CN109836885B - Liquid photosensitive ink, PCB and preparation method of PCB inner layer plate - Google Patents
Liquid photosensitive ink, PCB and preparation method of PCB inner layer plate Download PDFInfo
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Abstract
The invention provides liquid photosensitive ink, a PCB and a preparation method of the PCB. The invention provides liquid photosensitive ink which comprises, by weight, 1-50 parts of modified o-cresol epoxy resin acrylate, 1-50 parts of polymethacrylate copolymer, 2-80 parts of styrene acrylate copolymer, 5-30 parts of photoinitiator, 2-20 parts of acrylic monomer, 1-30 parts of pure polyester curing agent, 0.05-5 parts of sensitizer and 15-50 parts of other auxiliary agents. The liquid photosensitive ink, the PCB and the preparation method of the PCB provided by the invention have the advantage of simplifying the PCB manufacturing process.
Description
Technical Field
The invention belongs to the technical field of printing ink, and particularly relates to liquid photosensitive printing ink, a PCB (printed circuit board) and a preparation method of the PCB.
Background
Pcb (printed Circuit board), which is called printed Circuit board in chinese, is an important electronic component, is a support for electronic components, and is a carrier for electrical connection of electronic components. It is called a "printed" circuit board because it is made using electronic printing.
After the printing ink coating is carried out on the PCB, the steps of exposure, development, etching, film stripping, browning and the like are also required. Exposure: traditional exposure needs to adopt a film for developing exposure; and (3) developing: according to the characteristics of acid resistance and alkali resistance of the ink, unexposed monomer ink reacts with sodium carbonate, and is washed away by liquid medicine to expose unnecessary part of copper; etching: the copper which is exposed after the development and HCL are subjected to gasification-reduction reaction under the catalysis of PC-581F, and are etched away; removing the film: utilizing strong alkali to react with polymer printing ink for protecting the copper surface, and stripping off the surface printing ink to obtain a complete inner layer plate; browning: in the browning tank, due to H2O2The micro-etching of the copper substrate causes a micro-structure of crushed stone-like structure to be formed on the copper substrate surface, and a thin organic metal film is deposited immediately on the copper substrate surface due to the organic metalThe film is combined with the chemical bond on the copper surface of the substrate to form a brown plush structure, so that the bonding capability of the film and the bonding sheet is greatly improved.
The existing PCB printing ink needs a film removing step to obtain a desired pattern after being used, and browning is carried out after the film removing step to enable a copper surface of a substrate to have a layer of uniform fluff, so that the binding force between the substrate and PP is increased, the problems of layering, board explosion and the like are avoided, and the PCB manufacturing process is complicated. It is desirable to provide a PCB ink capable of simplifying the PCB manufacturing process, so that the PCB manufacturing efficiency is greatly improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the liquid photosensitive ink capable of simplifying the PCB manufacturing process, the PCB and the preparation method of the PCB.
The invention provides liquid photosensitive ink which comprises, by weight, 1-50 parts of modified o-cresol epoxy resin acrylate, 1-50 parts of polymethacrylate copolymer, 2-80 parts of styrene acrylate copolymer, 5-30 parts of photoinitiator, 2-20 parts of acrylic monomer, 1-30 parts of pure polyester curing agent, 0.05-5 parts of sensitizer and 15-50 parts of other auxiliary agents.
Preferably, the pure polyester curing agent is 1-20 parts.
Preferably, the pure polyester curing agent is 5-10 parts.
Preferably, the photoinitiator is a high-wavelength photoinitiator, and comprises one or more of a photoinitiator 369, a photoinitiator 819 and a photoinitiator 784.
Preferably, the acrylic monomer comprises a trifunctional acrylic monomer and a tetrafunctional acrylic monomer, and the weight ratio of the trifunctional acrylic monomer to the tetrafunctional acrylic monomer is 4-12: 0.5-4.
Preferably, the other auxiliary agents comprise a polymerization inhibitor, a solvent, a color-changing powder, fumed silica, a wetting agent, a defoaming agent and a filler, and the filler is preferably talcum powder with the particle size of less than 10000 meshes.
The invention also provides liquid photosensitive ink which comprises, by weight, 1-50 parts of modified o-cresol epoxy resin acrylate, 1-50 parts of polymethacrylate copolymer, 2-80 parts of styrene acrylate copolymer, 5-30 parts of photoinitiator, 2-20 parts of acrylic monomer, 1-30 parts of pure polyester curing agent, 0.05-5 parts of sensitizer, 0.05-1 part of polymerization inhibitor, 0.5-20 parts of solvent, 0.05-5 parts of color-changing powder, 0.05-5 parts of fumed silica, 0.05-5 parts of wetting agent, 0.05-10 parts of defoaming agent and 1-50 parts of talcum powder.
Preferably, the acrylic monomer consists of a trifunctional acrylic monomer and a tetrafunctional acrylic monomer, and the weight ratio of the trifunctional acrylic monomer to the tetrafunctional acrylic monomer is 4-12: 0.5-4.
Preferably, the photoinitiator consists of photoinitiator 369, photoinitiator 819 and photoinitiator 784.
Preferably, the weight ratio of the photoinitiator 369, the photoinitiator 819 and the photoinitiator 784 is from 1 to 6: 1-6: 1-6.
The invention also provides a PCB board which comprises a PCB inner layer board, wherein the PCB inner layer board comprises a substrate, copper layers arranged on one side or two sides of the substrate, and a film surface formed by the liquid photosensitive ink covering the outer sides of the copper layers.
Preferably, the PCB board comprises a plurality of PCB core board laminate combinations.
The invention also provides a preparation method of the PCB, which comprises the following steps:
1) carrying out pretreatment on the substrate with the copper layer;
2) coating the liquid photosensitive ink on the copper layer to form a film surface;
3) and carrying out exposure, development, etching and lamination to obtain the PCB.
The liquid photosensitive ink, the PCB and the preparation method of the PCB provided by the invention have the advantage of simplifying the PCB manufacturing process.
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 structure of an inner layer of a PCB according to embodiment 1 of the present invention.
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.
The embodiment of the invention provides liquid photosensitive ink which comprises, by weight, 1-50 parts of modified o-cresol epoxy resin acrylate, 1-50 parts of polymethacrylate copolymer, 2-80 parts of styrene acrylate copolymer, 5-30 parts of photoinitiator, 2-20 parts of acrylic monomer, 1-30 parts of pure polyester curing agent, 0.05-5 parts of sensitizer and 15-50 parts of other auxiliary agents.
The liquid photosensitive ink disclosed by the embodiment of the invention is etching ink, and the pure polyester curing agent is added, so that the preparation process of a PCB (printed circuit board) can be reduced when the prepared ink is applied to the PCB. The method has the advantages that the film removing and browning steps are not needed in the preparation process of the PCB, the flow is reduced, the production efficiency is accelerated, the film removing waste liquid treatment is reduced, the environmental pollution is reduced, the material cost and the labor cost are saved, the equipment investment is saved, the production field is saved, and the method has great significance to PCB manufacturers.
When the liquid photosensitive ink prepared by the embodiment of the invention is applied to a PCB, a film does not need to be removed in the PCB preparation process, and the film can have the same effect as a browning step, so that the browning step can be omitted.
The embodiment of the invention adopts the modified o-cresol epoxy resin acrylate, the polymethacrylate copolymer and the styrene acrylate copolymer for compounding, so that the printing ink has better quick-drying performance and can be applied to the LDI technology without generating larger rejection rate. Traditional printing ink exposure needs to use the film, and the printing ink of this embodiment does not need to use the film to expose, is applied to LDI technique (laser direct imaging) and exposes, can also be applied to ordinary halogen light source solidification or LED photocuring simultaneously, can satisfy the application that old technology can also satisfy new technology (LDI technique). Greatly broadens the application means of the ink.
In a preferred embodiment, 1-30 parts of modified o-cresol epoxy resin acrylate, and in a further preferred embodiment, 1-20 parts of modified o-cresol epoxy resin acrylate.
In a preferred embodiment, the polymethacrylate copolymer is 1-30 parts, and in a further preferred embodiment, the polymethacrylate copolymer is 1-20 parts.
In a preferred embodiment, the styrene acrylate copolymer is 2 to 50 parts, and in a further preferred embodiment, the styrene acrylate copolymer is 10 to 40 parts.
In a preferred embodiment, the photoinitiator is 5-20 parts.
In a preferred embodiment, the sensitizer is 0.05-2 parts.
In a preferred embodiment, the pure polyester curing agent is 1-20 parts. In a further preferred embodiment, 5-10 parts of pure polyester curing agent.
In a preferred embodiment, the photoinitiator is a high wavelength photoinitiator including one or more of photoinitiator 369, photoinitiator 819, and photoinitiator 784.
In order to ensure that the ink has higher sensitivity, the photoinitiator should be selected from those having higher wavelengths. The applicant obtains through a large number of experiments that the photoinitiators are matched with the modified o-cresol epoxy resin acrylate, the polymethacrylate copolymer and the styrene acrylate copolymer resin in the embodiment for compound use, so that the photosensitive effect is good, and the printing ink is easy to irradiate and is cured quickly. The molar extinction coefficients of the photoinitiator 369, the photoinitiator 819 and the photoinitiator 784 at each emission light of the high-pressure mercury lamp are shown in Table 1.
TABLE 1
In a preferred embodiment, the acrylic monomers include trifunctional acrylic monomers and tetrafunctional acrylic monomers, and the weight ratio of the trifunctional acrylic monomers to the tetrafunctional acrylic monomers is 4-12: 0.5-4. The trifunctional acrylic monomer and the tetrafunctional acrylic monomer are matched with the formula of the embodiment of the invention, so that the crosslinking curing effect is better.
In a preferred embodiment, the other auxiliary agents include a polymerization inhibitor, a solvent, a color-changing powder, fumed silica, a wetting agent, a defoaming agent and a filler, and in a preferred embodiment, the filler is talc with a particle size of less than 10000 meshes.
The invention also provides liquid photosensitive ink which comprises, by weight, 1-50 parts of modified o-cresol epoxy resin acrylate, 1-50 parts of polymethacrylate copolymer, 2-80 parts of styrene acrylate copolymer, 5-30 parts of photoinitiator, 2-20 parts of acrylic monomer, 1-30 parts of pure polyester curing agent, 0.05-5 parts of sensitizer, 0.05-1 part of polymerization inhibitor, 0.5-20 parts of solvent, 0.05-5 parts of color-changing powder, 0.05-5 parts of fumed silica, 0.05-5 parts of wetting agent, 0.05-10 parts of defoaming agent and 1-50 parts of talcum powder.
In the embodiment, the pure polyester curing agent and other components are added for compounding, the obtained etching ink is applied to the PCB preparation process, the film surface of the cured ink can have the same effect as a browning layer, and the PCB is not easy to layer, so that the steps of film stripping and browning can be omitted, the preparation efficiency is improved, and more cost is saved.
In this example, the talc powder is 12000 mesh superfine talc powder, and the solvent is quick-drying PMA
In a preferred embodiment, the acrylic monomer is composed of a trifunctional acrylic monomer and a tetrafunctional acrylic monomer, and the weight ratio of the trifunctional acrylic monomer to the tetrafunctional acrylic monomer is 4-12: 0.5-4.
In a preferred embodiment, the photoinitiator is a high wavelength photoinitiator, consisting of photoinitiator 369, photoinitiator 819, and photoinitiator 784.
In a preferred embodiment, the weight ratio of photoinitiator 369, photoinitiator 819 and photoinitiator 784 is from 1 to 6: 1-6: 1-6. The inventor finds that the 3 initiators are compounded with the resin of the embodiment to have better photosensitivity and faster curing speed through experiments. The yield of the ink applied to the LDI technology can be better improved.
In a preferred embodiment, 1-30 parts of modified o-cresol epoxy resin acrylate, and in a further preferred embodiment, 1-20 parts of modified o-cresol epoxy resin acrylate.
In a preferred embodiment, the polymethacrylate copolymer is 1-30 parts, and in a further preferred embodiment, the polymethacrylate copolymer is 1-20 parts.
In a preferred embodiment, the styrene acrylate copolymer is 2 to 50 parts, and in a further preferred embodiment, the styrene acrylate copolymer is 10 to 40 parts.
In a preferred embodiment, the photoinitiator is 5-20 parts.
In a preferred embodiment, the sensitizer is 0.05-2 parts.
In a preferred embodiment, the pure polyester curing agent is 1-20 parts. In a further preferred embodiment, 5-10 parts of pure polyester curing agent.
Referring to fig. 1, an embodiment of the present invention further provides a PCB including a PCB inner layer including a substrate 1, a copper layer 2 disposed on one side or both sides of the substrate, and a film surface 3 formed by the liquid photosensitive ink as described above and covering the outer side of the copper layer 2. In the traditional PCB preparation process, the ink after coating and curing is stripped, namely a film stripping step, and the PCB in the embodiment does not need to be stripped, so that the inner layer plate of the PCB also has a film surface. The film surface in the embodiment can increase the bonding capacity of the PCB inner layer plate, the bonding sheet and the like, so that the PCB inner layer plate does not need to be subjected to a browning step. In this embodiment, PP layers are laminated on both sides of the film surface 3 of the inner layer board of the PCB.
In a preferred embodiment, the PCB board comprises a plurality of PCB core board laminate assemblies. Traditional PCB inner plating needs to be browned to form a brown plush structure, and the condition that a plurality of inner plating laminates are bonded insecurely and are easy to delaminate is avoided. The layering is not easy, and meanwhile, the preparation cost of the PCB can be reduced.
The embodiment of the invention also provides a preparation method of the PCB, which comprises the following steps:
1) carrying out pretreatment on the substrate with the copper layer; such as brushing, degreasing, micro-etching, acid washing, water washing, drying and other pretreatment.
2) Coating the liquid photosensitive ink on the copper layer to form a film surface;
3) and carrying out exposure, development, etching and lamination to obtain the PCB inner layer board.
The traditional PCB preparation method comprises the steps of 1, preprocessing a substrate; 2. coating ink; 3. exposing by sticking film; 4. developing; 5. etching; 6. removing the film; 7. browning; 8. and (6) pressing. The preparation method of the PCB inner-layer board of the embodiment comprises the following steps of 1, preprocessing a substrate; 2. coating ink; 3. direct exposure (no need for a decal); 4. developing; 5. etching; 6. and pressing to obtain the PCB inner layer board. The method for preparing the inner layer board of the PCB does not need to remove the film after etching, namely, does not need to remove the film surface after coating and curing. And the step of browning to form a browned film is also not required. The PCB inner-layer plate can be obtained, due to the particularity of the liquid photosensitive ink in the embodiment, the adhesion between the film surface and the PP or the bonding sheet is good, so that the adhesion between the PCB inner-layer plate and the PP in the pressing process is good, a good bonding effect can be achieved, and the prepared PCB is not prone to layering.
In order that the technical solutions of the present invention may be further understood and appreciated, several preferred embodiments are now described in detail.
TABLE 2
According to the formula shown in the table 2, the raw materials of the formulas of example 1 to example 3 and comparative example 1 to comparative example 3 are mixed, ground in a three-roller machine to form a uniform mixed phase, and filtered by a mesh cloth to obtain the related ink.
The inks obtained in examples 1 to 3 and comparative examples 1 to 4 were exposed using a lissajous parallel light exposure machine from the frame and body frame type UVIA-5KD exposure machine. And then carrying out performance test on the circuit board after exposure.
1. And observing the appearance after curing, and judging whether the surface of the paint film is dry and not sticky.
2. The adhesion test method comprises the following steps: and (4) marking a grid, peeling off the adhesive tape, and marking the grid interval by 1 mm.
3. Pencil hardness: IS C5012-1993.8.6.3 Pencil scratch test, Pencil: coating films on the Mitsubishi pencil, the copper and the base material; IPC-TM-6502.4.27.2, minimum "F".
4. And (3) viscosity testing: Viscometer/Viscometer VT-06 at 25 ℃.
Specific test results are shown in table 3.
TABLE 3
As can be seen from the data in Table 3, the inks prepared in the examples 1 to 3 have the same performance as the ink prepared in the comparative example 1 without adding the pure polyester curing agent, have lower viscosity and quick drying performance, and are suitable for the laser direct imaging technology. After curing, the adhesive force and pencil hardness are better. And the proportion of the pure polyester curing agent added in the comparative example 2 and the proportion of the curing agent and other components in the comparative example 3 are not in the formula range of the invention, so that the performance of the obtained ink is relatively poor. The reasonable matching of the pure polyester curing agent and other components is added, so that the obtained ink has better performance.
The inks prepared in examples 1 to 3 and comparative examples 1 to 3 were applied to the preparation of PCB panels, and the preparation process was as follows:
copper plating of a substrate: copper plating is carried out on two sides of the substrate to form a substrate with a copper layer;
boiling oil: adding boiled oil water after uncovering, manually stirring for 3-5min, standing for 5-10min, and adding into a coating machine for use;
pretreatment of a substrate with a copper layer: performing the steps of scrubbing, degreasing, micro-etching, acid washing, water washing and drying, (the micro-etching speed is 40-60 mu in, the acid washing H2SO4Concentration: 3% -5%)
Coating: the inks prepared in examples 1 to 3 and comparative examples 1 to 3 were applied to a substrate with a copper layer at a roll coating production speed of about 4.5 to 5.0m/min, coating wheel: 420 meshes and the film thickness is controlled to be 12-15 mu m.
Pre-baking: 80-85-90-90-70 ℃ for 9-10min, and the exposure and development are completed within 24 hours after the pre-baking.
Exposure: wavelength of LDI laser: 405 nm; LDI exposure machine, 25-35mj/cm2,7-9 grade; laser scanning time: 10-14 seconds (the length of the scanning time depends on the size of the PCB).
And (3) developing: na (Na)2CO3Concentration: 0.8 to 1.2 percent; temperature: 28-32 ℃; spraying pressure: 0.5-1.2kg/cm2(ii) a Time: 40-60 sec.
Etching: acidity: typically an acidic copper chloride solution, temperature: 48-52 ℃, spray pressure: 1.5-2.5kg/cm2Time 40-50 sec. Alkalinity: typically an alkaline copper chloride solution, temperature: 48-52 ℃, spray pressure: 1.5-2.5kg/cm2Time 40-50 sec.
Pre-embedding: pre-stacking according to a stacking design, and embedding a copper core; the dimensional tolerance of the embedded part is controlled to be 0.05 mm.
And (3) laminating: the technical parameters of the pressing are as follows: the heating rate is 2.8 ℃/min, and the hot pressing time is 155min, so that the PCB is obtained.
The following tests were performed on the PCB boards prepared after the application of the inks corresponding to examples 1-3 and comparative examples 1-3, respectively:
X-Ray examination: and (5) checking whether the filling cavity condition exists by using an X-Ray machine, and making a micro-section for observation.
2. And (3) testing thermal stress: taking a laminated plate containing a copper-embedded core and having the size specification of 10cm by 10cm, and carrying out a tin bleaching test under the conditions that: 288 +/-5 ℃ for 10s for 3 times, checking whether the appearance has blistering and layering conditions, and making microtomes for observation.
The specific test results are shown in table 4.
TABLE 4
As can be seen from the data in table 4, the inks prepared in the embodiments 1 to 3 can be applied to the preparation process of the PCB without removing the cured ink, and the PCB obtained by browning can still have high reliability. It is demonstrated that the PCB prepared by the inks prepared in the embodiments 1-3 has the advantage of simplifying the PCB manufacturing process, and the manufacturing cost is reduced on the basis of ensuring the performance of the PCB.
In the comparative example 1, the ink formula is not added with a pure polyester curing agent, so that the reliability of the PCB obtained after the steps of film stripping and browning are reduced is poor, holes exist in the PCB in X-Ray inspection, and phenomena of board explosion and delamination and board surface foaming appear in a thermal stress test.
In the comparative example 2, the printing ink formula is added with a large proportion of pure polyester curing agent, so that the reliability of the PCB obtained after the steps of film stripping and browning are reduced is poor, the PCB is hollow in X-Ray inspection, and the phenomena of board explosion and delamination and board surface blistering occur in a thermal stress test.
In the comparative example 3, the proportion of the components of the printing ink is changed, and the foaming of the PCB thermal stress test board surface obtained after the steps of film stripping and browning are reduced.
The formula of the ink in the embodiments 1 to 3 is reasonable, and the prepared ink applied to the preparation process of the PCB can simplify the production flow of the PCB and improve the manufacturing efficiency of the PCB.
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 (8)
1. The liquid photosensitive ink is characterized by comprising, by weight, 1-50 parts of modified o-cresol epoxy resin acrylate, 1-50 parts of polymethacrylate copolymer, 2-80 parts of styrene acrylate copolymer, 5-30 parts of photoinitiator, 2-20 parts of acrylic monomer, 1-30 parts of pure polyester curing agent, 0.05-5 parts of sensitizer, 0.05-1 part of polymerization inhibitor, 0.5-20 parts of solvent, 0.05-5 parts of color-changing powder, 0.05-5 parts of fumed silica, 0.05-5 parts of wetting agent, 0.05-10 parts of defoaming agent and 1-50 parts of talcum powder.
2. The liquid photosensitive ink of claim 1, wherein said neat polyester curing agent is 1-20 parts.
3. The liquid photosensitive ink of claim 1, wherein said neat polyester curing agent is 5-10 parts.
4. The liquid photosensitive ink of claim 1, wherein said photoinitiator consists of photoinitiator 369, photoinitiator 819 and photoinitiator 784.
5. The liquid photosensitive ink of claim 1, wherein the acrylic monomer is composed of a trifunctional acrylic monomer and a tetrafunctional acrylic monomer, and the weight ratio of the trifunctional acrylic monomer to the tetrafunctional acrylic monomer is from 4 to 12: 0.5-4.
6. A PCB board comprising a PCB core comprising a substrate, a copper layer disposed on one or both sides of the substrate, a membrane formed of the liquid photosensitive ink of any one of claims 1 to 5 covering the outside of the copper layer.
7. The PCB panel of claim 6, comprising a plurality of PCB core board laminate assemblies.
8. A preparation method of a PCB board is characterized by comprising the following steps:
1) carrying out pretreatment on the substrate with the copper layer;
2) coating the liquid photosensitive ink according to any one of claims 1 to 5 on the outer side of the copper layer to form a film surface;
3) and carrying out exposure, development, etching and lamination to obtain the PCB.
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| CN110982348A (en) * | 2019-12-18 | 2020-04-10 | 江门市阪桥电子材料有限公司 | Matte black PCB character inkjet ink and preparation method thereof |
| CN111712057B (en) * | 2020-07-02 | 2023-05-30 | 江西景旺精密电路有限公司 | PCB inner layer processing method |
| CN111849242B (en) * | 2020-07-14 | 2022-04-22 | 深圳市德贝尔光电材料有限公司 | High-performance photosensitive wet film for LDI (laser direct immersion) and preparation method thereof |
| CN113263763A (en) * | 2021-04-23 | 2021-08-17 | 深圳万利科技有限公司 | Manufacturing method of mobile phone backboard with variable colors |
| CN113980510A (en) * | 2021-10-28 | 2022-01-28 | 江西超洋科技有限公司 | LDI high-sensitivity solder-resistant matte black ink and preparation method thereof |
| CN114716868B (en) * | 2022-04-19 | 2023-06-20 | 广州市红太电子科技有限公司 | Photo-curing ink for printed circuit board |
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| US20040106064A1 (en) * | 2002-11-14 | 2004-06-03 | Samsung Electronics Co., Ltd. | Silicon-containing polymer, negative type resist composition comprising the same, and patterning method for semiconductor device using the same |
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