weight ratio of the transition metal compound to the ion exchange resin is (1 to 5):1; more preferably, the weight ratio of the transition metal compound to the ion exchange resin is (1.5 to 2.5):1.

[0010] Further, the transition metal compound is selected from one or more of a pentavalent transition metal compound, a hexavalent transition metal compound or a heptavalent transition metal compound; preferably, the pentavalent transition metal compound is selected from one or more of vanadium pentoxide, hydrated vanadium pentoxide, titanium vanadate, aluminum vanadate, zirconium vanadate, phosphovanadic acid, vanadium molybdate, vanadium ferrocyanide, niobium pentoxide, hydrated niobium pentoxide, tantalum pentoxide, hydrated tantalum pentoxide, antimony pentoxide and hydrated antimony pentoxide; preferably, the hexavalent transition metal compound is selected from one or more of antimony tungstic acid, titanium antimonate, tin antimonate, iron antimonate, aluminum antimonate, chromium antimonate, tantalum antimonate, manganese antimonate, bismuth antimonate, phosphoantimonic acid and antimony molybdate; preferably, the heptavalent transition metal compound is selected from one or more of potassium permanganate, calcium permanganate and aluminum permanganate; preferably, the silicate is selected from one or more of metal silicates, borosilicates, aluminosilicates and beryllium silicates; preferably, the metal cation contained in the silicate is Na + , K + Mg 2+ , Ca 2+ , Ba 2+ or Al 3+ At least one of .

[0011] Further, the polyether organic matter is a polyether organic matter containing -COC- repeating units; more preferably, the polyether organic matter is at least one of polyethylene oxide, polyepichlorohydrin, epichlorohydrin-ethylene oxide copolymer and epichlorohydrin-ethylene oxide-propylene oxide copolymer; preferably, the weight average molecular weight of the polyether organic matter is 400 to 12000; preferably, the xanthate compound is selected from potassium xanthate, zinc xanthate, sodium xanthate, sodium ethyl xanthate, sodium isopropyl xanthate, xanthate, isopentyl xanthate, More preferably, the substituted or unsubstituted alkyl dixanthate is selected from one or more of methylene dixanthate, dipropylene glycol dixanthate, triethylene glycol dixanthate, ethylene bis(isobutyl xanthate), methylene bis(n-butyl xanthate), methylene bis(tetrahydrofurfuryl xanthate) and p-xylene bis(n-butyl xanthate); preferably, the dithiocarbamate derivative is selected from dibutyl dithiocarbamate. Preferably, the crown ether compound is a nitrogen-branched lariat crown ether compound containing a central functional group; further preferably, the crown ether compound is N-phenoxyethyl monoaza-18-crown-6 and / or N-phenoxyethyl monoaza-15-crown-5; preferably, the ion exchange resin is a cation exchange resin and / or an anion exchange resin; further preferably, the ion exchange resin is Styrene-based ion exchange resin and / or acrylic ion exchange resin; more preferably, the styrene-based ion exchange resin is selected from type 731, type 732, type D113 or type 110, and the acrylic ion exchange resin is selected from type D151 or type D152; preferably, the weight average molecular weight of the ion exchange resin is 300 to 8000; preferably, the cucurbitacin compound is a cucurbitacin homologue and / or a cucurbitacin derivative; more preferably, the cucurbitacin compound is a five-membered cucurbitacin compound and / or a symmetrical tetramethyl six-membered cucurbitacin compound.

[0012] Further, the alkali-soluble resin is selected from one or more of epoxy acrylic resin, styrene acrylic resin and polyurethane acrylic resin; preferably, the epoxy acrylic resin is selected from one or more of carboxylic acid-modified bisphenol A epoxy resin, carboxylic acid-modified bisphenol F epoxy resin, carboxylic acid-modified novolac epoxy resin and carboxylic acid-modified o-cresol epoxy resin; preferably, the styrene acrylic resin is carboxylic acid-modified styrene acrylic resin; more preferably, the weight average molecular weight of the carboxylic acid-modified styrene acrylic resin is 30,000 to 200,000 and the glass transition temperature is 90 to 150° C.; preferably, the polyurethane acrylic resin is selected from one or more of aliphatic polyurethane acrylic resin, alicyclic polyurethane acrylic resin and aromatic polyurethane acrylic resin; preferably, the weight average molecular weight of the alkali-soluble resin is 10,000 to 300,000; more preferably, the acid value of the alkali-soluble resin is 45 to 200 mgKOH / g; preferably, the photopolymerizable monomer is selected from one or more of monofunctional photopolymerizable monomers, difunctional photopolymerizable monomers, trifunctional photopolymerizable monomers or multifunctional photopolymerizable monomers;Preferably, the monofunctional photopolymerizable monomer is selected from methacrylamide, N-(hydroxymethyl)methacrylamide, N-(hydroxymethyl)acrylamide, N-(methoxymethyl)methacrylamide, N-(methoxymethyl)acrylamide, N-(ethoxymethyl)methacrylamide, N-(ethoxymethyl)acrylamide, N-(propoxymethyl)methacrylamide, N-(propoxymethyl)acrylamide, N-(butoxymethoxymethyl)methacrylamide, N-(butoxymethoxymethyl)acrylamide, methacrylic acid, acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, Acid, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylhexyl acrylate, cyclohexyl (meth)acrylate, cyclohexyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxybutyl acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, 2-acryloyloxy-2-hydroxypropyl phthalate, At least one of oil mono(meth)acrylate, glycerol monoacrylate, tetrahydrofurfuryl (meth)acrylate, tetrahydrofurfuryl acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminoethyl acrylate, glycidyl (meth)acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl acrylate or semi-(meth)acrylate of phthalic acid derivatives, semi-acrylate of phthalic acid derivatives; preferably, the difunctional photopolymerizable monomer is selected from tricyclodecane dimethanol diacrylate, propylene glycol di(meth)acrylate , propylene glycol diacrylate, pentaerythritol di(meth)acrylate, pentaerythritol diacrylate, butanediol di(meth)acrylate, butanediol diacrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol diacrylate, 1,6-hexanediol dipropionate or 1,6-hexanediol di(meth)propionate; preferably, the trifunctional photopolymerizable monomer is selected from at least one of trimethylolpropane tri(meth)acrylate, trimethylolpropane triacrylate, propoxy-modified trimethylolpropane tri(meth)acrylate, propoxy-modified trimethylolpropane triacrylate, tri(2-hydroxyethyl)isocyanuric acid triacrylate, pentaerythritol tri(meth)acrylate or pentaerythritol triacrylate;Preferably, the multifunctional photopolymerizable monomer is selected from at least one of di-trimethylolpropane tetraacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetraacrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate or dipentaerythritol hexa(meth)acrylate; preferably, the photoinitiator is selected from at least one of a cleavage-type free radical initiator or a hydrogen abstraction-type free radical initiator; preferably, the cleavage-type free radical initiator is selected from at least one of an α-hydroxyketone derivative initiator, an α-aminoketone derivative initiator, an acylphosphine oxide initiator or an oxime ester initiator; preferably, the hydrogen abstraction-type free radical initiator is selected from at least one of benzophenone and its derivative initiators, thioxanthone and its derivative initiators, anthraquinone and its derivative initiators or titanocene initiators; preferably, the thermal curing agent is selected from isocyanate compounds, blocked isocyanate compounds, amino resins, benzoxazine resins, carbodiimide resins, cyclic carbonates Preferably, the thermosetting agent is an epoxy compound; Preferably, the epoxy compound is an epoxy resin; Preferably, the softening point of the epoxy resin is 40 to 200°C, and the epoxy equivalent of the epoxy resin is 50 to 350 g / eq.; More preferably, the softening point of the epoxy resin is 50 to 100°C, and the epoxy equivalent of the epoxy resin is 50 to 300 g / eq.; Further preferably, the epoxy resin The epoxy equivalent is 100 to 200 g / eq.; preferably, the epoxy resin is selected from one or more of bisphenol epoxy resin, biphenyl epoxy resin, phenolic epoxy resin, epoxy resin containing naphthalene ring and alicyclic epoxy resin; preferably, the material of the filler is selected from one or more of titanium black, carbon black, iron oxide, titanium oxide, barium sulfate, silicon dioxide, calcium carbonate and zinc oxide; preferably, the particle size of the filler is 0.1 to 20 μm; more preferably, the particle size of the filler is 0.2 to 5 μm. ;

[0013] Furthermore, the chemical resistant nickel-gold precipitating additive is selected from polyether organic matter and / or ion exchange resin; preferably, the chemical resistant nickel-gold precipitating additive is selected from ion exchange resin.

[0014] According to the second aspect of the present invention, a photosensitive dry film is further provided. The photosensitive dry film is obtained by coating and baking the above-mentioned photosensitive resin composition.

[0015] According to the third aspect of the present invention, there is also provided a cured film, which is obtained by coating, baking and curing the above-mentioned photosensitive resin composition or by curing the above-mentioned photosensitive dry film.

[0016] According to a fourth aspect of the present invention, there is also provided a circuit board, which comprises a cured film obtained by coating, baking and curing the above-mentioned photosensitive resin composition or a cured film obtained by curing the above-mentioned photosensitive dry film or the above-mentioned cured film.

[0017] The present invention provides a photosensitive resin composition, which comprises: an alkali-soluble resin, a photoinitiator, a thermal curing agent and a chemical nickel-gold resistant additive; wherein the chemical nickel-gold resistant additive is selected from one or more of silicates, transition metal compounds, xanthate compounds, dithiocarbamate derivatives, cucurbitacin compounds, polyether organics, crown ether compounds or ion exchange resins. The present invention can effectively improve the chemical nickel-gold resistance, resolution, flexibility and deep curing performance of the photosensitive resin composition in the process of chemical nickel-gold treatment by adding the above-mentioned chemical nickel-gold resistant additive to the photosensitive resin composition, which is conducive to improving its comprehensive performance. DETAILED DESCRIPTION

[0018] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0019] Terminology explanation:

[0020] Chemical gold resistance (chemical nickel-gold resistance): Chemical nickel-gold is used for the surface treatment of circuit boards. It replaces palladium on the surface of copper circuits through chemical reactions, and then chemically plates a nickel-phosphorus alloy layer on the palladium core, and then plates a layer of gold on the surface of nickel through replacement reaction. It is used to prevent the copper on the surface of the circuit board from being oxidized or corroded, and is used for welding and contact. As a protective layer of the circuit board, the role of the solder mask is to protect the parts that do not need nickel-gold. Therefore, the solder mask needs to have a certain resistance to chemical gold, and will not turn white or even fall off due to the attack of nickel-gold solution, otherwise it will cause the circuit to short-circuit or even break under high temperature, humidity and other environmental conditions.

[0021] Softening point: The temperature at which a material begins to soften during heating. Specifically, the softening point of epoxy resin refers to the temperature at which the epoxy resin changes from hard to soft and exhibits a certain degree of fluidity during heating. The softening point numerical range in this application is the value measured according to the method described in JIS K 7234.

[0022] Resolution: refers to the minimum graphic size that the photosensitive dry film can bear, that is, the minimum line width and gap that the photosensitive dry film can distinguish.

[0023] According to the background technology of the present invention, the photosensitive resin composition in the prior art has the technical problems of poor chemical gold resistance, poor resolution or poor flexibility during the chemical nickel-gold treatment. In view of the above technical problems, the present invention provides a photosensitive resin composition, which includes: an alkali-soluble resin, a photoinitiator, a thermal curing agent and a chemical nickel-gold resistant additive; wherein the chemical nickel-gold resistant additive is selected from one or more of silicates, transition metal compounds, xanthate compounds, dithiocarbamate derivatives, cucurbitacin compounds, polyether organics, crown ether compounds or ion exchange resins.

[0024] The present invention is based on the conventional photosensitive resin composition in the prior art, and an additional chemical nickel-gold resistant additive is added to improve its chemical gold resistance. Wherein, the chemical nickel-gold resistant additive is selected from one or more of silicates, transition metal compounds, xanthate compounds, dithiocarbamate derivatives, cucurbitacin compounds, polyether organics, crown ether compounds or ion exchange resins. When the chemical nickel-gold resistant additive in the present invention is selected from silicates, the silicate ions in the silicates can capture the cations in the solder mask raw materials and the metal cations (such as sodium ions, potassium ions, copper ions or divalent iron ions and trivalent iron ions, etc.) that may be introduced in the subsequent development application by ion exchange, preventing the migration of cations in the solder mask under the action of the electric field and the attack on the hydrogen bonds at the copper-solder mask interface, thereby further improving its chemical gold resistance. And the silicate compound can be melted into an alkali-soluble resin for use, and most silicates are insoluble, so no new ions are introduced into the system. In addition, in the crystal structure of silicate minerals, the most basic structural unit is the Si-O anion. Most silicate minerals are tetraoxysilicates, and their Si 4+ It has 4 times coordination, forming Si-O4 coordinated tetrahedron. Such silicon-oxygen tetrahedron can exist in isolation in the structure and be connected to each other by other metal cations. Silicon-oxygen tetrahedrons can also share the O 2- (called bridging oxygen) to form siloxane backbones in different connection forms such as tetrahedral groups, rings, chains, layers and frames. The siloxane backbones are then connected with other metal cations, so that the ion complex formed can exist stably, thereby increasing the gold resistance of the photosensitive resin composition.

[0025] When the chemical nickel-gold resistant additive in the present invention is selected from transition metal compounds, the transition metal compound can capture metal ions and generate water-insoluble metal phosphates and metal-containing oxygen-anion salts through ion exchange reactions, thereby preventing the migration of cations in the solder mask layer under the action of an electric field and the attack on the hydrogen bonds at the copper-solder mask interface, thereby improving the chemical gold resistance. When the chemical nickel-gold resistant additive in the present invention is selected from xanthate compounds and dithiocarbamate derivatives, the xanthate compounds or dithiocarbamate derivatives can also play a role in capturing metal ions in the raw materials of the solder mask layer, and their ability to bind to metal ions is stronger, and their chelating capacity is greater than that of conventional metal ion capture agents, and the above-mentioned effects can occur continuously, thereby achieving the purpose of long-term capture.

[0026] When the chemical nickel-gold resistant additive in the present invention is selected from cucurbitacin compounds, the polar functional group carbonyl oxygen or hollow ring structure and the metal cation form a complex that self-assembles into a "molecular capsule" structure, and can also coordinate with trace water molecules in the system, which not only reduces the ion mobility, but also reduces the free water content in the system, thereby improving its chemical gold resistance and further improving its insulation. When the chemical nickel-gold resistant additive in the present invention is selected from polyether organic matter or crown ether compound, the electron-donating group on the side arm branch can be paired with the cation at an appropriate position to form a very stable complex, so that the cation hydrodynamic volume increases, thereby reducing the moving speed, improving the chemical gold resistance, reducing the system conductivity, improving the volume resistivity, and improving the insulation of the solder mask.

[0027] When the chemical nickel-gold resistant additive in the present invention is selected from an ion exchange resin, the ion exchange resin can exchange ions with metal ions in the external environment, thereby playing the role of adsorbing and fixing metal ions. And the ion exchange resin itself does not contain any metal ion components, so no new metal ion impurities are introduced. In addition, ion exchange resin is a type of polymer, which has better compatibility with solder mask than transition metal compounds. And the ion exchange resin has a loose and porous structure, so that the contact area of ​​adsorption can be increased, making it more evenly dispersed in the system, thereby improving its resistance to chemical gold while also improving its analytical properties and flexibility.

[0028] In summary, the present invention can effectively improve the chemical nickel-gold resistance, resolvability and flexibility of the photosensitive resin composition during the chemical nickel-gold treatment process by adding one or more chemical nickel-gold resistance additives selected from silicates, transition metal compounds, xanthate compounds, dithiocarbamate derivatives, cucurbitacin compounds, polyether organics, crown ether compounds or ion exchange resins to the photosensitive resin composition.

[0029] In a preferred embodiment, the photosensitive resin composition further includes: a photopolymerizable monomer and an optional filler; the alkali-soluble resin may contain double bonds, and a photocuring reaction occurs during the exposure process. Adding a photopolymerizable monomer to the photosensitive resin composition can further promote the photocuring reaction. Preferably, the ingredients of the photosensitive resin composition include: 100 parts of alkali-soluble resin, 0.1 to 50 parts of photopolymerizable monomer, 0.1 to 5 parts of photoinitiator, 5 to 20 parts of thermal curing agent, 0.01 to 30 parts of chemical nickel-gold resistant additive, and 0 to 150 parts of filler. Compounding the various components in the photosensitive resin composition according to the above proportions can better exert the synergistic effect between the various components in the photosensitive resin composition, and further improve the chemical gold resistance, resolution and flexibility of the photosensitive resin composition. Preferably, the components of the photosensitive resin composition include: 100 parts of alkali-soluble resin, 10 to 50 parts of photopolymerizable monomers, 1 to 5 parts of photoinitiators, 10 to 20 parts of thermal curing agents, 0.02 to 30 parts of chemical nickel-gold resistant additives, and 1 to 100 parts of fillers. More preferably, the components of the photosensitive resin composition include: 100 parts of alkali-soluble resin, 20 to 50 parts of photopolymerizable monomers, 1 to 5 parts of photoinitiators, 10 to 20 parts of thermal curing agents, 0.05 to 30 parts of chemical nickel-gold resistant additives, and 5 to 100 parts of fillers. Controlling each component in the photosensitive resin composition within the above preferred range will result in better performance of the photosensitive resin composition.

[0030] Preferably, the chemical resistant nickel-gold precipitating additive is selected from silicates, transition metal compounds, xanthate compounds, dithiocarbamate derivatives, cucurbitacin compounds, and crown ether compounds, and the components of the photosensitive resin composition include, by weight: 100 parts of alkali-soluble resin, 0.1 to 50 parts of photopolymerizable monomers, 0.1 to 5 parts of photoinitiators, 5 to 20 parts of thermal curing agents, 0.01 to 5 parts of chemical resistant nickel-gold precipitating additives, and 0 to 150 parts of fillers; or, the chemical resistant nickel-gold precipitating additive is selected from polyether organics, and by weight, the components of the photosensitive resin composition include: The composition comprises: 100 parts of alkali-soluble resin, 0.1 to 50 parts of photopolymerizable monomer, 0.1 to 5 parts of photoinitiator, 5 to 20 parts of thermal curing agent, 0.01 to 15 parts of chemical nickel-gold resistant additive, and 0 to 150 parts of filler; or, the chemical nickel-gold resistant additive is selected from ion exchange resin, and the components of the photosensitive resin composition include, by mass, 100 parts of alkali-soluble resin, 0.1 to 50 parts of photopolymerizable monomer, 0.1 to 5 parts of photoinitiator, 5 to 20 parts of thermal curing agent, 1 to 30 parts of chemical nickel-gold resistant additive, and 0 to 150 parts of filler. According to the difference in the type of chemical nickel-gold resistant additive, the addition ratio is further controlled within the above preferred range, which can further improve the chemical gold resistance, resolution and flexibility of the photosensitive resin composition, and at the same time, the amount of chemical nickel-gold resistant additive can be controlled, thereby further reducing the preparation cost.

[0031] In a preferred embodiment, the chemical nickel-gold resistant additive is a compound of a silicate and an ion exchange resin, and the components of the photosensitive resin composition include, by weight: 100 parts of an alkali-soluble resin, 0.1 to 50 parts of a photopolymerizable monomer, 0.1 to 5 parts of a photoinitiator, 5 to 20 parts of a thermal curing agent, 0.02 to 30 parts of a chemical nickel-gold resistant additive, and 0 to 150 parts of a filler; wherein the silicate and the ion exchange resin are each independently selected from 0.01 to 15 parts; preferably, the weight ratio of the silicate to the ion exchange resin is (1 to 5):1; specifically, for example, 1:1, 1.5:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1 or any ratio between any two of the above ratios. More preferably, the weight ratio of silicate to ion exchange resin is (1.5-2.5):1; or, the chemical nickel-gold resistant additive is a compound of the transition metal compound and the ion exchange resin, and the components of the photosensitive resin composition include, by weight: 100 parts of alkali-soluble resin, 0.1-50 parts of photopolymerizable monomers, 0.1-5 parts of photoinitiators, 5-20 parts of thermal curing agents, 0.02-30 parts of chemical nickel-gold resistant additives, and 0-150 parts of fillers; wherein the transition metal compound and the ion exchange resin are each independently selected from 0.01-15 parts. Preferably, the weight ratio of the transition metal compound to the ion exchange resin is (1-5):1; specifically, for example, 1:1, 1.5:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1 or any ratio between any two of the above ratios. More preferably, the weight ratio of the transition metal compound to the ion exchange resin is (1.5-2.5): 1. The silicate or transition metal compound is compounded with the ion exchange resin to better utilize the advantages of the ion exchange resin being loose and porous and having a large adsorption contact area. While exerting the adsorption and fixation of metal ions of the ion exchange resin, the silicate or transition metal compound therein can also have better dispersibility in the system and be less likely to agglomerate, further exerting the role of the silicate or transition metal compound in improving the chemical gold resistance and analytical properties of the photosensitive resin composition, and the two types of chemical nickel-gold resistant additives work synergistically, and the overall effect is better.

[0032] In order to further enhance the chemical resistance, flexibility and resolving power of the photosensitive resin composition and improve its comprehensive performance, the alkali-soluble resin is preferably selected from one or more of epoxy acrylic resin, styrene acrylic resin and polyurethane acrylic resin; preferably, the epoxy acrylic resin is selected from one or more of carboxylic acid-modified bisphenol A epoxy resin, carboxylic acid-modified bisphenol F epoxy resin, carboxylic acid-modified novolac epoxy resin and carboxylic acid-modified o-cresol epoxy resin; preferably, the styrene acrylic resin is carboxylic acid-modified styrene acrylic resin; more preferably, the weight average molecular weight of the carboxylic acid-modified styrene acrylic resin is 30,000 to 200,000 and the glass transition temperature is 90 to 150°C; preferably, the polyurethane acrylic resin is selected from one or more of aliphatic polyurethane acrylic resin, alicyclic polyurethane acrylic resin and aromatic polyurethane acrylic resin; preferably, the weight average molecular weight of the alkali-soluble resin is 10,000 to 300,000; preferably, the acid value of the alkali-soluble resin is 45 to 200 mgKOH / g.

[0033] Preferably, the photopolymerizable monomer is selected from one or more of a monofunctional photopolymerizable monomer, a difunctional photopolymerizable monomer, a trifunctional photopolymerizable monomer or a multifunctional photopolymerizable monomer. By way of example but not limitation, the monofunctional photopolymerizable monomer is selected from methacrylamide, N-(hydroxymethyl)methacrylamide, N-(hydroxymethyl)acrylamide, N-(methoxymethyl)methacrylamide, N-(methoxymethyl)acrylamide, N-(ethoxymethyl)methacrylamide, N-(ethoxymethyl)acrylamide, N-(propoxymethyl)methacrylamide, N-(propoxymethyl)acrylamide, N-(butoxymethoxymethyl)methacrylamide, N-(butoxymethoxymethyl)acrylamide, methacrylic acid, acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citric acid, Aconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylhexyl acrylate, cyclohexyl (meth)acrylate, cyclohexyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxybutyl acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate Acrylates, 2-phenoxy-2-hydroxypropyl acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, 2-acryloyloxy-2-hydroxypropyl phthalate, glyceryl mono(meth)acrylate, glyceryl monoacrylate, tetrahydrofurfuryl (meth)acrylate, tetrahydrofurfuryl acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminoethyl acrylate, glycidyl (meth)acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate ester, 2,2,3,3-tetrafluoropropyl acrylate or half (meth) acrylate of phthalic acid derivative, half acrylate of phthalic acid derivative; preferably, the difunctional photopolymerizable monomer is selected from at least one of tricyclodecane dimethanol diacrylate, propylene glycol di(meth) acrylate, propylene glycol diacrylate, pentaerythritol di(meth) acrylate, pentaerythritol diacrylate, butanediol di(meth) acrylate, butanediol diacrylate, neopentyl glycol di(meth) acrylate, neopentyl glycol diacrylate, 1,6-hexanediol dipropionate or 1,6-hexanediol di(meth) propionate;Preferably, the trifunctional photopolymerizable monomer is selected from at least one of trimethylolpropane tri(meth)acrylate, trimethylolpropane triacrylate, propoxy-modified trimethylolpropane tri(meth)acrylate, propoxy-modified trimethylolpropane triacrylate, tri(2-hydroxyethyl)isocyanuric acid triacrylate, pentaerythritol tri(meth)acrylate or pentaerythritol triacrylate; preferably, the multifunctional photopolymerizable monomer is selected from at least one of di-trimethylolpropane tetraacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetraacrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate or dipentaerythritol hexa(meth)acrylate; the selection of the above-mentioned photopolymerizable monomer, difunctional photopolymerizable monomer, trifunctional photopolymerizable monomer or multifunctional photopolymerizable monomer can further improve the chemical resistance, flexibility and resolution of the photosensitive resin composition. ;

[0034] In order to further improve the cation capture ability of the chemical nickel-gold resistant additive during the treatment process, so that the photosensitive resin composition has stronger chemical gold resistance and better comprehensive performance of resolution and flexibility, preferably, the photoinitiator is selected from at least one of a cleavage-type free radical initiator or a hydrogen abstraction-type free radical initiator; preferably, the cleavage-type free radical initiator is selected from at least one of an α-hydroxyketone derivative initiator, an α-aminoketone derivative initiator, an acylphosphine oxide initiator or an oxime ester initiator; preferably, the hydrogen abstraction-type free radical initiator is selected from at least one of benzophenone and its derivative initiators, thioxanthone and its derivative initiators, anthraquinone and its derivative initiators or titanocene initiators.

[0035] By way of example but not limitation, the α-hydroxyketone derivative initiator may be 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-[4-(2-hydroxy)-phenyl]-3-hydroxy-2-methyl-1-propanone-1-one, and commercially available products may be Omnirad 184 and Omnirad 1173 manufactured by IGM Resins. The α-aminoketone derivative initiator may be 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, 2-phenylbenzyl-2-dimethylamino-1-(4-morpholinylbenzylphenyl)butanone, 2-p-methylbenzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, and commercially available products may be Omnirad 907, Omnirad 369, and Omnirad 379 manufactured by IGM Resins. Acylphosphine oxide initiators may be 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, etc., and commercially available products may be Omnirad TPO, Omnirad 819, Omnirad TPO-L, etc. manufactured by IGM Resins. Oxime ester initiators may be 1,8-bis[9-ethyl-6-nitro-9H-carbazole-3-yl]-, 1,8-bis(O-acetyl oxime), 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), etc., and commercially available products may be OXE-01 and OXE-02 manufactured by BASF and NCI-831 and N-1919 manufactured by ADEKA CORPORATION. Thioxanthone and its derivative initiators may be 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, etc., and commercially available products may be ITX, DETX, etc. Titanocene initiators may be bis(cyclopentadienyl)-diphenyltitanium, bis(cyclopentadienyl)-titanium dichloride, bis(cyclopentadienyl)-bis(2,3,4,5,6-pentafluorophenyl)titanium, bis(cyclopentadienyl)-bis(2,6,-difluoro-3-(pyrrol-1-yl)phenyl)titanium, etc., and commercially available products may include Omnirad 784 manufactured by IGM Resins BV, etc.

[0036] In a preferred embodiment, the thermal curing agent is selected from one or more of isocyanate compounds, blocked isocyanate compounds, amino resins, benzoxazine resins, carbodiimide resins, cyclic carbonate compounds, epoxy compounds, multifunctional oxetane compounds and episulfide resins; preferably, the thermal curing agent is an epoxy compound; preferably, the epoxy compound is an epoxy resin; preferably, the softening point of the epoxy resin is 40 to 200°C, and the epoxy equivalent of the epoxy resin is 50 to 350 g / eq.; more preferably, the softening point of the epoxy resin is 50 to 100°C, and the epoxy equivalent of the epoxy resin is 50 to 300 g / eq.; further preferably, the epoxy equivalent of the epoxy resin is 100 to 200 g / eq.; preferably, the epoxy resin is selected from one or more of bisphenol epoxy resins, biphenyl epoxy resins, novolac epoxy resins, epoxy resins containing naphthalene rings and alicyclic epoxy resins.

[0037] In a preferred embodiment, the material of the filler is selected from one or more of titanium black, carbon black, iron oxide, titanium oxide, barium sulfate, silicon dioxide, calcium carbonate and zinc oxide; preferably, the particle size of the filler is 0.1-20 μm; more preferably, the particle size of the filler is 0.2-5 μm. The preferred filler particle size reduces the adverse effect of inorganic fillers on chemical resistance, emphasizes the beneficial effect of inorganic fillers within a certain particle size range on heat resistance, and thus has a certain improvement effect on chemical resistance.

[0038] In order to further improve the cation capture ability of the chemical nickel-gold resistant additive during the treatment process, so that the photosensitive resin composition has stronger chemical gold resistance, better analytical and flexibility comprehensive performance, in a preferred embodiment, the silicate is selected from one or more of metal silicates, borosilicates, aluminosilicates and beryllium silicates; preferably, the metal cation contained in the silicate is Na + , K + Mg 2+ , Ca 2+ , Ba 2+ and Al 3+ More preferably, the silicate is one or more of calcium silicate, beryllium aluminum silicate and borosilicate aluminum.

[0039] In a preferred embodiment, the transition metal compound is selected from one or more of a pentavalent transition metal compound, a hexavalent transition metal compound or a heptavalent transition metal compound; preferably, the pentavalent transition metal compound is selected from one or more of vanadium pentoxide, hydrated vanadium pentoxide, titanium vanadate, aluminum vanadate, zirconium vanadate, phosphovanadic acid, vanadium molybdate, vanadium ferrocyanide, niobium pentoxide, hydrated niobium pentoxide, tantalum pentoxide, hydrated tantalum pentoxide, antimony pentoxide and hydrated antimony pentoxide; preferably, the hexavalent transition metal compound is selected from one or more of antimony tungstic acid, titanium antimonate, tin antimonate, iron antimonate, aluminum antimonate, chromium antimonate, tantalum antimonate, manganese antimonate, bismuth antimonate, phosphoantimonic acid and antimony molybdate; preferably, the heptavalent transition metal compound is selected from one or more of potassium permanganate, calcium permanganate and aluminum permanganate. Using the above transition metal compound as a chemical nickel-gold resistant additive can better capture metal ions, thereby further improving the chemical gold resistance and analytical properties of the photosensitive resin composition. More preferably, the transition metal compound is selected from a hexavalent transition metal compound or a heptavalent transition metal compound. The hexavalent transition metal compound or the heptvalent transition metal compound has a stronger force of electrons in the transition metal ions, so that it can better prevent the migration of cations in the solder mask layer under the action of the electric field and the attack on the hydrogen bonds at the copper-solder mask interface, which is conducive to further improving the resistance to gold. More preferably, the hexavalent transition metal compound is selected from antimony molybdic acid and antimony tungstic acid, and the heptvalent transition metal compound is selected from aluminum permanganate. The above transition metal compounds have a better effect on improving the resistance to gold of the photosensitive resin composition.

[0040] In a preferred embodiment, the polyether organic compound is a polyether organic compound containing -COC- repeating units; more preferably, the polyether organic compound is at least one of polyethylene oxide, polyepichlorohydrin, epichlorohydrin-ethylene oxide copolymer and epichlorohydrin-ethylene oxide-propylene oxide copolymer; preferably, the weight average molecular weight of the polyether organic compound is 400 to 12000; preferably, the xanthate compound is selected from potassium xanthate, zinc xanthate, sodium xanthate, sodium ethyl xanthate, sodium isopropyl xanthate, xanthate esters, isopentyl xanthate propylene ester, substituted or unsubstituted alkyl di- Xanthate; more preferably, the substituted or unsubstituted alkyl dixanthate is selected from one or more of methylene dixanthate, dipropylene glycol dixanthate, triethylene glycol dixanthate, ethylene bis(isobutyl xanthate), methylene bis(n-butyl xanthate), methylene bis(tetrahydrofurfuryl xanthate) and p-xylene bis(n-butyl xanthate); preferably, the dithiocarbamate derivative is selected from one or more of zinc dibutyl dithiocarbamate, zinc diethyl dithiocarbamate, zinc dibutyl dithiocarbamate and zinc ethylphenyl dithiocarbamate. Preferably, the crown ether compound is a nitrogen-branched lariat crown ether compound containing a central functional group; further preferably, the crown ether compound is N-phenoxyethyl monoaza-18-crown-6 and / or N-phenoxyethyl monoaza-15-crown-5.

[0041] In a preferred embodiment, the ion exchange resin is a cation exchange resin and / or an anion exchange resin; further preferably, the ion exchange resin is a styrene ion exchange resin and / or an acrylic ion exchange resin; preferably, the styrene ion exchange resin is selected from 731, 732, D113 or 110, and the acrylic ion exchange resin is selected from D151 or D152; preferably, the weight average molecular weight of the ion exchange resin is 300 to 8000. Selecting the ion exchange resin within the above preferred range is conducive to improving the ion exchange between it and the metal ions in the external environment, thereby further promoting the adsorption and fixation of metal ions.

[0042] In a preferred embodiment, the cucurbitacin compound is a cucurbitacin homologue and / or a cucurbitacin derivative; more preferably, the cucurbitacin compound is a five-membered cucurbitacin compound and / or a symmetrical tetramethyl six-membered cucurbitacin compound, which promotes the direct coordination of the carbonyl oxygen functional group therein with the metal cation and simultaneously coordinates with the trace amount of water molecules in the system, thereby reducing the ion mobility and the free water content in the system, further improving the gold resistance and insulation properties of the photosensitive resin composition.

[0043] In a preferred embodiment, the chemical nickel-gold resistant additive is selected from polyether organic matter and / or ion exchange resin. Polyether organic matter and ion exchange resin are organic compounds, which have better compatibility with the components in the photosensitive resin composition. At the same time, the above-mentioned type of chemical nickel-gold resistant additive does not have the influence of volume, particle size and other aspects, so it will not affect the resolvability of the photosensitive dry film, and the comprehensive performance of the obtained photosensitive resin composition is better. More preferably, the chemical nickel-gold resistant additive is selected from ion exchange resin. The photosensitive resin composition provided by the present invention includes an alkali-soluble resin, and the alkali-soluble resin and the ion exchange resin have better compatibility. Therefore, when the ion exchange resin is selected as the chemical nickel-gold resistant additive, it is better to improve the chemical resistance, flexibility and resolvability of the photosensitive resin composition, thereby making its comprehensive performance better.

[0044] Another aspect of the present invention provides a photosensitive dry film, which is obtained by coating and baking the above-mentioned photosensitive resin composition. The photosensitive dry film has excellent gold resistance, flexibility and resolution, and has better comprehensive performance.

[0045] Another aspect of the present invention provides a cured film, which is obtained by coating, baking and curing the above-mentioned photosensitive resin composition, or by curing the above-mentioned photosensitive dry film. The cured film has excellent chemical resistance, flexibility and resolution, and has better comprehensive performance.

[0046] Another aspect of the present invention provides a circuit board, which includes the above-mentioned photosensitive dry film or the above-mentioned cured film and has better comprehensive performance.

[0047] The present application is further described in detail below in conjunction with specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in the present application.

[0048] Here is the purchase information of some of the materials used in the examples and comparative examples:

[0049] Bisphenol F type acid-modified epoxy acrylate resin: (Nippon Kayaku ZFR-1401H, solid content 60%, acid value 98mgKOH / g); acrylate resin: (Daichol CYCLOMER P(ACA)Z250, solid content 45%, acid value 70mgKOH / g); 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole: (Changzhou Qiangli Electronics); 9-phenylacridine: (Shanghai TCI Chemical); cresol novolac type epoxy resin: (DIC EPICLON N-660, epoxy equivalent 202-212g / eq, softening point 61~69℃); bisphenol F type epoxy resin (Nippon Kayaku jER828NER-7403, epoxy equivalent 300g / eq, softening point 58℃); chlorine method rutile titanium oxide: (DuPont R931, particle size 0.3 micron); barium sulfate: (Sakai Chemical BARIACE B-30, particle size 0.1 micron); sulfated rutile titanium oxide: (Sakai Chemical R-7E, particle size 1.5 micron); sulfated rutile titanium oxide: (Sakai Chemical R-7E, particle size 5.0 micron); silica: (Zhongke Keyou, particle size 10 micron); silica: (Zhongke Keyou, particle size 20 micron); stearic acid acrylate: (Osaka Organic Chemical, double bond equivalent is 325g / mol); ethoxylated nonylphenol acrylate: (Kedi Chemical LM158, double bond equivalent 450g / mol); poly(propylene glycol) diacrylate: (McLean, double bond equivalent 527g / mol); propoxylated trihydroxyethylpropane tri(propyl) acrylate: (Sartomer, double bond equivalent 213g / mol).

[0050] Example 1

[0051] The components of the photosensitive resin composition include, by weight:

[0052]

[0053] Example 2

[0054] The components of the photosensitive resin composition include, by weight:

[0055]

[0056]

[0057] Example 3

[0058] The components of the photosensitive resin composition include, by weight:

[0059]

[0060]

[0061] Example 4

[0062] The components of the photosensitive resin composition include, by weight:

[0063]

[0064] Example 5

[0065] The components of the photosensitive resin composition include, by weight:

[0066]

[0067]

[0068] Example 6

[0069] The components of the photosensitive resin composition include, by weight:

[0070]

[0071]

[0072] Example 7

[0073] The components of the photosensitive resin composition include, by weight:

[0074]

[0075] Example 8

[0076] The components of the photosensitive resin composition include, by weight:

[0077]

[0078]

[0079] Example 9

[0080] The components of the photosensitive resin composition include, by weight:

[0081]

[0082]

[0083] Example 10

[0084] The components of the photosensitive resin composition include, by weight:

[0085]

[0086] Embodiment 11

[0087] The components of the photosensitive resin composition include, by weight:

[0088]

[0089]

[0090] Example 12

[0091] The components of the photosensitive resin composition include, by weight:

[0092]

[0093]

[0094] Embodiment 13

[0095] The components of the photosensitive resin composition include, by weight:

[0096]

[0097] Embodiment 14

[0098] The components of the photosensitive resin composition include, by weight:

[0099]

[0100]

[0101] Embodiment 15

[0102] The components of the photosensitive resin composition include, by weight:

[0103]

[0104]

[0105] Example 16

[0106] The components of the photosensitive resin composition include, by weight:

[0107]

[0108] Embodiment 17

[0109] The components of the photosensitive resin composition include, by weight:

[0110]

[0111]

[0112] Embodiment 18

[0113] The components of the photosensitive resin composition include, by weight:

[0114]

[0115]

[0116] Embodiment 19

[0117] The components of the photosensitive resin composition include, by weight:

[0118]

[0119] Embodiment 20

[0120] The components of the photosensitive resin composition include, by weight:

[0121]

[0122]

[0123] Embodiment 21

[0124] The components of the photosensitive resin composition include, by weight:

[0125]

[0126]

[0127] Embodiment 22

[0128] The components of the photosensitive resin composition include, by weight:

[0129]

[0130] Embodiment 23

[0131] The components of the photosensitive resin composition include, by weight:

[0132]

[0133]

[0134] Embodiment 24

[0135] The components of the photosensitive resin composition include, by weight:

[0136]

[0137]

[0138] Embodiment 25

[0139] The components of the photosensitive resin composition include, by weight:

[0140]

[0141] Embodiment 26

[0142] The components of the photosensitive resin composition include, by weight:

[0143]

[0144]

[0145] Embodiment 27

[0146] The components of the photosensitive resin composition include, by weight:

[0147]

[0148]

[0149] Embodiment 28

[0150] The components of the photosensitive resin composition include, by weight:

[0151]

[0152] Embodiment 29

[0153] The components of the photosensitive resin composition include, by weight:

[0154]

[0155] Embodiment 30

[0156] The components of the photosensitive resin composition include, by weight:

[0157]

[0158]

[0159] Embodiment 31

[0160] The components of the photosensitive resin composition include, by weight:

[0161]

[0162] Embodiment 32

[0163] The components of the photosensitive resin composition include, by weight:

[0164]

[0165] Embodiment 33

[0166] The components of the photosensitive resin composition include, by weight:

[0167]

[0168]

[0169] Embodiment 34

[0170] The components of the photosensitive resin composition include, by weight:

[0171]

[0172]

[0173] Embodiment 35

[0174] The components of the photosensitive resin composition include, by weight:

[0175]

[0176] Embodiment 36

[0177] The components of the photosensitive resin composition include, by weight:

[0178]

[0179]

[0180] Embodiment 37

[0181] The difference between Example 37 and Example 1 is that the filler is silicon dioxide, and its particle size is 20 μm. In terms of mass fraction, the components of the photosensitive resin composition include:

[0182]

[0183]

[0184] Embodiment 38

[0185] The components of the photosensitive resin composition include, by weight:

[0186]

[0187] Comparative Example 1

[0188] The difference between Comparative Example 1 and Example 1 is that no chemical nickel-gold resistant additive is added.

[0189] The photosensitive resin compositions in the above-mentioned embodiments and comparative examples were used to prepare cured films by the following method to test the related properties such as chemical resistance, flexibility, and analytical properties. The results are shown in Table 1. The preparation process includes: coating, drying, film lamination, exposure, development, and thermal curing. The specific preparation method and test method are as follows:

[0190] (1) Preparation method:

[0191] Coating process: coating the photosensitive resin composition on the support film, preferably using a coater, a rod coater, a wire rod coater, a roller coater, or a curtain coater. The material of the support film is preferably polyethylene terephthalate (PET) or polycarbonate (PC). In the test of the present invention, a coater is used for coating, the coating thickness is 25 μm, and the material of the support film is polyethylene terephthalate (PET).

[0192] Drying process: Place the support film coated with the photosensitive resin composition in an electric hot air drying oven to remove the solvent by drying to form a photosensitive dry film. The oven drying temperature is preferably below 100°C, preferably 85°C, and the drying time is 15 to 45 minutes. In the test of the present invention, 85°C and 30 minutes are selected.

[0193] Laminating process: The pre-dried photosensitive dry film is falsely pasted on the surface of the PCB (printed circuit board), and then the photosensitive dry film is compacted with a vacuum laminating machine to form a laminated sample of "support film + photosensitive layer + copper clad board"; this process must ensure that the bubbles between the circuits are completely exhausted.

[0194] Exposure process: Select appropriate film or LDI design according to the target pattern, and selectively expose the photosensitive layer. High-pressure mercury lamp, LED exposure machine, LDI exposure machine, ultra-high-pressure mercury lamp, xenon lamp, carbon arc lamp and other ultraviolet light sources can be used for exposure. The test of this invention takes high-pressure mercury lamp as an example, and the exposure energy is 400mJ / cm 2 .

[0195] Development process: Development refers to dissolving the unexposed part of the photosensitive layer in the exposure process by an alkaline developer, while the exposed part remains unchanged. The unexposed area is soluble, and the exposed area is insoluble. The difference in solubility before and after exposure is the key to development. Horizontal development or vertical development can be used. The concentration, temperature and development time of the developer are very important. If the concentration is too high or the temperature is too high, the developer will dissolve the photosensitive adhesive layer too strongly, causing the circuit pattern to deform or distort. If the concentration is too low or the temperature is too low, the developer cannot effectively dissolve the unexposed part, resulting in unclear or incomplete circuit patterns. The developer recommends 1wt% sodium carbonate aqueous solution or 1wt% potassium carbonate aqueous solution, the development temperature is recommended to be 28-32°C, and the development pressure is recommended to be 0.2-0.4MPa. The developer tested in the present invention is a 1wt% sodium carbonate aqueous solution, the development temperature is 30°C, and the development pressure is 0.3MPa.

[0196] Thermal curing process: The developed photosensitive layer is cured by heating to form a patterned cured film. The thermal curing temperature is recommended to be 125-165° C. and the thermal curing time is recommended to be 0.5-1 hour. In the test of the present invention, the thermal curing temperature is selected to be 150° C. and the thermal curing time is 1 hour.

[0197] (2) Performance Characterization

[0198] Resistance to electroplating: First, perform electroplating nickel-gold surface treatment on the surface of the cured film. The treatment process includes the following steps in sequence: degreasing → water washing → micro-etching → water washing → acid washing → pre-immersion → nickel activation → water washing → post-immersion → water washing → nickel immersion → water washing → drying. Then, use a grid knife to cut the surface after electroplating nickel-gold surface treatment. Then, use 3M 600 tape to pull it up at 90° to see if it falls off. Record the number of grids that fall off when it is pulled up for the first time. If no abnormality occurs, repeat the 3M 600 tape pull up at 90° (new tape needs to be replaced each time). If there is an abnormality, record the number of times it falls off.

[0199] Resolution: The resolution was evaluated using film RP-4: um, L / S = n / 400. After development, it was observed using a scanning electron microscope (SEM). The minimum line width with good side morphology and complete development was used as the evaluation standard.

[0200] Flexibility: The cured film was folded in half at 180° (R = 0 mm) and a load of 1 kg was applied. The film was then restored to a flat surface. The folded portion was then folded 180° with the substrate inside and a load of 1 kg was applied. The film was observed under a ×200 optical microscope. The number of cracks that began to appear was recorded and evaluated based on the following criteria:

[0201] ◎: No cracks on the cured film after folding 20 times;

[0202] ○: After folding 10 times, there are slight cracks on the cured film;

[0203] △: Folded 6 times, slight cracks on the cured film;

[0204] ×: The cured film was cracked after being folded in half twice.

[0205] Undercut (side etching): Slice the cured film after thermal curing, observe the cross section with a metallographic microscope, obtain the size of the side etching and record the data (which can reflect the deep curing performance of the cured film).

[0206] Table 1

[0207]

[0208]

[0209]

[0210] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0211] Examples 1 to 38 are cured films prepared using the photosensitive resin composition formula proposed in the present invention. According to the data in Table 1, the present invention can effectively improve the chemical gold resistance, resolvability, flexibility and deep curing performance of the photosensitive resin composition during the chemical nickel-gold treatment process by adding different types of chemical nickel-gold resistant additives to the photosensitive resin composition, thereby improving the comprehensive performance of the cured film. In particular, by controlling the proportion of each component in the photosensitive resin composition formula within the preferred range, the comprehensive performance of the cured film, such as chemical gold resistance, resolvability, flexibility and deep curing performance, is better. The photosensitive resin composition in Comparative Example 1 does not add a chemical nickel-gold resistant additive. According to the data in Table 1, the prepared cured film has poor chemical gold resistance, especially, it is far from the comprehensive effect under the preferred conditions in the embodiments of the present invention.

[0212] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that: The photosensitive resin composition comprises: an alkali-soluble resin, a photoinitiator, a thermal curing agent and a chemical-resistant nickel-gold additive; wherein: The chemical resistant nickel-gold deposition additive is selected from one or more of silicates, transition metal compounds, xanthate compounds, dithiocarbamate derivatives, cucurbitacin compounds, polyether organics, crown ether compounds or ion exchange resins.

2. The photosensitive resin composition according to claim 1, characterized in that: The photosensitive resin composition further comprises: a photopolymerizable monomer and an optional filler; Preferably, the components of the photosensitive resin composition include, by weight: 100 parts of the alkali-soluble resin, 0.1 to 50 parts of the photopolymerizable monomer, 0.1 to 5 parts of the photoinitiator, 5 to 20 parts of the thermal curing agent, 0.01 to 30 parts of the chemical nickel-gold resistant additive, and 0 to 150 parts of the filler; Preferably, the chemical nickel-gold resistant additive is selected from one or more of the silicate, the transition metal compound, the xanthate compound, the dithiocarbamate derivative, the cucurbitacin compound or the crown ether compound, and the components of the photosensitive resin composition include, by weight: 100 parts of the alkali-soluble resin, 0.1 to 50 parts of the photopolymerizable monomer, 0.1 to 5 parts of the photoinitiator, 5 to 20 parts of the thermal curing agent, 0.01 to 5 parts of the chemical nickel-gold resistant additive, and 0 to 150 parts of the filler; or, The chemical resistant nickel-gold precipitating additive is selected from the polyether organic matter, and the components of the photosensitive resin composition include, by weight: 100 parts of the alkali-soluble resin, 0.1 to 50 parts of the photopolymerizable monomer, 0.1 to 5 parts of the photoinitiator, 5 to 20 parts of the thermal curing agent, 0.01 to 15 parts of the chemical resistant nickel-gold precipitating additive, and 0 to 150 parts of the filler; or, The chemical nickel-gold resistant additive is selected from the ion exchange resin, and the components of the photosensitive resin composition include, by mass: 100 parts of the alkali-soluble resin, 0.1 to 50 parts of the photopolymerizable monomer, 0.1 to 5 parts of the photoinitiator, 5 to 20 parts of the thermal curing agent, 1 to 30 parts of the chemical nickel-gold resistant additive, and 0 to 150 parts of the filler.

3. The photosensitive resin composition according to claim 1, characterized in that: The chemical nickel-gold resistant additive is a compound of the silicate and the ion exchange resin, and the components of the photosensitive resin composition include, by weight: 100 parts of the alkali-soluble resin, 0.1-50 parts of the photopolymerizable monomer, 0.1-5 parts of the photoinitiator, 5-20 parts of the thermal curing agent, 0.02-30 parts of the chemical nickel-gold resistant additive, and 0-150 parts of the filler; wherein the silicate and the ion exchange resin are each independently selected from 0.01-15 parts; preferably, the weight ratio of the silicate to the ion exchange resin is (1-5):1; more preferably, the weight ratio of the silicate to the ion exchange resin is (1.5-2.5):1; or, The chemical nickel-gold resistant additive is a compound of the transition metal compound and the ion exchange resin, and the components of the photosensitive resin composition include, by weight: 100 parts of the alkali-soluble resin, 0.1 to 50 parts of the photopolymerizable monomer, 0.1 to 5 parts of the photoinitiator, 5 to 20 parts of the thermal curing agent, 0.02 to 30 parts of the chemical nickel-gold resistant additive, and 0 to 150 parts of the filler; wherein the transition metal compound and the ion exchange resin are each independently selected from 0.01 to 15 parts; preferably, the weight ratio of the transition metal compound to the ion exchange resin is (1 to 5):1; more preferably, the weight ratio of the transition metal compound to the ion exchange resin is (1.5 to 2.5):

1.

4. The photosensitive resin composition according to any one of claims 1 to 3, characterized in that: The transition metal compound is selected from one or more of a pentavalent transition metal compound, a hexavalent transition metal compound or a heptavalent transition metal compound; Preferably, the pentavalent metal compound is selected from one or more of vanadium pentoxide, hydrated vanadium pentoxide, titanium vanadate, aluminum vanadate, zirconium vanadate, phosphovanadic acid, vanadium molybdate, vanadium ferrocyanide, niobium pentoxide, hydrated niobium pentoxide, tantalum pentoxide, hydrated tantalum pentoxide, antimony pentoxide and hydrated antimony pentoxide; Preferably, the hexavalent transition metal compound is selected from one or more of antimony tungstate, titanium antimonate, tin antimonate, iron antimonate, aluminum antimonate, chromium antimonate, tantalum antimonate, manganese antimonate, bismuth antimonate, phosphoantimonic acid and antimony molybdic acid; Preferably, the heptavalent transition metal compound is selected from one or more of potassium permanganate, calcium permanganate and aluminum permanganate; Preferably, the silicate is selected from one or more of metal silicates, borosilicates, aluminosilicates and beryllium silicates; Preferably, the metal cation contained in the silicate is Na + , K + Mg 2+ , Ca 2+ , Ba 2+ or Al 3+ At least one of .

5. The photosensitive resin composition according to any one of claims 1 to 3, characterized in that: The polyether organic compound is a polyether organic compound containing -COC- repeating units; more preferably, the polyether organic compound is at least one of polyethylene oxide, polyepichlorohydrin, epichlorohydrin-ethylene oxide copolymer and epichlorohydrin-ethylene oxide-propylene oxide copolymer; preferably, the weight average molecular weight of the polyether organic compound is 400 to 12000; Preferably, the xanthate compound is selected from one or more of potassium xanthate, zinc xanthate, sodium xanthate, sodium ethyl xanthate, sodium isopropyl xanthate, xanthate esters, isopentyl xanthate propylene esters, and substituted or unsubstituted alkyl dixanthate; More preferably, the substituted or unsubstituted alkyl dixanthate is selected from one or more of methylene dixanthate, dipropylene glycol dixanthate, triethylene glycol dixanthate, ethylene bis(isobutyl xanthate), methylene bis(n-butyl xanthate), methylene bis(tetrahydrofurfuryl xanthate), and p-xylene bis(n-butyl xanthate); Preferably, the dithiocarbamate derivative is selected from one or more of zinc dibutyl dithiocarbamate, zinc diethyl dithiocarbamate, zinc dibutyl dithiocarbamate and zinc ethylphenyl dithiocarbamate; Preferably, the crown ether compound is a nitrogen-branched lariat crown ether compound containing a central functional group; further preferably, the crown ether compound is N-phenoxyethyl monoaza-18-crown-6 and / or N-phenoxyethyl monoaza-15-crown-5; Preferably, the ion exchange resin is a cation exchange resin and / or an anion exchange resin; further preferably, the ion exchange resin is a styrene ion exchange resin and / or an acrylic ion exchange resin; more preferably, the styrene ion exchange resin is selected from type 731, type 732, type D113 or type 110, and the acrylic ion exchange resin is selected from type D151 or type D152; Preferably, the weight average molecular weight of the ion exchange resin is 300 to 8000; Preferably, the cucurbitacin compound is a cucurbitacin homologue and / or a cucurbitacin derivative; more preferably, the cucurbitacin compound is a five-membered cucurbitacin compound and / or a symmetrical tetramethyl six-membered cucurbitacin compound.

6. The photosensitive resin composition according to any one of claims 1 to 3, characterized in that: The alkali-soluble resin is selected from one or more of epoxy acrylic resin, styrene acrylic resin and polyurethane acrylic resin; Preferably, the epoxy acrylic resin is selected from one or more of carboxylic acid-modified bisphenol A epoxy resin, carboxylic acid-modified bisphenol F epoxy resin, carboxylic acid-modified novolac epoxy resin, and carboxylic acid-modified o-cresol epoxy resin; Preferably, the styrene acrylic resin is a carboxylic acid-modified styrene acrylic resin; more preferably, the carboxylic acid-modified styrene acrylic resin has a weight average molecular weight of 30,000 to 200,000 and a glass transition temperature of 90 to 150° C.; Preferably, the polyurethane acrylic resin is selected from one or more of aliphatic polyurethane acrylic resin, alicyclic polyurethane acrylic resin and aromatic polyurethane acrylic resin; Preferably, the weight average molecular weight of the alkali-soluble resin is 10,000 to 300,000; more preferably, the acid value of the alkali-soluble resin is 45 to 200 mgKOH / g; Preferably, the photopolymerizable monomer is selected from one or more of a monofunctional photopolymerizable monomer, a difunctional photopolymerizable monomer, a trifunctional photopolymerizable monomer or a multifunctional photopolymerizable monomer; Preferably, the monofunctional photopolymerizable monomer is selected from methacrylamide, N-(hydroxymethyl)methacrylamide, N-(hydroxymethyl)acrylamide, N-(methoxymethyl)methacrylamide, N-(methoxymethyl)acrylamide, N-(ethoxymethyl)methacrylamide, N-(ethoxymethyl)acrylamide, N-(propoxymethyl)methacrylamide, N-(propoxymethyl)acrylamide, N-(butoxymethoxymethyl)methacrylamide, N-(butoxymethoxymethyl)acrylamide, Amide, methacrylic acid, acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, cyclohexyl acrylate, 2-hydroxyethyl (meth) acrylate Ester, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxybutyl acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, 2-acryloyloxy-2-hydroxypropyl phthalate, glyceryl mono (meth) acrylate, glyceryl mono acrylate, tetrahydrofurfuryl (meth) acrylate , tetrahydrofurfuryl acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminoethyl acrylate, glycidyl (meth) acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl acrylate or at least one of a semi-(meth) acrylate of a phthalic acid derivative, and a semi-acrylate of a phthalic acid derivative; Preferably, the difunctional photopolymerizable monomer is selected from at least one of tricyclodecane dimethanol diacrylate, propylene glycol di(meth)acrylate, propylene glycol diacrylate, pentaerythritol di(meth)acrylate, pentaerythritol diacrylate, butanediol di(meth)acrylate, butanediol diacrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol diacrylate, 1,6-hexanediol dipropionate or 1,6-hexanediol di(meth)propionate; Preferably, the trifunctional photopolymerizable monomer is selected from at least one of trimethylolpropane tri(meth)acrylate, trimethylolpropane triacrylate, propoxy-modified trimethylolpropane tri(meth)acrylate, propoxy-modified trimethylolpropane triacrylate, tri(2-hydroxyethyl)isocyanuric acid triacrylate, pentaerythritol tri(meth)acrylate or pentaerythritol triacrylate; Preferably, the multifunctional photopolymerizable monomer is selected from at least one of di-trimethylolpropane tetraacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetraacrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate or dipentaerythritol hexa(meth)acrylate; Preferably, the photoinitiator is selected from at least one of a cleavage-type free radical initiator or a hydrogen abstraction-type free radical initiator; Preferably, the cleavage-type free radical initiator is selected from at least one of α-hydroxyketone derivative initiators, α-aminoketone derivative initiators, acylphosphorus oxide initiators or oxime ester initiators; Preferably, the hydrogen abstraction free radical initiator is selected from at least one of benzophenone and its derivative initiators, thioxanthone and its derivative initiators, anthraquinone and its derivative initiators, or titanocene initiators; Preferably, the thermal curing agent is selected from one or more of isocyanate compounds, blocked isocyanate compounds, amino resins, benzoxazine resins, carbodiimide resins, cyclic carbonate compounds, epoxy compounds, multifunctional oxetane compounds and episulfide resins; Preferably, the thermosetting agent is an epoxy compound; preferably, the epoxy compound is an epoxy resin; preferably, the softening point of the epoxy resin is 40 to 200°C, and the epoxy equivalent of the epoxy resin is 50 to 350 g / eq.; more preferably, the softening point of the epoxy resin is 50 to 100°C, and the epoxy equivalent of the epoxy resin is 50 to 300 g / eq.; further preferably, the epoxy equivalent of the epoxy resin is 100 to 200 g / eq.; Preferably, the epoxy resin is selected from one or more of bisphenol epoxy resin, biphenyl epoxy resin, novolac epoxy resin, epoxy resin containing naphthalene ring and alicyclic epoxy resin; Preferably, the material of the filler is selected from one or more of titanium black, carbon black, iron oxide, titanium oxide, barium sulfate, silicon dioxide, calcium carbonate and zinc oxide; Preferably, the particle size of the filler is 0.1-20 μm; more preferably, the particle size of the filler is 0.2-5 μm.

7. The photosensitive resin composition according to any one of claims 1 to 6, characterized in that: The chemical resistant nickel-gold precipitate additive is selected from polyether organic matter and / or ion exchange resin; Preferably, the chemical resistant nickel-gold deposition additive is selected from ion exchange resin.

8. A photosensitive dry film, characterized in that: The photosensitive dry film is obtained by coating and baking the photosensitive resin composition according to any one of claims 1 to 7.

9. A cured film, characterized in that: The cured film is obtained by coating, baking and curing the photosensitive resin composition according to any one of claims 1 to 7 or by curing the photosensitive dry film according to claim 8.

10. A circuit board, characterized in that: The circuit board comprises a cured film obtained by coating, baking and curing the photosensitive resin composition described in any one of 1 to 7, or a cured film obtained by curing the photosensitive dry film described in claim 8, or a cured film described in claim 9.

Images