CN114262537A - Solder resist ink, preparation method thereof, solder resist layer and Mini-LED printed circuit board - Google Patents
Solder resist ink, preparation method thereof, solder resist layer and Mini-LED printed circuit board Download PDFInfo
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- CN114262537A CN114262537A CN202111654621.8A CN202111654621A CN114262537A CN 114262537 A CN114262537 A CN 114262537A CN 202111654621 A CN202111654621 A CN 202111654621A CN 114262537 A CN114262537 A CN 114262537A
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- 238000002360 preparation method Methods 0.000 title abstract description 17
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
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- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims abstract description 17
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
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- 239000002253 acid Substances 0.000 claims description 7
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
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- 238000005530 etching Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 239000011342 resin composition Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- WDFFWUVELIFAOP-UHFFFAOYSA-N 2,6-difluoro-4-nitroaniline Chemical compound NC1=C(F)C=C([N+]([O-])=O)C=C1F WDFFWUVELIFAOP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
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- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
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Images
Abstract
The invention provides white photosensitive solder resist ink which comprises a main agent and a curing agent, wherein the main agent comprises alkali development type photosensitive resin, titanium dioxide and a photoinitiator, and the total content of nitrogen, phosphorus and sulfur in the main agent and the curing agent is less than 2000 ppm. The invention provides solder resist ink capable of avoiding silica gel poisoning, a preparation method thereof, a solder resist layer and a Mini-LED printed circuit board.
Description
Technical Field
The invention belongs to the field of printed circuit board preparation, and particularly relates to solder resist ink, a preparation method thereof, a solder resist layer and a Mini-LED printed circuit board.
Background
With the rapid development of LED display technology, especially the miniaturization of LEDs, 100 micrometer (Mini-LED) and even micrometer scale LEDs (Micro-LED) have been manufactured, making the manufacture of high resolution LED displays possible, since Mini-LED and Micro-LED are active light emitting, but unlike the current mass production Organic Light Emitting Display (OLED), it does not rely on organic compounds to emit light, theoretically, it is as bright as OLED but has no aging problem and is cheaper than OLED in the long run, and Mini-LED and Micro-LED can be directly attached on a PCB circuit board to manufacture the display, the manufacturing process is very simple, but it puts new technical requirements on the PCB board.
The existing Mini-LED printed circuit board usually needs to coat silica gel on the outer surface of a solder mask, and due to incompatibility of the solder mask and the silica gel, the silica gel is poisoned and is difficult to cure, and the yield is very low. So that the existing solder resist ink is difficult to realize better application in the Mini-LED printed circuit board.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the solder resist ink, the preparation method thereof, the solder resist layer and the Mini-LED printed circuit board provided by the invention can avoid silica gel poisoning.
The invention provides white photosensitive solder resist ink which comprises a main agent and a curing agent, wherein the main agent comprises alkali development type photosensitive resin, titanium dioxide and a photoinitiator, and the total content of nitrogen, phosphorus and sulfur in the main agent and the curing agent is less than 2000 ppm.
Preferably, the photoinitiator has a phosphorus content of less than 1500 ppm; the photoinitiator comprises one or more of photoinitiator TPO, photoinitiator 819 and photoinitiator 784.
Preferably, the sulfur content of the titanium dioxide is less than 50 ppm; the nitrogen content of the alkali developable photosensitive resin is less than 500 ppm.
Preferably, the weight average molecular weight of the alkali-developable photosensitive resin is 15000-25000, and the acid value of the solid component of the alkali-developable photosensitive resin is 65 to 85 mgKOH/g.
Preferably, in the main agent, by weight, 40-50 parts of alkali-developable photosensitive resin, 30-50 parts of titanium dioxide and 2-6 parts of photoinitiator are used, and the curing agent comprises 30-50 parts of epoxy resin, 15-25 parts of acrylic monomer and 20-30 parts of titanium dioxide;
the weight ratio of the main agent to the curing agent is (1-2): (1-2).
Preferably, the alkali-developable photosensitive resin comprises polyacrylic acid photo-etching resin, the main agent comprises 35-55 parts by weight of polyacrylic acid photo-etching resin, 25-55 parts by weight of titanium oxide, 2-10 parts by weight of photoinitiator and 0.1-15 parts by weight of other auxiliary agents, and the curing agent comprises 25-55 parts by weight of epoxy resin, 10-30 parts by weight of polyfunctional group acrylic monomer, 15-35 parts by weight of titanium oxide, 0.1-5 parts by weight of melamine, 0.5-4 parts by weight of auxiliary agent and 5-20 parts by weight of solvent.
The invention also provides a preparation method of the white photosensitive solder resist ink, and the nitrogen content of the catalyst used in the synthesis process of the alkali-developable photosensitive resin is less than 200 ppm.
The invention also provides a printed circuit board solder mask layer which comprises the solder mask layer, wherein the total content of nitrogen, phosphorus and sulfur in the solder mask layer is less than 2000 ppm.
Preferably, the printed circuit board solder mask layer further comprises a solder mask layer and a silica gel layer, and the silica gel layer is coated on the outer surface of the solder mask layer.
The invention also provides a Mini-LED printed circuit board which sequentially comprises a substrate layer, a circuit layer, a solder mask layer and a silica gel layer from inside to outside, wherein the total content of nitrogen, phosphorus and sulfur in the solder mask layer is less than 2000 ppm.
The invention provides solder resist ink capable of avoiding silica gel poisoning, a preparation method thereof, a solder resist layer and a Mini-LED printed circuit board.
Drawings
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of preferred embodiments of the invention, as illustrated in the accompanying drawings. Like reference numerals refer to like parts throughout the drawings, and the drawings are not intended to be drawn to scale in actual dimensions, emphasis instead being placed upon illustrating the principles of the invention.
Fig. 1 is a schematic diagram of a printed circuit board structure according to an embodiment of the present invention.
Wherein: 1-a layer of material; 2-a line layer; 3-a solder mask layer; 4-silica gel layer.
Detailed Description
The technical solutions of the present invention are further described in detail with reference to specific examples so that those skilled in the art can better understand the present invention and can implement the present invention, but the examples are not intended to limit the present invention.
Referring to fig. 1, an embodiment of the present invention provides a white photosensitive solder resist ink, which includes a main agent and a curing agent, wherein the main agent includes an alkali-developable photosensitive resin, titanium dioxide, and a photoinitiator, and the total content of nitrogen, phosphorus, and sulfur in the main agent and the curing agent is less than 2000 ppm.
The white photosensitive solder resist ink provided by the embodiment can be applied to preparation of a Mini-LED printed circuit board, and cannot cause silica gel poisoning of the printed circuit board, so that a silica gel layer is difficult to cure.
In a preferred embodiment, the photoinitiator has a phosphorus content of less than 1500 ppm. In the embodiment, the photoinitiator containing no phosphorus is selected as much as possible, so that the problems that the solder resist ink contains more phosphorus, the silica gel is poisoned when the silica gel is matched with the photoinitiator, and the silica gel is difficult to cure are avoided. The silica gel poisoning referred to in this example means that the catalytic curing agent in the silica gel coating liquid is ineffective, and the coated silica gel is difficult to cure.
In a preferred embodiment, the sulfur content of the titanium dioxide is less than 50 ppm. In the embodiment, proper titanium dioxide is selected, and titanium dioxide with low sulfur content is selected, so that the problems that solder resist ink has high phosphorus content and is poisoned by silica gel when being matched with the silica gel are avoided.
In a preferred embodiment, the nitrogen content of the alkali developable photosensitive resin is less than 500 ppm. The nitrogen content of the alkali development type photosensitive resin is controlled, so that the silica gel poisoning when the alkali development type photosensitive resin is matched with silica gel can be well avoided. In a further preferred embodiment, the nitrogen content of the catalyst used in the synthesis of the alkali developable photosensitive resin is less than 200 ppm. The nitrogen content of the alkali development type photosensitive resin is controlled by controlling the nitrogen content of a catalyst in the synthetic process of synthesizing the alkali development type photosensitive resin.
In a preferred embodiment, the photoinitiator comprises one or more of photoinitiator TPO, photoinitiator 819, and photoinitiator 784. In a preferred embodiment, the photoinitiator comprises photoinitiator TPO, photoinitiator 819 and photoinitiator 784, wherein the weight ratio of photoinitiator TPO, photoinitiator 819 and photoinitiator 784 is (0.5-5): (0.5-5): (0.01-0.1).
In a preferred embodiment, the weight average molecular weight of the alkali-developable photosensitive resin is 15000-25000, and the acid value of the solid component of the alkali-developable photosensitive resin is 65 to 85 mgKOH/g. The acid number of the resin in this example refers to the number of milligrams of KOH consumed per gram of acid content of the sample. The total content of nitrogen, phosphorus and sulfur is limited to be less than 2000ppm in the embodiment, the poisoning of silica gel can be better avoided, meanwhile, in order to ensure the photocuring effect and the developing performance of the solder resist ink, the weight average molecular weight and the acid value of the alkali developing type photosensitive resin are reasonably limited, the solder resist ink of the embodiment can be ensured to avoid the poisoning of silica gel, and meanwhile, the developing performance and the curing performance of the solder resist ink can not be deteriorated. The weight average molecular weight of the alkali developable photosensitive resin in this example was measured by Gel Permeation Chromatography (GPC).
In addition, the solder resist ink provided by the embodiment selects the alkali-developable photosensitive resin with a certain range of weight average and a proper acid value, so that the alkali-developable photosensitive resin has moderate solubility in a developing solution, thereby reducing the side etching of the solder resist ink, improving the resolution of a solder resist layer, and realizing the solder resist ink capable of achieving the resolution of 100 μm × 100 μm.
Meanwhile, the reflectivity of the solder resist ink provided by the embodiment to light with the wavelength of 430-700nm can reach more than 85%, and the reflectivity to light with the wavelength of more than 500nm can reach 90%. The solder resist ink provided by the embodiment also has the advantages of gold resistance, no redness and the like.
In a preferred embodiment, the main agent comprises, by weight, 40-50 parts of alkali-developable photosensitive resin, 30-50 parts of titanium dioxide and 2-6 parts of photoinitiator. In the embodiment, the solder resist ink prepared by the method has high reflectivity through reasonable raw material proportion.
In a preferred embodiment, the curing agent comprises 30-50 parts by weight of epoxy resin, 15-25 parts by weight of acrylic monomer and 20-30 parts by weight of titanium dioxide.
In a preferred embodiment, the weight ratio of the main agent to the curing agent is (1-2): (1:2).
In a preferred embodiment, the alkali development type photosensitive resin comprises polyacrylic acid photo-etching resin, the main agent comprises 35-55 parts by weight of polyacrylic acid photo-etching resin, 25-55 parts by weight of titanium oxide, 2-10 parts by weight of photoinitiator and 0.1-15 parts by weight of other auxiliary agents, and the curing agent comprises 25-55 parts by weight of epoxy resin, 10-30 parts by weight of polyfunctional group acrylic acid monomer, 15-35 parts by weight of titanium oxide, 0.1-5 parts by weight of melamine, 0.5-4 parts by weight of auxiliary agent and 5-20 parts by weight of solvent.
The embodiment also provides solder resist ink which comprises a main agent and a curing agent, wherein the main agent comprises 35-55 parts by weight of polyacrylic acid photoetching resin, 25-55 parts by weight of titanium oxide, 2-10 parts by weight of photoinitiator and 0.1-15 parts by weight of other additives, and the curing agent comprises 25-55 parts by weight of epoxy resin, 10-30 parts by weight of polyfunctional group acrylic monomer, 15-35 parts by weight of titanium oxide, 0.1-5 parts by weight of melamine, 0.5-4 parts by weight of auxiliary agent and 5-20 parts by weight of solvent.
In a preferred embodiment, the alkali development type photosensitive resin composition is obtained by mixing a main agent and a curing agent, wherein the main agent comprises 35-55 parts by weight of polyacrylic acid photoetching resin, 25-55 parts by weight of titanium oxide, 2-10 parts by weight of photoinitiator and 0.1-15 parts by weight of other auxiliary agents, and the curing agent comprises 25-55 parts by weight of epoxy resin, 10-30 parts by weight of polyfunctional group acrylic monomer, 15-35 parts by weight of titanium oxide, 0.1-5 parts by weight of melamine, 0.5-4 parts by weight of auxiliary agent and 5-20 parts by weight of solvent.
In a further preferred embodiment, the other auxiliary agents are a dispersing agent, a leveling agent, an antioxidant, a defoaming agent and fumed silica; the auxiliary agents are a dispersing agent and gas phase silicon dioxide; in a further preferred embodiment, the main agent consists of 40-50 parts of polyacrylic acid photoetching resin, 30-50 parts of titanium oxide, 2-8 parts of photoinitiator, 0.2-0.8 part of dispersant, 0.1-0.4 part of flatting agent, 0.2-1 part of antioxidant, 0.5-2 parts of defoaming agent and 0.5-2 parts of fumed silica; the curing agent consists of 30 to 50 parts of epoxy resin, 16 to 24 parts of polyfunctional group acrylic monomer, 20 to 30 parts of titanium dioxide, 0.5 to 2 parts of melamine, 5 to 15 parts of solvent, 0.2 to 0.8 part of dispersant and 0.5 to 2 parts of fumed silica.
In a preferred embodiment, the multifunctional acrylic monomer comprises a trifunctional acrylic monomer and/or a difunctional acrylic monomer, and the trifunctional acrylic monomer comprises one or more of tris (2-hydroxyethyl) isocyanurate triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, and ethoxylated trimethylolpropane triacrylate; the bifunctional acrylic monomer comprises one or more of hexanediol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, MPGDA and 2-hydroxyethyl methacrylate phosphate.
The embodiment of the invention also provides a printed circuit board solder mask layer, which comprises a solder mask layer and a silica gel layer, wherein the silica gel layer is coated on the outer surface of the solder mask layer, and the total content of nitrogen, phosphorus and sulfur in the solder mask layer is less than 2000 ppm.
Referring to fig. 1, an embodiment of the present invention further provides a mini LED printed circuit board, which sequentially includes, from inside to outside, a substrate layer 1, a circuit layer 2, a solder mask layer 3, and a silica gel layer 4, where a total content of nitrogen, phosphorus, and sulfur in the solder mask layer is less than 2000 ppm. The Mini-LED printed circuit board provided by the embodiment can better avoid silica gel poisoning, realize better silica gel curing effect, improve the yield of printed circuit board preparation, and simultaneously has stronger resolution, higher reflectivity and gold resistance without redness.
The invention also provides a preparation method of the alkali development type photosensitive resin composition, which comprises the following steps:
preparation of the main agent:
(1) adding the components of the main agent into a dispersing barrel according to a proportion;
(2) dispersing at high speed in a high-speed dispersion machine;
(3) grinding for 2-5 times with three-roller machine or grinding with sand mill until the particle diameter is below 20 μm;
(4) adding a diluent to adjust the viscosity to 200-400P;
(5) then filtering with filter cloth to obtain a main agent;
preparation of the curing agent:
(1) adding the curing agent components into a dispersing barrel according to a proportion;
(2) dispersing at high speed in a high-speed dispersion machine;
(3) grinding for 2-5 times with a three-roller machine or grinding with a sand mill until the particle size is below 20 μm;
(4) adding diluent to adjust the viscosity to 50-200P;
(5) then filtering with filter cloth to obtain a curing agent;
in order that the technical solutions of the present invention may be further understood and appreciated, several preferred embodiments are now described in detail. The formulations of example 1, example 2 and comparative example are shown in table 1:
TABLE 1
The solder resist ink 1 and the solder resist ink 2 are prepared according to the following preparation method by using the formula of the solder resist ink 1 and the formula of the solder resist ink 2.
Preparation of the main agent:
(1) adding the components of the main agent into a dispersing barrel according to a proportion;
(2) dispersing at high speed in a high-speed dispersion machine;
(3) grinding for 2-5 times with three-roller machine or grinding with sand mill until the particle diameter is below 20 μm;
(4) adding a diluent to adjust the viscosity to 200-400P;
(5) then filtering with filter cloth to obtain a main agent;
preparation of the curing agent:
(1) adding the curing agent components into a dispersing barrel according to a proportion;
(2) dispersing at high speed in a high-speed dispersion machine;
(3) grinding for 2-5 times with a three-roller machine or grinding with a sand mill until the particle size is below 20 μm;
(4) adding diluent to adjust the viscosity to 50-200P;
(5) then filtering with filter cloth to obtain a curing agent;
the main agent and the curing agent are mixed according to the proportion of 2: 1.
The test pieces prepared in examples and comparative examples were subjected to the following tests, respectively.
Test 1: test for lateral erosion
The substrates (glass epoxy substrate, "FR 4", Cu thickness 25 μm) were surface-treated with dilute sulfuric acid (5 mass%), and then the solder resist inks of examples and comparative examples prepared as described above were applied by screen printing, respectively. After coating, pre-drying was carried out in a BOX furnace at 80 ℃ for 20 minutes. After the predrying, exposure was performed under the exposure conditions of an exposure machine, and after the exposure, development was performed using a 1 mass% sodium carbonate aqueous solution at a development temperature of 30 ℃ under a spray pressure of 0.2 MPa. After the development, post-curing was performed at 150 ℃ for 60 minutes in a BOX furnace, thereby forming a cured coating film on the substrate. The thickness of the cured coating is 20 to 23 μm.
Respectively slicing the sample wafer, observing the lateral erosion condition of the sample wafer from the side surface, and judging the standard as follows: 1. the lateral erosion is serious when the lateral erosion depth of the single side is more than 10 mu m; 2. the unilateral lateral erosion depth is between 5 and 10 mu m, and the unilateral lateral erosion is slight; 3. the unilateral undercut depth is less than 5 μm without undercut.
And (3) testing 2: resolution test
The substrates (glass epoxy substrate, "FR 4", Cu thickness 25 μm) were surface-treated with dilute sulfuric acid (5 mass%), and then the solder resist inks of examples and comparative examples prepared as described above were applied by screen printing, respectively. Each window of the screen printing was rectangular with dimensions of 100 μm by 100 μm. After coating, pre-drying was carried out in a BOX furnace at 80 ℃ for 20 minutes. After the predrying, exposure was performed under the exposure conditions of an exposure machine, and after the exposure, development was performed using a 1 mass% sodium carbonate aqueous solution at a development temperature of 30 ℃ under a spray pressure of 0.2 MPa. After the development, post-curing was performed at 150 ℃ for 60 minutes in a BOX furnace, thereby forming a cured coating film on the substrate. The thickness of the cured coating is 20 to 23 μm.
Observing the condition that each window is covered by the solder resist ink after the development by using a microscope after the development, wherein the judgment standard is as follows: 1. the maximum width of the window covered by the solder resist ink after development is more than 20 μm, and the window is judged to be poor in resolution; 2. the maximum width of the window covered by the solder resist ink after development is 6-20 μm, and the resolution is judged to be general; 3. the developed window was not substantially covered with the resist ink, and the size was maintained at 100. mu. m.times.100. mu.m (measurement error was not more than 2 μm), and the resolution was judged to be good.
And (3) testing: silica gel curing test
The substrates (glass epoxy substrate, "FR 4", Cu thickness 25 μm) were surface-treated with dilute sulfuric acid (5 mass%), and then the solder resist inks of examples and comparative examples prepared as described above were applied by screen printing, respectively. After coating, pre-drying was carried out in a BOX furnace at 80 ℃ for 20 minutes. After the predrying, exposure was performed under the exposure conditions of an exposure machine, and after the exposure, development was performed using a 1 mass% sodium carbonate aqueous solution at a development temperature of 30 ℃ under a spray pressure of 0.2 MPa. After the development, post-curing was performed at 150 ℃ for 60 minutes in a BOX furnace, thereby forming a cured coating film on the substrate. The thickness of the cured coating is 20 to 23 μm.
Coating silica gel on the outer surface of the cured coating film, wherein the silica gel contains platinum catalyst, observing whether the cured silica gel is cured or not 10 minutes after coating, and judging the standard as follows: 1. observing the cured film layer by naked eyes, and judging that the film layer is completely cured if no liquid exists and no liquid touch feeling is generated when the film layer is touched by hands; 2. observing the cured film layer by naked eyes, not observing the existence of liquid, and judging that the film layer is basically cured if a small amount of liquid can be sensed by touching the film layer by hands; 3. and (4) observing the cured film layer by naked eyes, obviously observing the existence of the liquid, and judging that the film layer is not cured basically if the film layer is touched by hands to feel the existence of lower liquid. 10 samples were prepared for each example and then counted.
The results of the above tests 1, 2 and 3 are shown in table 3.
TABLE 2
And (4) testing: reflectance test
The solder resist inks prepared in examples and comparative examples were coated on glass substrates, respectively, and after completion of curing, a reflectance test was performed using a spectrocolorimeter CM-26 d. The conditions of the primary reflow soldering are as follows: 260 ℃ + 270 ℃ for 6 minutes, and the secondary reflow soldering conditions are as follows: 260 ℃. about.270 ℃ for 6 minutes, the specific data are shown in Table 3.
TABLE 3
In Table 4, the reflectance is Y, L is black > white, and A is green > red; the B value is green > yellow.
From the data in tables 2 and 3, it can be seen that the solder resist inks provided in examples 1 and 2 can prevent the silicone poisoning well. The silica gel has better curing effect after being coated. The prepared ink has a good side etching prevention effect and a good resolution, can realize the preparation of a circuit size of 100 micrometers multiplied by 100 micrometers, and can be well applied to Mini-LED printed circuit boards. The solder resist ink provided by the embodiment 1 and the embodiment 2 has better reflectivity, the reflow oven value is more stable, and as can be seen from the value A, the value A is basically about 1.3, and the color of the solder resist layer does not become red.
In the comparative example, the total content of nitrogen, phosphorus and sulfur was more than 2000ppm, and the resulting ink poisoned the silica gel after coating and the silica gel was hard to cure.
In conclusion, the total content of nitrogen, phosphorus and sulfur in the solder resist ink provided by the invention can better prevent the poisoning of silica gel, and meanwhile, the solder resist ink provided by the invention also has higher reflectivity, better lateral erosion prevention effect and better resolution.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The white photosensitive solder resist ink is characterized by comprising a main agent and a curing agent, wherein the main agent comprises alkali-developable photosensitive resin, titanium dioxide and a photoinitiator, and the total content of nitrogen, phosphorus and sulfur in the main agent and the curing agent is less than 2000 ppm.
2. The white photosensitive solder resist ink of claim 1, wherein the photoinitiator has a phosphorus content of less than 1500 ppm; the photoinitiator comprises one or more of photoinitiator TPO, photoinitiator 819 and photoinitiator 784.
3. The white photosensitive solder resist ink of claim 1, wherein the titanium dioxide has a sulfur content of less than 50 ppm; the nitrogen content of the alkali developable photosensitive resin is less than 500 ppm.
4. The white photosensitive solder resist ink according to claim 1, wherein the weight average molecular weight of the alkali-developable photosensitive resin is 15000-25000, and the acid value of the solid content of the alkali-developable photosensitive resin is 65-85 mgKOH/g.
5. The white photosensitive solder resist ink of claim 1, wherein the base agent comprises, by weight, 40-50 parts of alkali-developable photosensitive resin, 30-50 parts of titanium dioxide, 2-6 parts of photoinitiator, and the curing agent comprises 30-50 parts of epoxy resin, 15-25 parts of acrylic monomer, and 20-30 parts of titanium dioxide;
the weight ratio of the main agent to the curing agent is (1-2): (1-2).
6. The white photosensitive solder resist ink of claim 1, wherein the alkali-developable photosensitive resin comprises polyacrylic acid photo-etching resin, the main agent comprises 35-55 parts by weight of polyacrylic acid photo-etching resin, 25-55 parts by weight of titanium oxide, 2-10 parts by weight of photoinitiator, and 0.1-15 parts by weight of other auxiliaries, and the curing agent comprises 25-55 parts by weight of epoxy resin, 10-30 parts by weight of polyfunctional acrylic monomer, 15-35 parts by weight of titanium oxide, 0.1-5 parts by weight of melamine, 0.5-4 parts by weight of auxiliary agent, and 5-20 parts by weight of solvent.
7. A method for preparing a white photosensitive solder resist ink according to any one of claims 1 to 6, wherein the nitrogen content of the catalyst used in the synthesis of the alkali-developable photosensitive resin is less than 200 ppm.
8. The printed circuit board solder mask is characterized by comprising the solder mask, wherein the total content of nitrogen, phosphorus and sulfur in the solder mask is less than 2000 ppm.
9. A printed wiring board solder resist according to claim 8, further comprising a solder resist layer and a silicone layer, said silicone layer being coated on an outer surface of said solder resist layer.
10. The Mini-LED printed circuit board is characterized by sequentially comprising a substrate layer, a circuit layer, a solder mask layer and a silica gel layer from inside to outside, wherein the total content of nitrogen, phosphorus and sulfur in the solder mask layer is less than 2000 ppm.
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