CN114488691A - Photosensitive solder resist dry film and preparation method thereof - Google Patents

Photosensitive solder resist dry film and preparation method thereof Download PDF

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CN114488691A
CN114488691A CN202210192270.1A CN202210192270A CN114488691A CN 114488691 A CN114488691 A CN 114488691A CN 202210192270 A CN202210192270 A CN 202210192270A CN 114488691 A CN114488691 A CN 114488691A
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hollow porous
porous sio
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parts
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CN114488691B (en
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杨仁鸿
张海深
杨忠平
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Guangdong Chengzhan Technology Co.,Ltd.
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Heyuan Chengzhan Technology Co ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds

Abstract

The invention provides a photosensitive solder resist dry film and a preparation method thereof, belonging to the technical field of photosensitive materials of chip carrier plates and electronic circuit boards. The preparation method comprises the following steps: s1, preparing resin; s2, preparing and dispersing; and S3, coating. Compared with the photosensitive solder resist ink, the photosensitive solder resist dry film prepared by the invention not only becomes a solid film, but also has greatly reduced VOC content, and is more green, safe and environment-friendly; the manufacturing process of the photosensitive solder mask process of the electronic circuit board is greatly simplified; meanwhile, the material proportion and parameters are adjusted according to the requirements of a chip carrier plate, a similar carrier plate, a high-density interconnection HDI plate and a multilayer circuit board, so that the photosensitive solder mask meets the characteristics of products in the industries, and the photosensitive solder mask has a wide application prospect.

Description

Photosensitive solder resist dry film and preparation method thereof
Technical Field
The invention relates to the technical field of photosensitive dry films, in particular to a photosensitive solder resist dry film and a preparation method thereof.
Background
In general, in a printed circuit board used for electronic equipment and the like, particularly an integrated circuit, a solder resist layer is formed in a region other than a connection hole on a substrate on which a circuit pattern is formed, in order to prevent solder from adhering to an unnecessary portion and prevent a conductor of a circuit from being exposed and corroded by oxidation and humidity when an electronic component is mounted.
With the recent trend toward higher precision and higher density of printed wiring boards due to the reduction in weight, size, and size of electronic devices, it is now becoming mainstream to form solder resists using so-called photo solder resists by applying a photosensitive resin ink on a substrate, patterning the ink by exposure and development, and then completely curing the patterned resin by heating and/or light irradiation.
Further, there has been proposed a technique for forming a solder resist layer using a so-called photosensitive dry film, which does not use a liquid photosensitive resin ink as described above and does not require a drying step after ink application. When the photosensitive dry film solder resist is used, the ink drying step can be omitted as compared with the case of forming by wet coating as described above, and since the dry film is pressed against the circuit board, air bubbles are less likely to be introduced between the board and the solder resist, and the filling property of the concave portion on the board surface is improved. Further, since the exposure is performed in a state where the photosensitive solder resist dry film is covered with the support film, the influence of the inhibition of curing by oxygen is small, the obtained solder resist layer has higher surface smoothness and surface hardness than those in the case of wet coating, and the discharge of VOC can be reduced by replacing the photosensitive solder resist ink with the photosensitive solder resist dry film, which is safer and more environmentally friendly.
Although the reliability of the dry film solder mask is better, the existing dry film solder mask has some problems in use, such as the strict curing condition of the existing dry film solder mask, insufficient curing if the curing temperature is low or the curing time is short, the dry film solder mask is affected by a solvent during cleaning, cracks can be generated during thermal stress, the dry film solder mask has poor thermal shock resistance, and the circuit board covered with the dry film solder mask has the cracks of the solder mask after being circulated for 100 times at the temperature of-40 ℃ to +100 ℃. Meanwhile, since the printed circuit board and the flexible circuit board carry electronic instruments, they are required to have good flame retardancy. Among them, the flexible printed circuit board is usually a polyimide substrate, which is a different film from a printed circuit board of a glass epoxy substrate, and has poor flame retardancy. Therefore, the photosensitive dry film solder resist on the substrate is required to have a good flame retardant property.
Jp 2012-141605 a teaches that good design properties can be obtained by roughening the surface of the solder resist layer to improve wiring hiding power or suppress glossiness, and describes that the surface of the solder resist layer can be roughened by setting the surface roughness Ra of the support film to a range of 0.2 to 3 μm when the solder resist layer is formed using a photosensitive dry film.
Jp 2007-41107 a proposes an alkali aqueous solution-soluble resin obtained by adding a polybasic acid anhydride to a reaction product of a diphenol novolak type epoxy resin and an unsaturated monocarboxylic acid, and an alkali aqueous solution-soluble photosensitive resin composition containing a diphenol novolak type epoxy resin as a curing agent and a photopolymerization initiator, but the low warpage and bendability are insufficient.
Disclosure of Invention
Compared with photosensitive barrier ink, the photosensitive solder-resist dry film and the preparation method thereof provided by the invention have the advantages that the VOC content is greatly reduced, the green, safe and environment-friendly effects are realized, and meanwhile, the photosensitive solder-resist dry film has good flame retardance, high and low temperature resistance, good mechanical property, low warpage, excellent bending property, excellent welding heat resistance, gold plating resistance and other characteristics.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a photosensitive solder resist dry film, which comprises the following steps:
s1, resin preparation: reacting a solvent, o-cresol formaldehyde epoxy resin, triphenylphosphine, a polymerization inhibitor and methacrylic acid at 90-120 ℃ for 4-24h, and then adding tetrahydrophthalic anhydride to react at 80-120 ℃ for 4-12h to obtain reacted resin;
s2, burdening and dispersing: the resin, the pigment, the photoinitiator, the melamine, the barium sulfate, the defoaming agent, the dibasic ester, the thermal curing agent and the bentonite modified hollow porous SiO reacted in the step S1 are mixed2/Al(OH)3Dispersing and mixing the nano microspheres and the flame retardant uniformly at a high speed to obtain a photosensitive solder resist composition;
s3, coating: and (4) uniformly coating the photosensitive solder mask composition obtained in the step (S2) on a bright-face or pressed-face PET (polyethylene terephthalate) film by using an extrusion film head, baking the film by using a tunnel oven, compounding a layer of PE (polyethylene) protective film on the film to obtain a semi-finished photosensitive solder mask dry film, and finally cutting the film into finished photosensitive solder masks with different widths and lengths according to requirements.
As a further improvement of the present invention, the thermal curing agent is triglycidyl isocyanurate; the defoaming agent is at least one selected from emulsified silicone oil, a higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane; the polymerization inhibitor is selected from at least one of ferric chloride, tert-butyl catechol, copper naphthenate, p-tert-butyl catechol, phenothiazine, hydroquinone, diphenylamine, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butyl hydroquinone and 2, 5-di-tert-butyl hydroquinone; the photoinitiator is selected from 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, methyl benzoylformate, methyl acetate, and the like, Benzoin, benzoin bis-methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diphenylethanone, α -dimethoxy- α -phenylacetophenone, α -diethoxyacetophenone, α -hydroxyalkylphenone, α -aminoalkylphenone, aroylphosphine oxide, bisbenzoylphenylphosphine oxide, benzophenone, 2, 4-dihydroxybenzophenone, Michler's ketone, thiopropoxythioxanthone, isopropylthioxanthone, diaryliodonium salts, triaryliodonium salts, alkyliodonium salts, cumeneferrocene hexafluorophosphate; the pigment is selected from at least one of phthalocyanine blue, phthalocyanine green, permanent violet, permanent orange, pigment yellow, golden light red and permanent red; the flame retardant is at least one selected from the group consisting of ammonium polyphosphate, phosphamine, tricresyl phosphate, n-butyl bis (hydroxypropyl) phosphine oxide, trishydroxypropyl phosphine oxide, cyclooctyl hydroxypropyl phosphine oxide, and p-bis (2, 2-cyanoethyl phosphine oxide methyl) tetramethylbenzene.
As a further improvement of the invention, in step S1, the mass ratio of the o-cresol formaldehyde epoxy resin, the triphenylphosphine, the tetrahydrophthalic anhydride, the polymerization inhibitor and the methacrylic acid is 178: (0.9-1.5): (90-170): (0.05-0.15): (80-90); the solvent comprises tetramethylbenzene and dibasic ester, the content of the solvent is 35-45 wt% of the total weight, wherein the weight ratio of the tetramethylbenzene to the dibasic ester is 1: (2-4).
As a further improvement of the invention, the reacted resin, pigment, photoinitiator, melamine, barium sulfate, defoamer, dibasic ester, thermal curing agent and bentonite modified hollow porous SiO in the step S22/Al(OH)3The mass ratio of the nano microspheres to the flame retardant is (20-40): (0.1-0.5): (2-7): (2-7): (10-30): (1-3): (10-30): (5-10): (10-15): (0.5-1); the high-speed dispersion rotating speed is 10000-12000r/min, and the time is 15-30 min.
As a further improvement of the invention, the bentonite modified hollow porous SiO in the step S22/Al(OH)3The preparation method of the nano-microsphere comprises the following steps:
(1) hollow porous SiO2/Al(OH)3Preparing the nano microspheres: dissolving a surfactant and a pore-forming agent in water, adding aminosilane, stirring for reaction, then adding an ethanol solution of aluminum isopropoxide, continuing the reaction, centrifugally washing and drying to obtain the hollow porous SiO2/Al(OH)3Nano-microspheres;
(2) preparation of the catalyst: dissolving cobalt salt in Tris-HCl buffer solution to obtain catalyst solution;
(3) polydopamine-coated hollow porous SiO2/Al(OH)3Preparing the nano microspheres: the hollow porous SiO prepared in the step (1) is used2/Al(OH)3Dispersing the nano microspheres in water, adding dopamine hydrochloride, adding the catalyst solution prepared in the step (2), heating, stirring, reacting, centrifuging, washing and drying to obtain the polydopamine-coated hollow porous SiO2/Al(OH)3Nano-microspheres;
(4) and (3) bentonite treatment: grinding and sieving bentonite, adding the bentonite into alkali liquor, stirring for reaction, filtering, washing with water to be neutral, and drying to obtain pretreated bentonite;
(5) bentonite modified hollowPorous SiO2/Al(OH)3Preparing the nano microspheres: coating the polydopamine prepared in the step (3) with hollow porous SiO2/Al(OH)3Adding the nano microspheres and the pretreated bentonite prepared in the step (4) into an ethanol water solution, heating and stirring for reaction, centrifuging, washing and drying to obtain the bentonite modified hollow porous SiO2/Al(OH)3And (4) nano microspheres.
As a further improvement of the invention, in the step (1), the mass ratio of the aminosilane, the aluminum isopropoxide, the surfactant and the pore-foaming agent is 100: (30-50): (1-3): (2-4); the aminosilane is selected from at least one of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldiethoxysilane and diethylenetriaminopropyltrimethoxysilane; the surfactant is at least one selected from hexadecyl sodium benzene sulfonate, hexadecyl sodium sulfate, octadecyl sodium benzene sulfonate, octadecyl sodium sulfonate, dodecyl sodium benzene sulfonate, dodecyl sodium sulfate, dodecyl sodium sulfonate and tween-80; the pore-foaming agent is selected from at least one of polyoxyethylene sorbitan fatty acid ester and polyethylene glycol octyl phenyl ether; the drying temperature is 50-70 ℃, and the drying time is 2-4 h; in the step (2), the cobalt salt is selected from at least one of cobalt chloride, cobalt sulfate and cobalt bromide; the pH value of the Tris-HCl buffer solution is 7.8-8.2; co in the catalyst solution2+The ion concentration is 0.5-2 wt%.
As a further improvement of the present invention, the hollow porous SiO in step (3)2/Al(OH)3The mass ratio of the nano microspheres to the dopamine hydrochloride to the catalyst solution is 100: (20-50): (3-7); the heating temperature is 40-60 ℃, and the reaction time is 3-5 h; the mesh number of the sieving screen in the step (4) is 500-1000 meshes; the alkali liquor is NaOH or KOH solution, and OH in the alkali liquor-The concentration of the ions is 0.5-2 mol/L; the stirring reaction time is 1-2 h; in the step (5), the polydopamine-coated nano-microspheres and pretreatmentThe mass ratio of the treated bentonite is 20: (3-7); the ethanol content in the ethanol water solution is 35-60 wt%, and the balance is water; the heating temperature is 60-70 ℃, and the reaction time is 2-4 h.
As a further improvement of the invention, the bentonite modified hollow porous SiO in the step S22/Al(OH)3The preparation method of the nano-microsphere comprises the following steps:
(1) hollow porous SiO2/Al(OH)3Preparing the nano microspheres: dissolving 1-3 parts by weight of surfactant and 2-4 parts by weight of pore-forming agent in water, adding 100 parts by weight of aminosilane, stirring and reacting for 1-2h, then adding an ethanol solution containing 30-50 parts by weight of aluminum isopropoxide, continuing to react for 3-5h, centrifugally washing, and drying at 50-70 ℃ for 2-4h to obtain hollow porous SiO2/Al(OH)3Nano-microspheres;
(2) preparation of the catalyst: dissolving cobalt salt in Tris-HCl buffer solution with the pH value of 7.8-8.2 to obtain catalyst solution, wherein Co in the catalyst solution2+The ion concentration is 0.5-2 wt%;
(3) polydopamine-coated hollow porous SiO2/Al(OH)3Preparing the nano microspheres: 100 parts by weight of the hollow porous SiO prepared in the step (1)2/Al(OH)3Dispersing the nano microspheres in water, adding 20-50 parts by weight of dopamine hydrochloride, adding 3-7 parts by weight of the catalyst solution prepared in the step (2), heating to 40-60 ℃, stirring and reacting for 3-5h, centrifuging, washing and drying to obtain the polydopamine-coated hollow porous SiO2/Al(OH)3Nano-microspheres;
(4) and (3) bentonite treatment: grinding bentonite, sieving with 500-sand-plus-1000-mesh sieve, adding into alkali liquor, stirring and reacting for 1-2h, wherein OH in the alkali liquor-The concentration of ions is 0.5-2mol/L, filtering, washing with water to be neutral, and drying to obtain pretreated bentonite;
(5) bentonite modified hollow porous SiO2/Al(OH)3Preparing the nano microspheres: 20 parts by weight of polydopamine prepared in the step (3) coated hollow porous SiO2/Al(OH)3Adding the nano-microspheres and 3-7 parts by weight of the pretreated bentonite prepared in the step (4) into an ethanol water solution,heating ethanol solution with ethanol content of 35-60 wt% and water in balance to 60-70 deg.C, stirring for 2-4 hr, centrifuging, washing, and drying to obtain bentonite modified hollow porous SiO2/Al(OH)3And (4) nano microspheres.
As a further improvement of the invention, the flame retardant is trishydroxypropyl phosphine oxide.
The invention further protects the photosensitive solder resist dry film prepared by the preparation method.
The invention has the following beneficial effects: the unexposed active group in the photosensitive barrier dry film prepared by the invention reacts with diluted alkali to generate soluble substances which are dissolved, and during development, the active carboxyl of the photosensitive material methacrylic acid of the resin part in the photosensitive barrier dry film and OH in the sodium carbonate solution-Act to form a hydrophilic group-COO-Thus, the unexposed part is dissolved, and the exposed part is not dissolved, thereby playing a good role in imaging;
the invention prepares bentonite modified hollow porous SiO2/Al(OH)3The nano microsphere is prepared by mixing amino silane and water, wherein the amino silane cannot be dissolved in water initially, but forms tiny liquid drops in the process of continuous stirring and dispersion. As the reaction proceeds, the amino groups become protonated, becoming amphiphilic molecules, further stabilizing the silane droplets. After adding aluminum isopropoxide, the aluminum isopropoxide is easily dissolved in silane liquid drops, the protonated amino provides an alkaline environment, the aluminum isopropoxide is efficiently catalyzed to generate a sol-gel process, meanwhile, a hollow sphere structure is gradually formed along with consumption of internal silane, in the presence of a surfactant in the whole process, the microspheres can form a better spherical shape, and meanwhile, under the action of a pore-forming agent, the obtained microspheres have a porous structure, so that the hollow porous SiO is prepared2/Al(OH)3The porous hollow structure enables reacted resin to enter the microspheres in the later preparation of the photosensitive solder-resist dry film, so that the mechanical property is prevented from being influenced;
further, by containing Co2+Under the action of ionic catalyst, the prepared hollow porous SiO2/Al(OH)3The surface of the nano microsphere is coated with a layer of thinner polydopamine, the polydopamine has rich hydroxyl and amino structures, and a large number of hydroxyl structures are formed on the surface of the bentonite after alkali treatment, so that the polydopamine is coated on the hollow porous SiO2/Al(OH)3The nanometer microsphere is easy to be subjected to hydrogen bond adhesion with the bentonite after alkali treatment so as to prepare the bentonite modified hollow porous SiO2/Al(OH)3Nano-microspheres;
the invention modifies the hollow porous SiO by adding bentonite2/Al(OH)3The nano microspheres have a nano rigid structure, so that after the nano rigid structure is added into the photosensitive solder resist composition, the surface of the prepared photosensitive solder resist dry film has relatively uniform roughness Ra, the filling property during underfill filling can be improved, and the adhesion between a curing coated film and a mold material can also be improved;
meanwhile, due to the filler bentonite modified hollow porous SiO2/Al(OH)3The addition of the nano microspheres obviously improves the high temperature resistance and low temperature resistance of the photosensitive solder-resisting dry film, improves the mechanical property of the photosensitive solder-resisting dry film to a certain extent, and obtains the dry film with excellent characteristics such as low warpage, excellent bending property, soldering heat resistance, gold plating resistance and the like;
in the invention, the bentonite modified hollow porous SiO2/Al(OH)3The shell layer of the inner layer of the nano microsphere contains rich SiO2And Al (OH)3The aluminum hydroxide part can release crystal water after being heated, absorb a large amount of heat, inhibit the temperature rise of the polymer, prevent flame retardation, generate a large amount of water vapor in the dehydration decomposition reaction, dilute combustible gas and achieve the flame retardant effect; the photosensitive solder-resist dry film also adds an organic phosphorus flame retardant, particularly tris (hydroxy propyl) phosphine oxide, and most of the organic phosphorus flame retardants have the advantages of low smoke, no toxicity, low halogen, no halogen and the like, and the action mechanism is that the organic phosphorus flame retardant can generate a cross-linked solid substance or a carbonized layer with a more stable structure when being heated, and the formation of the carbonized layer can prevent the polymer from further pyrolysis on one hand and prevent the thermal decomposition products in the carbonized layer from entering a gas phase to participate in the combustion process on the other hand; addition of both trishydroxypropyl phosphine oxide and nanospheresBetter synergistic effect is achieved; the trishydroxypropyl phosphine oxide contains rich hydroxyl structures and is easy to modify with bentonite into hollow porous SiO2/Al(OH)3The amino and the hydroxyl on the surface of the nano microsphere are in hydrogen bond connection, so that a stable compound is formed, and the high-efficiency flame retardant effect is achieved.
The photosensitive solder resist dry film prepared by the invention has the physical characteristics of welding resistance, flame retardance, insulating property and high and low temperature resistance; low warpage, bendability, high glass transition temperature (Tg value) in terms of mechanical properties; meanwhile, the material has the advantages of chemical resistance (gold plating property and other chemicals), high adhesion, high resolution, high precision thickness, rough surface brightness calendaring, thermal expansion coefficient, light sensitivity regulation and control and the like, and the performance is more excellent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a view showing a bentonite-modified hollow porous SiO prepared in production example 12/Al(OH)3TEM images of the nanospheres;
FIG. 2 is a view showing a bentonite-modified hollow porous SiO prepared in production example 12/Al(OH)3SEM image of nanospheres.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The bentonite is purchased from Shijiazhuangdu Yandu mining processing factory, has pH of 8-10, water content less than 5%, and mesh number of 40About 0 mesh, density of 2.5g/cm3Left and right.
Preparation example 1
Bentonite modified hollow porous SiO2/Al(OH)3The preparation method of the nano microsphere comprises the following steps:
(1) hollow porous SiO2/Al(OH)3Preparing the nano microspheres: dissolving 1 part by weight of sodium octadecyl sulfonate and 2 parts by weight of polyoxyethylene sorbitan fatty acid ester in 200 parts by weight of water, adding 100 parts by weight of gamma-aminopropyltrimethoxysilane, stirring for reaction for 1 hour, then adding 50 parts by weight of ethanol solution containing 30 parts by weight of aluminum isopropoxide, continuing to react for 3 hours, centrifuging at 3000r/min for 10 minutes, washing with deionized water, and drying at 50 ℃ for 2 hours to obtain the hollow porous SiO2/Al(OH)3Nano-microspheres;
(2) preparation of the catalyst: dissolving cobalt bromide in Tris-HCl buffer solution with the pH value of 7.8 to obtain catalyst solution, wherein Co in the catalyst solution2+The ion concentration is 0.5 wt%;
(3) polydopamine-coated hollow porous SiO2/Al(OH)3Preparing the nano microspheres: 100 parts by weight of the hollow porous SiO prepared in the step (1)2/Al(OH)3Dispersing the nano microspheres in 200 parts by weight of water, adding 20 parts by weight of dopamine hydrochloride, adding 3 parts by weight of the catalyst solution prepared in the step (2), heating to 40 ℃, stirring and reacting for 3 hours, centrifuging at 3000r/min for 10 minutes, washing with deionized water, and drying at 60 ℃ for 2 hours to obtain the polydopamine-coated hollow porous SiO2/Al(OH)3Nano-microspheres;
(4) and (3) bentonite treatment: grinding 50 parts by weight of bentonite, sieving with a 500-mesh sieve, adding 70 parts by weight of alkali liquor, stirring and reacting for 1h, wherein OH in the alkali liquor-The concentration of ions is 0.5mol/L, the filtration is carried out, the water washing is carried out until the ion concentration is neutral, and the drying is carried out for 2 hours at the temperature of 60 ℃ to obtain the pretreated bentonite;
(5) bentonite modified hollow porous SiO2/Al(OH)3Preparing the nano microspheres: 20 parts by weight of polydopamine prepared in the step (3) coated hollow porous SiO2/Al(OH)3Adding 100 parts by weight of nano microspheres and 3 parts by weight of pretreated bentonite prepared in the step (4)Heating ethanol solution with the ethanol content of 35 wt% and the balance water to 60 ℃ in the ethanol solution, stirring and reacting for 2h, centrifuging at 3000r/min for 10min, washing with deionized water, and drying at 60 ℃ for 2h to obtain the bentonite modified hollow porous SiO2/Al(OH)3And (4) nano microspheres. FIG. 1 shows the prepared bentonite modified hollow porous SiO2/Al(OH)3The TEM image of the nano-microsphere shows that the microsphere is a hollow structure; FIG. 2 shows the prepared bentonite modified hollow porous SiO2/Al(OH)3The SEM image of the nano microsphere shows that the particle size of the microsphere is between 180 nm and 250 nm.
Preparation example 2
Bentonite modified hollow porous SiO2/Al(OH)3The preparation method of the nano microsphere comprises the following steps:
(1) hollow porous SiO2/Al(OH)3Preparing the nano microspheres: dissolving 3 parts by weight of sodium dodecyl benzene sulfonate and 4 parts by weight of polyethylene glycol octyl phenyl ether in 200 parts by weight of water, adding 100 parts by weight of N-beta (aminoethyl) -gamma-aminopropyltriethoxysilane, stirring for reaction for 2 hours, then adding 50 parts by weight of ethanol solution containing 50 parts by weight of aluminum isopropoxide, continuing to react for 5 hours, centrifuging at 3000r/min for 10 minutes, washing with deionized water, and drying at 70 ℃ for 4 hours to obtain the hollow porous SiO2/Al(OH)3Nano-microspheres;
(2) preparation of the catalyst: dissolving cobalt sulfate in Tris-HCl buffer solution with the pH value of 8.2 to obtain catalyst solution, wherein Co in the catalyst solution2+The ion concentration is 2 wt%;
(3) polydopamine-coated hollow porous SiO2/Al(OH)3Preparing the nano microspheres: 100 parts by weight of the hollow porous SiO prepared in the step (1)2/Al(OH)3Dispersing the nano microspheres in 200 parts by weight of water, adding 50 parts by weight of dopamine hydrochloride, adding 7 parts by weight of the catalyst solution prepared in the step (2), heating to 60 ℃, stirring and reacting for 5 hours, centrifuging at 3000r/min for 10 minutes, washing with deionized water, and drying at 60 ℃ for 2 hours to obtain the polydopamine-coated hollow porous SiO2/Al(OH)3Nano-microspheres;
(4) and (3) bentonite treatment: will 50Grinding bentonite in parts by weight, sieving with a 1000-mesh sieve, adding 70 parts by weight of alkali liquor, stirring and reacting for 2 hours, wherein OH in the alkali liquor-The ion concentration is 2mol/L, the filtration and the water washing are carried out until the ion concentration is neutral, and the bentonite after the pretreatment is obtained after the drying for 2 hours at the temperature of 60 ℃;
(5) bentonite modified hollow porous SiO2/Al(OH)3Preparing the nano microspheres: 20 parts by weight of polydopamine prepared in the step (3) coated hollow porous SiO2/Al(OH)3Adding the nano microspheres and 7 parts by weight of the pretreated bentonite prepared in the step (4) into 100 parts by weight of ethanol aqueous solution, heating the ethanol aqueous solution to 70 ℃, stirring and reacting for 4 hours, centrifuging at 3000r/min for 10 minutes, washing with deionized water, and drying at 60 ℃ for 2 hours to obtain the bentonite modified hollow porous SiO2/Al(OH)3And (4) nano microspheres.
Preparation example 3
Bentonite modified hollow porous SiO2/Al(OH)3The preparation method of the nano microsphere comprises the following steps:
(1) hollow porous SiO2/Al(OH)3Preparing the nano microspheres: dissolving 2 parts by weight of sodium hexadecylsulfonate and 3 parts by weight of polyoxyethylene sorbitan fatty acid ester in 200 parts by weight of water, adding 100 parts by weight of gamma-aminopropyltriethoxysilane, stirring for reaction for 1.5h, then adding 50 parts by weight of ethanol solution containing 30-50 parts by weight of aluminum isopropoxide, continuing to react for 4h, centrifuging at 3000r/min for 10min, washing with deionized water, and drying at 60 ℃ for 3h to obtain the hollow porous SiO2/Al(OH)3Nano-microspheres;
(2) preparation of the catalyst: dissolving cobalt chloride in Tris-HCl buffer solution with the pH value of 8 to obtain catalyst solution, wherein Co in the catalyst solution2+The ion concentration is 1 wt%;
(3) polydopamine-coated hollow porous SiO2/Al(OH)3Preparing the nano microspheres: 100 parts by weight of the hollow porous SiO prepared in the step (1)2/Al(OH)3Dispersing the nano microspheres in 200 parts by weight of water, adding 35 parts by weight of dopamine hydrochloride, adding 5 parts by weight of the catalyst solution prepared in the step (2), heating to 50 ℃, and stirringCentrifuging for 10min at 3000r/min for 4h, washing with deionized water, and drying at 60 deg.C for 2h to obtain hollow porous SiO coated with polydopamine2/Al(OH)3Nano-microspheres;
(4) and (3) bentonite treatment: grinding 50 parts by weight of bentonite, sieving with a 700-mesh sieve, adding 70 parts by weight of alkali liquor, stirring and reacting for 1.5h, wherein OH in the alkali liquor-The concentration of ions is 1mol/L, filtering, washing to be neutral, and drying for 2h at 60 ℃ to obtain pretreated bentonite;
(5) bentonite modified hollow porous SiO2/Al(OH)3Preparing the nano microspheres: 20 parts by weight of polydopamine prepared in the step (3) coated hollow porous SiO2/Al(OH)3Adding the nano-microspheres and 5 parts by weight of the pretreated bentonite prepared in the step (4) into 100 parts by weight of ethanol aqueous solution, heating the ethanol aqueous solution to 65 ℃, stirring and reacting for 3 hours, centrifuging at 3000r/min for 10 minutes, washing with deionized water, and drying at 60 ℃ for 2 hours to obtain the bentonite modified hollow porous SiO2/Al(OH)3And (4) nano microspheres.
Comparative preparation example 1
Compared with preparation example 3, the ethanol solution of aluminum isopropoxide was not added in step (1), and other conditions were not changed.
Bentonite modified hollow porous SiO2The preparation method of the nano microsphere comprises the following steps:
(1) hollow porous SiO2Preparing the nano microspheres: dissolving 2 parts by weight of sodium hexadecylsulfonate and 3 parts by weight of polyoxyethylene sorbitan fatty acid ester in 200 parts by weight of water, adding 100 parts by weight of gamma-aminopropyltriethoxysilane, stirring for reaction for 5.5h, centrifuging at 3000r/min for 10min, washing with deionized water, and drying at 60 ℃ for 3h to obtain the hollow porous SiO2Nano-microspheres;
(2) preparation of the catalyst: dissolving cobalt chloride in Tris-HCl buffer solution with the pH value of 8 to obtain catalyst solution, wherein Co in the catalyst solution2+The ion concentration is 1 wt%;
(3) polydopamine-coated hollow porous SiO2Preparing the nano microspheres: 100 parts by weight of the hollow porous material prepared in the step (1)SiO2Dispersing the nano-microspheres in 200 parts by weight of water, adding 35 parts by weight of dopamine hydrochloride, adding 5 parts by weight of the catalyst solution prepared in the step (2), heating to 50 ℃, stirring and reacting for 4 hours, centrifuging at 3000r/min for 10 minutes, washing with deionized water, and drying at 60 ℃ for 2 hours to obtain the polydopamine-coated hollow porous SiO2Nano-microspheres;
(4) and (3) bentonite treatment: grinding 50 parts by weight of bentonite, sieving with a 700-mesh sieve, adding into 70 parts by weight of alkali liquor, stirring and reacting for 1.5h, wherein OH in the alkali liquor-The concentration of ions is 1mol/L, filtering, washing to be neutral, and drying for 2h at 60 ℃ to obtain pretreated bentonite;
(5) bentonite modified hollow porous SiO2Preparing the nano microspheres: adding 20 parts by weight of polydopamine-coated hollow porous SiO2/Al (OH)3 nano microspheres prepared in the step (3) and 5 parts by weight of pretreated bentonite prepared in the step (4) into 100 parts by weight of ethanol aqueous solution, heating the ethanol aqueous solution to 65 ℃, stirring and reacting for 3 hours, centrifuging for 10 minutes at 3000r/min, washing with deionized water, and drying for 2 hours at 60 ℃ to obtain bentonite modified hollow porous SiO2And (4) nano microspheres.
Comparative preparation example 2
Compared with preparation example 3, no pore-forming agent is added, and other conditions are not changed.
Bentonite modified hollow SiO2/Al(OH)3The preparation method of the nano microsphere comprises the following steps:
(1) hollow SiO2/Al(OH)3Preparing the nano microspheres: dissolving 5 parts by weight of sodium hexadecylsulfonate in 200 parts by weight of water, adding 100 parts by weight of gamma-aminopropyltriethoxysilane, stirring for reaction for 1.5h, then adding 50 parts by weight of ethanol solution containing 30-50 parts by weight of aluminum isopropoxide, continuing the reaction for 4h, centrifuging at 3000r/min for 10min, washing with deionized water, and drying at 60 ℃ for 3h to obtain hollow SiO2/Al(OH)3Nano-microspheres;
(2) preparation of the catalyst: dissolving cobalt chloride in Tris-HCl buffer solution with the pH value of 8 to obtain catalyst solution, wherein Co in the catalyst solution2+The ion concentration is 1 wt%;
(3) polydopamine coated hollow SiO2/Al(OH)3Preparing the nano microspheres: 100 parts by weight of the hollow SiO prepared in the step (1)2/Al(OH)3Dispersing the nano microspheres in 200 parts by weight of water, adding 35 parts by weight of dopamine hydrochloride, adding 5 parts by weight of the catalyst solution prepared in the step (2), heating to 50 ℃, stirring and reacting for 4 hours, centrifuging at 3000r/min for 10 minutes, washing with deionized water, and drying at 60 ℃ for 2 hours to obtain the polydopamine-coated hollow SiO2/Al(OH)3Nano-microspheres;
(4) and (3) bentonite treatment: grinding 50 parts by weight of bentonite, sieving with a 700-mesh sieve, adding 70 parts by weight of alkali liquor, stirring and reacting for 1.5h, wherein OH in the alkali liquor-The concentration of ions is 1mol/L, filtering, washing to be neutral, and drying for 2h at 60 ℃ to obtain pretreated bentonite;
(5) bentonite modified hollow SiO2/Al(OH)3Preparing the nano microspheres: 20 parts by weight of polydopamine prepared in the step (3) coated hollow SiO2/Al(OH)3Adding the nano-microspheres and 5 parts by weight of the pretreated bentonite prepared in the step (4) into 100 parts by weight of ethanol aqueous solution, heating the ethanol aqueous solution to 65 ℃, stirring and reacting for 3 hours, centrifuging at 3000r/min for 10 minutes, washing with deionized water, and drying at 60 ℃ for 2 hours to obtain the bentonite modified hollow SiO22/Al(OH)3And (4) nano microspheres.
Comparative preparation example 3
Step (4) was not performed, and other conditions were not changed, as compared with preparation example 3.
Bentonite modified hollow porous SiO2/Al(OH)3The preparation method of the nano microsphere comprises the following steps:
(1) hollow porous SiO2/Al(OH)3Preparing the nano microspheres: dissolving 2 parts by weight of sodium hexadecylsulfonate and 3 parts by weight of polyoxyethylene sorbitan fatty acid ester in 200 parts by weight of water, adding 100 parts by weight of gamma-aminopropyltriethoxysilane, stirring for reaction for 1.5h, then adding 50 parts by weight of ethanol solution containing 30-50 parts by weight of aluminum isopropoxide, continuing to react for 4h, centrifuging at 3000r/min for 10min, washing with deionized water, and dryingDrying at 60 ℃ for 3h to obtain hollow porous SiO2/Al(OH)3Nano-microspheres;
(2) preparation of the catalyst: dissolving cobalt chloride in Tris-HCl buffer solution with the pH value of 8 to obtain catalyst solution, wherein Co in the catalyst solution2+The ion concentration is 1 wt%;
(3) polydopamine-coated hollow porous SiO2/Al(OH)3Preparing the nano microspheres: 100 parts by weight of the hollow porous SiO prepared in the step (1)2/Al(OH)3Dispersing the nano-microspheres in 200 parts by weight of water, adding 35 parts by weight of dopamine hydrochloride, adding 5 parts by weight of the catalyst solution prepared in the step (2), heating to 50 ℃, stirring and reacting for 4 hours, centrifuging at 3000r/min for 10 minutes, washing with deionized water, and drying at 60 ℃ for 2 hours to obtain the polydopamine-coated hollow porous SiO2/Al(OH)3Nano-microspheres;
(4) bentonite modified hollow porous SiO2/Al(OH)3Preparing the nano microspheres: 20 parts by weight of polydopamine prepared in the step (3) coated hollow porous SiO2/Al(OH)3Adding the nano-microspheres and 5 parts by weight of bentonite into 100 parts by weight of ethanol aqueous solution, heating the ethanol aqueous solution to 65 ℃, stirring and reacting for 3 hours, centrifuging at 3000r/min for 10 minutes, washing with deionized water, and drying at 60 ℃ for 2 hours to obtain the bentonite modified hollow porous SiO22/Al(OH)3And (4) nano microspheres.
Comparative preparation example 4
Compared with preparation example 3, steps (4) and (5) are not carried out, and other conditions are not changed
Polydopamine-coated hollow porous SiO2/Al(OH)3The preparation method of the nano microsphere comprises the following steps:
(1) hollow porous SiO2/Al(OH)3Preparing the nano microspheres: dissolving 2 parts by weight of sodium hexadecylsulfonate and 3 parts by weight of polyoxyethylene sorbitan fatty acid ester in 200 parts by weight of water, adding 100 parts by weight of gamma-aminopropyltriethoxysilane, stirring for reaction for 1.5h, then adding 50 parts by weight of ethanol solution containing 30-50 parts by weight of aluminum isopropoxide, continuing the reaction for 4h, centrifuging at 3000r/min for 10min,washing with deionized water, and drying at 60 deg.C for 3 hr to obtain hollow porous SiO2/Al(OH)3Nano-microspheres;
(2) preparation of the catalyst: dissolving cobalt chloride in Tris-HCl buffer solution with the pH value of 8 to obtain catalyst solution, wherein Co in the catalyst solution2+The ion concentration is 1 wt%;
(3) polydopamine-coated hollow porous SiO2/Al(OH)3Preparing the nano microspheres: 100 parts by weight of the hollow porous SiO prepared in the step (1)2/Al(OH)3Dispersing the nano-microspheres in 200 parts by weight of water, adding 35 parts by weight of dopamine hydrochloride, adding 5 parts by weight of the catalyst solution prepared in the step (2), heating to 50 ℃, stirring and reacting for 4 hours, centrifuging at 3000r/min for 10 minutes, washing with deionized water, and drying at 60 ℃ for 2 hours to obtain the polydopamine-coated hollow porous SiO2/Al(OH)3And (4) nano microspheres.
Comparative preparation example 5
Compared with preparation example 3. Steps (2) to (5) are not carried out, and other conditions are not changed
Hollow porous SiO2/Al(OH)3Preparing the nano microspheres: dissolving 2 parts by weight of sodium hexadecylsulfonate and 3 parts by weight of polyoxyethylene sorbitan fatty acid ester in 200 parts by weight of water, adding 100 parts by weight of gamma-aminopropyltriethoxysilane, stirring for reaction for 1.5h, then adding 50 parts by weight of ethanol solution containing 30-50 parts by weight of aluminum isopropoxide, continuing to react for 4h, centrifuging at 3000r/min for 10min, washing with deionized water, and drying at 60 ℃ for 3h to obtain the hollow porous SiO2/Al(OH)3And (4) nano microspheres.
Example 1
The embodiment provides a preparation method of a photosensitive solder resist dry film, which comprises the following steps:
s1, resin reaction: reacting a solvent, 178 parts by weight of o-cresol formaldehyde epoxy resin, 0.9 part by weight of triphenylphosphine, 0.05 part by weight of 2, 5-di-tert-butyl hydroquinone and 80 parts by weight of methacrylic acid at 90 ℃ for 4-24h, and then adding 90 parts by weight of tetrahydrophthalic anhydride to react at 80 ℃ for 4h to obtain reacted resin; the solvent comprises tetramethylbenzene and dibasic ester, the content of the solvent is 35 wt% of the total weight, wherein the weight ratio of the tetramethylbenzene to the dibasic ester is 1: 2;
s2, burdening and dispersing: 20 parts by weight of the resin reacted in the step S1, 0.1 part by weight of phthalocyanine blue, 2 parts by weight of 2-hydroxy-2-methyl-1-phenylpropanone, 2 parts by weight of melamine, 10 parts by weight of barium sulfate, 1 part by weight of polyoxyethylene polyoxypropylene pentaerythritol ether, 10 parts by weight of dibasic ester, 5 parts by weight of triglycidyl isocyanurate, and 10 parts by weight of the bentonite-modified hollow porous SiO prepared in preparation example 1 were mixed together2/Al(OH)3Dispersing the nano-microspheres and 0.5 part by weight of p-bis (2, 2-cyanoethyl phosphine oxide methyl) tetramethylbenzene at the rotating speed of 10000r/min for 15min until the mixture is uniformly mixed to obtain the photosensitive solder resist composition;
s3, coating: and (4) uniformly coating the photosensitive solder mask composition obtained in the step (S2) on a bright-face or pressed-face PET (polyethylene terephthalate) film by using an extrusion film head, baking the film by using a tunnel oven, compounding a layer of PE (polyethylene) protective film on the film to obtain a semi-finished photosensitive solder mask dry film, and finally cutting the film into small rolls with different widths and lengths according to the requirements of customers.
When in use: and (4) storing, transporting and using the photosensitive solder mask prepared in the step (S3) in a non-ultraviolet environment with the low temperature of-10 ℃ and the humidity of 40%, attaching the photosensitive solder mask to a circuit board by using a vacuum or common film sticking machine when a photosensitive solder mask is used for preparing a photosensitive solder mask process, and carrying out exposure, development and curing to obtain the photosensitive solder mask.
Example 2
The embodiment provides a preparation method of a photosensitive solder resist dry film, which comprises the following steps:
s1, resin reaction: reacting a solvent, 178 parts by weight of o-cresol formaldehyde epoxy resin, 1.5 parts by weight of triphenylphosphine, 0.15 part by weight of tert-butyl catechol and 80-90 parts by weight of methacrylic acid at 120 ℃ for 24 hours, and then adding 170 parts by weight of tetrahydrophthalic anhydride to react at 120 ℃ for 12 hours to obtain reacted resin; the solvent comprises tetramethylbenzene and dibasic ester, the content of the solvent is 45 wt% of the total weight, wherein the weight ratio of the tetramethylbenzene to the dibasic ester is 1: 4;
s2, burdening and dispersing: 40 parts by weight of the resin reacted in the step S1, 0.5 part by weight of permanent violet,7 parts by weight of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl]-1-propanone, 7 parts by weight of melamine, 30 parts by weight of barium sulfate, 3 parts by weight of polyoxypropylene glycerol ether, 30 parts by weight of dibasic ester, 10 parts by weight of triglycidyl isocyanurate, 15 parts by weight of the bentonite-modified hollow porous SiO obtained in preparation example 22/Al(OH)3Dispersing the nano-microspheres and 1 part by weight of n-butyl bis (hydroxypropyl) phosphine oxide for 30min at the rotating speed of 12000r/min until the nano-microspheres and the n-butyl bis (hydroxypropyl) phosphine oxide are uniformly mixed to obtain a photosensitive solder resist composition;
s3, coating: and (4) uniformly coating the photosensitive solder mask composition obtained in the step (S2) on a bright-face or pressed-face PET (polyethylene terephthalate) film by using an extrusion film head, baking the film by using a tunnel oven, compounding a layer of PE (polyethylene) protective film on the film to obtain a semi-finished photosensitive solder mask dry film, and finally cutting the film into small rolls with different widths and lengths according to the requirements of customers.
When in use: and (4) storing, transporting and using the photosensitive solder mask prepared in the step (S3) in a non-ultraviolet environment with the low temperature of-20 ℃ and the humidity of 60%, attaching the photosensitive solder mask to a circuit board by using a vacuum or common film sticking machine when a photosensitive solder mask is used for preparing a photosensitive solder mask process, and carrying out exposure, development and curing to obtain the photosensitive solder mask.
Example 3
The embodiment provides a preparation method of a photosensitive solder resist dry film, which comprises the following steps:
s1, resin reaction: reacting a solvent, 178 parts by weight of o-cresol formaldehyde epoxy resin, 0.9-1.5 parts by weight of triphenylphosphine, 0.1 part by weight of 2-tert-butylhydroquinone and 80-90 parts by weight of methacrylic acid at 100 ℃ for 18h, and then adding 120 parts by weight of tetrahydrophthalic anhydride to react at 100 ℃ for 8h to obtain reacted resin; the solvent comprises tetramethylbenzene and dibasic ester, the content of the solvent is 40 wt% of the total weight, wherein the weight ratio of the tetramethylbenzene to the dibasic ester is 1: 3;
s2, burdening and dispersing: 30 parts by weight of the resin reacted in step S1, 0.2 part by weight of phthalocyanine green, 5 parts by weight of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 5 parts by weight of melamine, 20 parts by weight of barium sulfate, 2 parts by weight of polyoxypropylene polyoxyethylene glycerol ether, and 20 parts by weight of dibasic ester6 parts by weight of triglycidyl isocyanurate and 12 parts by weight of the bentonite-modified hollow porous SiO prepared in preparation example 32/Al(OH)3Dispersing the nano-microspheres and 0.7 part by weight of trishydroxypropyl phosphine oxide at the rotating speed of 11000r/min for 22min until the nano-microspheres and the trishydroxypropyl phosphine oxide are uniformly mixed to obtain a photosensitive solder resist composition;
s3, coating: and (4) uniformly coating the photosensitive solder mask composition obtained in the step (S2) on a bright-face or pressed-face PET (polyethylene terephthalate) film by using an extrusion film head, baking the film by using a tunnel oven, compounding a layer of PE (polyethylene) protective film on the film to obtain a semi-finished photosensitive solder mask dry film, and cutting the semi-finished photosensitive solder mask dry film into small rolls with different widths and lengths according to the requirements of customers.
When in use: and (4) storing, transporting and using the photosensitive solder mask prepared in the step (S3) in a non-ultraviolet environment with the low temperature of-15 ℃ and the humidity of 50%, wherein when the photosensitive solder mask is used for manufacturing a photosensitive solder mask process, the photosensitive solder mask is attached to a circuit board by a vacuum or common film sticking machine, and exposure, development and curing are carried out to obtain the photosensitive solder mask.
Comparative example 1
Compared with example 3, the bentonite modified hollow porous SiO prepared in preparation example 32/Al(OH)3The nanospheres were replaced with the microspheres obtained in comparative preparation example 1, and the other conditions were not changed.
Comparative example 2
Compared with example 3, the bentonite modified hollow porous SiO prepared in preparation example 32/Al(OH)3The nanospheres were replaced with the microspheres obtained in comparative preparation example 2, and the other conditions were not changed.
Comparative example 3
Compared with example 3, the bentonite modified hollow porous SiO prepared in preparation example 32/Al(OH)3The nanospheres were replaced with the microspheres obtained in comparative preparation example 3, and the other conditions were not changed.
Comparative example 4
Compared with example 3, the bentonite modified hollow porous SiO prepared in preparation example 32/Al(OH)3The nanospheres were replaced with the microspheres obtained in comparative preparation example 4, and the other conditions were not changed.
Comparative example 5
Compared with example 3, the bentonite modified hollow porous SiO prepared in preparation example 32/Al(OH)3The nanospheres were replaced with the microspheres obtained in comparative preparation example 5, and the other conditions were not changed.
Comparative example 6
As compared with example 3, no trimethylolpropane phosphine oxide was added as a flame retardant, and other conditions were not changed.
The method comprises the following steps:
s1, resin reaction: reacting a solvent, 178 parts by weight of o-cresol formaldehyde epoxy resin, 0.9-1.5 parts by weight of triphenylphosphine, 0.1 part by weight of 2-tert-butylhydroquinone and 80-90 parts by weight of methacrylic acid at 100 ℃ for 18h, and then adding 120 parts by weight of tetrahydrophthalic anhydride to react at 100 ℃ for 8h to obtain reacted resin; the solvent comprises tetramethylbenzene and dibasic ester, the content of the solvent is 40 wt% of the total weight, wherein the weight ratio of the tetramethylbenzene to the dibasic ester is 1: 3;
s2, burdening and dispersing: 30 parts by weight of the resin reacted in step S1, 0.2 part by weight of phthalocyanine green, 5 parts by weight of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 5 parts by weight of melamine, 20 parts by weight of barium sulfate, 2 parts by weight of polyoxypropylene polyoxyethylene glycerol ether, 20 parts by weight of a dibasic ester, 6 parts by weight of triglycidyl isocyanurate, and 12.7 parts by weight of the bentonite-modified hollow porous SiO prepared in preparation example 32/Al(OH)3Dispersing the nano microspheres for 22min at the rotating speed of 11000r/min until the nano microspheres are uniformly mixed to obtain a photosensitive solder resist composition;
s3, coating: and (4) uniformly coating the photosensitive solder mask composition obtained in the step (S2) on a bright-face or pressed-face PET (polyethylene terephthalate) film by using an extrusion film head, baking the film by using a tunnel oven, compounding a layer of PE (polyethylene) protective film on the film to obtain a semi-finished photosensitive solder mask dry film, and further cutting the semi-finished photosensitive solder mask dry film into small rolls with different widths and lengths according to the requirements of customers.
When in use: and (4) storing, transporting and using the photosensitive solder mask prepared in the step (S3) in a non-ultraviolet environment with the low temperature of-15 ℃ and the humidity of 50%, attaching the photosensitive solder mask to a circuit board by using a vacuum or common film sticking machine when a photosensitive solder mask is used for preparing a photosensitive solder mask process, and carrying out exposure, development and curing to obtain the photosensitive solder mask.
Comparative example 7
Compared with the example 3, the bentonite modified hollow porous SiO prepared in the preparation example 3 is not added2/Al(OH)3The nano microsphere has no change in other conditions.
The method comprises the following steps:
s1, resin reaction: reacting a solvent, 178 parts by weight of o-cresol formaldehyde epoxy resin, 0.9-1.5 parts by weight of triphenylphosphine, 0.1 part by weight of 2-tert-butylhydroquinone and 80-90 parts by weight of methacrylic acid at 100 ℃ for 18h, and then adding 120 parts by weight of tetrahydrophthalic anhydride to react at 100 ℃ for 8h to obtain reacted resin; the solvent comprises tetramethylbenzene and dibasic ester, the content of the solvent is 40 wt% of the total weight, wherein the weight ratio of the tetramethylbenzene to the dibasic ester is 1: 3;
s2, burdening and dispersing: dispersing 30 parts by weight of the resin reacted in the step S1, 0.2 part by weight of phthalocyanine green, 5 parts by weight of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 5 parts by weight of melamine, 20 parts by weight of barium sulfate, 2 parts by weight of polyoxypropylene polyoxyethylene glycerol ether, 20 parts by weight of dibasic ester, 6 parts by weight of triglycidyl isocyanurate and 12.7 parts by weight of trishydroxypropyl phosphine oxide at the rotating speed of 11000r/min for 22min until the components are uniformly mixed to obtain a photosensitive solder resist composition;
s3, coating: and (4) uniformly coating the photosensitive solder mask composition obtained in the step (S2) on a bright-face or pressed-face PET (polyethylene terephthalate) film by using an extrusion film head, baking the film by using a tunnel oven, compounding a layer of PE (polyethylene) protective film on the film to obtain a semi-finished photosensitive solder mask dry film, and further cutting the semi-finished photosensitive solder mask dry film into small rolls with different widths and lengths according to the requirements of customers.
When in use: and (4) storing, transporting and using the photosensitive solder mask prepared in the step (S3) in a non-ultraviolet environment with the low temperature of-15 ℃ and the humidity of 50%, attaching the photosensitive solder mask to a circuit board by using a vacuum or common film sticking machine when a photosensitive solder mask is used for preparing a photosensitive solder mask process, and carrying out exposure, development and curing to obtain the photosensitive solder mask.
Test example 1
The dry films prepared in examples 1 to 3 and comparative examples 1 to 7 were laminated on an acid-washed, mechanically brushed FR-4 copper clad laminate having a thickness of 1.6mm by a laminator, and exposed to light by a high-pressure mercury lamp exposure machine at an energy of 300mj/cm2And stripping the PE protective film, developing, and curing for 1H at 150 ℃. A test piece was obtained. The test pieces were subjected to the performance test, and the results are shown in table 1:
TABLE 1
Figure BDA0003524821590000231
Test example 2
The dry films prepared in examples 1 to 3 and comparative examples 1 to 7 were pressed on a copper clad laminate using polyimide as a substrate, which was subjected to acid cleaning and microetching, using a pressing machine, and exposed to light using a high pressure mercury lamp exposure machine with an energy of 300mj/cm2And stripping the PE protective film, developing, and curing for 1H at 150 ℃. A test piece was obtained. The test pieces were subjected to warpage, bendability and surface roughness tests, and the results are shown in Table 2.
Warping property: the cured photosensitive dry film for solder resist thus obtained was cut to 50X 50mm, and warpage at 4 corners was measured to obtain an average value, which was evaluated according to the following criteria.
A: the warpage is less than 0-3 mm;
b: the warpage is more than 3mm and less than 7 mm;
c: the warp is 7mm or more.
Bending property: the prepared cured photosensitive solder resist dry film is cut to 50mm × 50mm and bent, and the times before cracks appear are recorded.
Underfill filling property: the obtained cured photosensitive solder resist dry film was subjected to plasma treatment (argon, 500W, 60 seconds), and then, a silicon mold was mounted. After mounting, underfill was poured into the gap between the silicon mold and the substrate, and cured at 170 ℃. Then, the silicon mold was cut out using a grinder, and the underfill filling property was evaluated.
A: the underfill is uniformly filled on the lower front surface of the silicon mold;
b: locally contains bubbles.
Surface roughness: and measuring the surface roughness Ra of the prepared photosensitive solder resist dry film by using an electric contourgraph.
TABLE 2
Figure BDA0003524821590000241
Comparative example 1 compared with example 3, the bentonite modified hollow porous SiO prepared in preparation example 32/Al(OH)3NanopalesNano-microspheres Bentonite-modified hollow porous SiO prepared in comparative preparation example 12Replacement of nano-microspheres without Al (OH)3Partially, the flame retardant property and the high temperature resistance of the prepared photosensitive solder resist dry film are obviously reduced.
Comparative example 2 compared with example 3, the bentonite modified hollow porous SiO prepared in preparation example 32/Al(OH)3Nano-microsphere Bentonite modified hollow SiO prepared in comparative preparation example 22/Al(OH)3The nano microspheres are replaced, and the microspheres have no porous structure, so that other components are not easy to enter the microspheres in the preparation of the photosensitive solder-resist dry film, the mechanical property is reduced, and the hardness, low warpage and bendability are reduced. The porous hollow structure of the microsphere enables the reacted resin to enter the microsphere in the later preparation of the photosensitive solder-resisting dry film, so that the mechanical property is prevented from being influenced.
Comparative example 3 compared with example 3, the bentonite modified hollow porous SiO prepared in preparation example 32/Al(OH)3Nano-microsphere Bentonite modified hollow porous SiO prepared in comparative preparation example 32/Al(OH)3The nano-microsphere is replaced, and in the preparation of the microsphere, because the bentonite is not subjected to alkali treatment, a large amount of hydroxyl groups are not formed on the surface, so that the content of the bentonite loaded on the surface of the microsphere is greatly reduced, the high-temperature resistance and the mechanical property of the prepared microsphere are reduced, and the hardness, the low warpage and the bending property of the prepared microsphere are reduced.
Comparative example 4 compared with example 3, the bentonite modified hollow porous SiO prepared in preparation example 32/Al(OH)3Nano-microsphere Polydopamine coated hollow porous SiO prepared in comparative preparation example 42/Al(OH)3Replacement of nano-microspheresBecause the surface of the microsphere is not loaded by bentonite, the high temperature resistance and the mechanical property of the microsphere are greatly reduced. Because of the filler bentonite modified hollow porous SiO2/Al(OH)3The addition of the nano microspheres obviously improves the high temperature resistance and low temperature resistance of the photosensitive solder-resisting dry film, improves the mechanical property of the photosensitive solder-resisting dry film to a certain extent, and obtains the dry film with excellent characteristics such as low warpage, excellent bending property, soldering heat resistance, gold plating resistance and the like.
Comparative example 5 compared with example 3, the bentonite-modified hollow porous SiO prepared in preparation example 32/Al(OH)3Nanospheres hollow porous SiO from comparative preparation 52/Al(OH)3The nano-microsphere is used for substitution, and the surface of the microsphere is not subjected to polydopamine and bentonite load modification, so that the high temperature resistance and the mechanical property of the prepared photosensitive solder resist dry film are greatly reduced, and the adhesive force, the humidity resistance, the underfill filling property and the surface roughness are obviously reduced. The polyhydroxy and amino structure of the polydopamine enables the surface of the microsphere to have better adhesion and wettability, and meanwhile, the surface of the photosensitive solder-resisting dry film can keep stable roughness.
Comparative examples 6 and 7 in comparison with example 3, without adding trishydroxypropyl phosphine oxide as a flame retardant or bentonite-modified hollow porous SiO prepared in production example 32/Al(OH)3The flame retardant performance of the nano-microsphere in comparative example 6 is obviously reduced, and the performances in comparative example 7 are obviously reduced. In the invention, the bentonite modified hollow porous SiO2/Al(OH)3The shell layer of the inner layer of the nano microsphere contains rich SiO2And Al (OH)3The aluminum hydroxide part can release crystal water after being heated, absorb a large amount of heat, inhibit the temperature rise of the polymer, prevent flame retardation, generate a large amount of water vapor in the dehydration decomposition reaction, dilute combustible gas and achieve the flame retardant effect; the photosensitive solder-resisting dry film also contains an organic phosphorus flame retardant, particularly trihydroxypropylphosphine oxide, which has the advantages of low smoke, no toxicity, low halogen, no halogen and the like, and the action mechanism is that the organic phosphorus flame retardant can generate cross-linked solid substances or carbon with more stable structure when being heatedThe formation of the carbonized layer can prevent the polymer from further pyrolysis on the one hand and prevent the thermal decomposition products in the carbonized layer from entering the gas phase to participate in the combustion process on the other hand; the addition of the trihydroxypropyl phosphine oxide and the nano microspheres has better synergistic effect; the trishydroxypropyl phosphine oxide contains rich hydroxyl structures and is easy to modify with bentonite into hollow porous SiO2/Al(OH)3The amino and the hydroxyl on the surface of the nano microsphere are in hydrogen bond connection, so that a stable compound is formed, and the high-efficiency flame retardant effect is achieved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A preparation method of a photosensitive solder resist dry film is characterized by comprising the following steps:
s1, resin preparation: reacting a solvent, o-cresol formaldehyde epoxy resin, triphenylphosphine, a polymerization inhibitor and methacrylic acid at 90-120 ℃ for 4-24h, and then adding tetrahydrophthalic anhydride to react at 80-120 ℃ for 4-12h to obtain reacted resin;
s2, burdening and dispersing: the resin, the pigment, the photoinitiator, the melamine, the barium sulfate, the defoaming agent, the dibasic ester, the thermal curing agent and the bentonite modified hollow porous SiO reacted in the step S1 are mixed2/Al(OH)3Dispersing and mixing the nano microspheres and the flame retardant uniformly at a high speed to obtain a photosensitive solder resist composition;
s3, coating: and (4) uniformly coating the photosensitive solder mask composition obtained in the step (S2) on a bright-face or pressed-face PET (polyethylene terephthalate) film by using an extrusion film head, baking the film by using a tunnel oven, compounding a layer of PE (polyethylene) protective film on the film to obtain a semi-finished photosensitive solder mask dry film, and finally cutting the film into finished photosensitive solder masks with different widths and lengths according to requirements.
2. The method for preparing photosensitive solder resist dry film according to claim 1, wherein the thermal curing agent is triglycidyl isocyanurate; the defoaming agent is at least one selected from emulsified silicone oil, a higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane; the polymerization inhibitor is selected from at least one of ferric chloride, tert-butyl catechol, copper naphthenate, p-tert-butyl catechol, phenothiazine, hydroquinone, diphenylamine, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butyl hydroquinone and 2, 5-di-tert-butyl hydroquinone; the photoinitiator is selected from 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone, methyl benzoylformate, methyl acetate, and the like, Benzoin, benzoin bis-methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diphenylethanone, α -dimethoxy- α -phenylacetophenone, α -diethoxyacetophenone, α -hydroxyalkylphenone, α -aminoalkylphenone, aroylphosphine oxide, bisbenzoylphenylphosphine oxide, benzophenone, 2, 4-dihydroxybenzophenone, Michler's ketone, thiopropoxythioxanthone, isopropylthioxanthone, diaryliodonium salts, triaryliodonium salts, alkyliodonium salts, cumeneferrocene hexafluorophosphate; the pigment is selected from at least one of phthalocyanine blue, phthalocyanine green, permanent violet, permanent orange, pigment yellow, golden light red and permanent red; the flame retardant is at least one selected from the group consisting of ammonium polyphosphate, phosphamine, tricresyl phosphate, n-butyl bis (hydroxypropyl) phosphine oxide, trishydroxypropyl phosphine oxide, cyclooctyl hydroxypropyl phosphine oxide, and p-bis (2, 2-cyanoethyl phosphine oxide methyl) tetramethylbenzene.
3. The method for preparing the photosensitive solder resist dry film according to claim 1, wherein the mass ratio of the o-cresol formaldehyde epoxy resin, the triphenylphosphine, the tetrahydrophthalic anhydride, the polymerization inhibitor and the methacrylic acid in step S1 is 178: (0.9-1.5): (90-170): (0.05-0.15): (80-90); the solvent comprises tetramethylbenzene and dibasic ester, the content of the solvent is 35-45 wt% of the total weight, wherein the weight ratio of the tetramethylbenzene to the dibasic ester is 1: (2-4).
4. The method for preparing photosensitive dry film solder resist according to claim 1, wherein the reacted resin, pigment, photoinitiator, melamine, barium sulfate, defoamer, dibasic ester, thermal curing agent, bentonite modified hollow porous SiO in step S22/Al(OH)3The mass ratio of the nano microspheres to the flame retardant is (20-40): (0.1-0.5): (2-7): (2-7): (10-30): (1-3): (10-30): (5-10): (10-15): (0.5-1); the high-speed dispersion rotating speed is 10000-12000r/min, and the time is 15-30 min.
5. The method for preparing photosensitive solder resist dry film according to claim 1, wherein the bentonite modified hollow porous SiO in step S22/Al(OH)3The preparation method of the nano-microsphere comprises the following steps:
(1) hollow porous SiO2/Al(OH)3Preparing the nano microspheres: dissolving a surfactant and a pore-forming agent in water, adding aminosilane, stirring for reaction, then adding an ethanol solution of aluminum isopropoxide, continuing the reaction, centrifugally washing and drying to obtain the hollow porous SiO2/Al(OH)3Nano-microspheres;
(2) preparation of the catalyst: dissolving cobalt salt in Tris-HCl buffer solution to obtain catalyst solution;
(3) polydopamine-coated hollow porous SiO2/Al(OH)3Preparing the nano microspheres: the hollow porous SiO prepared in the step (1) is used2/Al(OH)3Dispersing the nano microspheres in water, adding dopamine hydrochloride, adding the catalyst solution prepared in the step (2), heating, stirring, reacting, centrifuging, washing and drying to obtain the polydopamine-coated hollow porous SiO2/Al(OH)3Nano-microspheres;
(4) and (3) bentonite treatment: grinding and sieving bentonite, adding the bentonite into alkali liquor, stirring for reaction, filtering, washing with water to be neutral, and drying to obtain pretreated bentonite;
(5) bentonite modified hollow porous SiO2/Al(OH)3Preparing the nano microspheres: coating the polydopamine prepared in the step (3) with hollow porous SiO2/Al(OH)3Adding the nano microspheres and the pretreated bentonite prepared in the step (4) into an ethanol water solution, heating and stirring for reaction, centrifuging, washing and drying to obtain the bentonite modified hollow porous SiO2/Al(OH)3And (4) nano microspheres.
6. The method for preparing the photosensitive solder resist dry film according to claim 5, wherein the mass ratio of the aminosilane, the aluminum isopropoxide, the surfactant and the pore-forming agent in the step (1) is 100: (30-50): (1-3): (2-4); the aminosilane is selected from at least one of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldiethoxysilane and diethylenetriaminopropyltrimethoxysilane; the surfactant is at least one selected from sodium hexadecylbenzene sulfonate, sodium hexadecyl sulfate, sodium octadecyl benzene sulfonate, sodium octadecyl sulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl sulfonate and tween-80; the pore-foaming agent is selected from at least one of polyoxyethylene sorbitan fatty acid ester and polyethylene glycol octyl phenyl ether; the drying temperature is 50-70 ℃, and the drying time is 2-4 h; in the step (2), the cobalt salt is selected from at least one of cobalt chloride, cobalt sulfate and cobalt bromide; the pH value of the Tris-HCl buffer solution is 7.8-8.2; co in the catalyst solution2+The ion concentration is 0.5-2 wt%.
7. The method for preparing photosensitive dry film solder resist according to claim 5, wherein the hollow porous SiO in step (3)2/Al(OH)3The mass ratio of the nano microspheres to the dopamine hydrochloride to the catalyst solution is 100: (20-50): (3-7); the heating temperature is 40-60 ℃, andthe reaction time is 3-5 h; the mesh number of the sieving screen in the step (4) is 500-1000 meshes; the alkali liquor is NaOH or KOH solution, and OH in the alkali liquor-The concentration of the ions is 0.5-2 mol/L; the stirring reaction time is 1-2 h; the mass ratio of the polydopamine coated nano microspheres to the pretreated bentonite in the step (5) is 20: (12-25); the ethanol content in the ethanol water solution is 35-60 wt%, and the balance is water; the heating temperature is 60-70 ℃, and the reaction time is 2-4 h.
8. The method for preparing photosensitive solder resist dry film according to claim 5, wherein the bentonite modified hollow porous SiO in step S22/Al(OH)3The preparation method of the nano-microsphere comprises the following steps:
(1) hollow porous SiO2/Al(OH)3Preparing the nano microspheres: dissolving 1-3 parts by weight of surfactant and 2-4 parts by weight of pore-forming agent in water, adding 100 parts by weight of aminosilane, stirring and reacting for 1-2h, then adding an ethanol solution containing 30-50 parts by weight of aluminum isopropoxide, continuing to react for 3-5h, centrifugally washing, and drying at 50-70 ℃ for 2-4h to obtain hollow porous SiO2/Al(OH)3Nano-microspheres;
(2) preparation of the catalyst: dissolving cobalt salt in Tris-HCl buffer solution with the pH value of 7.8-8.2 to obtain catalyst solution, wherein Co in the catalyst solution2+The ion concentration is 0.5-2 wt%;
(3) polydopamine-coated hollow porous SiO2/Al(OH)3Preparing the nano microspheres: 100 parts by weight of the hollow porous SiO prepared in the step (1)2/Al(OH)3Dispersing the nano microspheres in water, adding 20-50 parts by weight of dopamine hydrochloride, adding 3-7 parts by weight of the catalyst solution prepared in the step (2), heating to 40-60 ℃, stirring and reacting for 3-5h, centrifuging, washing and drying to obtain the polydopamine-coated hollow porous SiO2/Al(OH)3Nano-microspheres;
(4) and (3) bentonite treatment: grinding bentonite, sieving with a sieve of 500-1000 meshes, adding the bentonite into alkali liquor, stirring and reacting for 1-2h, wherein OH in the alkali liquor-The concentration of the ions is 0.5-2mol/L, filtering, washing with water to be neutral, drying,obtaining pretreated bentonite;
(5) bentonite modified hollow porous SiO2/Al(OH)3Preparing the nano microspheres: 20 parts by weight of polydopamine prepared in the step (3) coated hollow porous SiO2/Al(OH)3Adding the nano-microspheres and 12-25 parts by weight of the pretreated bentonite prepared in the step (4) into an ethanol aqueous solution, heating the ethanol aqueous solution to 60-70 ℃, stirring and reacting for 2-4h, centrifuging, washing and drying to obtain the bentonite modified hollow porous SiO2/Al(OH)3And (4) nano microspheres.
9. The method for preparing the photosensitive solder resist dry film according to claim 2, wherein the flame retardant is trishydroxypropyl phosphine oxide.
10. A photosensitive dry film solder resist obtained by the production method as described in any one of claims 1 to 9.
CN202210192270.1A 2022-02-28 2022-02-28 Photosensitive solder resist dry film and preparation method thereof Active CN114488691B (en)

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