CN115368609A - Preparation method of UV (ultraviolet) cured PCB (printed Circuit Board) dry film for copper-clad plate photoetching - Google Patents
Preparation method of UV (ultraviolet) cured PCB (printed Circuit Board) dry film for copper-clad plate photoetching Download PDFInfo
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- CN115368609A CN115368609A CN202210947553.2A CN202210947553A CN115368609A CN 115368609 A CN115368609 A CN 115368609A CN 202210947553 A CN202210947553 A CN 202210947553A CN 115368609 A CN115368609 A CN 115368609A
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- dry film
- photoinitiator
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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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
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
- H05K3/064—Photoresists
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a preparation method of a UV curing PCB dry film for copper-clad plate photoetching, which comprises the synthesis of acrylic resin oligomer; preparing photosensitive resin glue solution; and (5) preparing a photosensitive dry film. According to the invention, acrylic resin oligomer, photoreaction monomer reacting under different energies, low-energy photoinitiator, high-energy photoinitiator and auxiliary agent are prepared into photosensitive resin glue solution, the photosensitive resin glue solution is coated on PET, the existing thermosetting coating process is replaced by a UV curing coating process, a PCB dry film is obtained by low-energy UV irradiation curing, and a client transfers a required negative film pattern to a PCB plate after high-energy UV irradiation.
Description
Technical Field
The invention belongs to the technical field of photosensitive materials, relates to preparation of a photosensitive dry film, and particularly relates to a preparation method of a UV (ultraviolet) curing PCB (printed Circuit Board) dry film for photoetching of a copper-clad plate.
Background
The photosensitive dry film is developed by DuPont company in 1968, and is widely applied to pattern transfer from the beginning, and the photosensitive dry film becomes an important material in the modern electronic field, particularly the field of printed circuit boards. In recent years, with miniaturization and lightness of electronic devices, the requirement of the market on circuit boards is higher, how to realize extremely narrow line width and line pitch becomes the ultimate goal of various large circuit board manufacturers, and the photosensitive dry film is the core electronic material for realizing the goal.
Because a back-end customer needs exposure to transfer the circuit of the negative film to a circuit board, the existing photosensitive film is prepared by adding a photoinitiator, active acrylic resin and other additives to acrylic resin oligomer and a large amount of solvent, drying the solvent by using an oven to form a film and rolling.
The preparation of current sensitization light film needs to consume a large amount of organic solvent, and the heat of oven leads to production to produce a large amount of VOC gas and produces, is unfavorable for the protection of environment.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a UV curing PCB dry film for copper-clad plate photoetching, the solid content of resin used for coating is 100%, the curing mode of the invention is UV curing, VOC gas can not be discharged in the production process, and the environment-friendly, economic and efficient production mode is achieved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a UV curing PCB dry film for copper-clad plate photoetching comprises the following steps:
1) Synthesis of acrylic resin oligomer: adding a mixture of a hydroxyl acrylate monomer, an initiator and a relative molecular mass control agent into a container, reacting for a period of time under the condition of water bath, and then cooling to react to obtain an acrylic resin oligomer;
2) Preparing photosensitive resin glue solution: adding the acrylic resin oligomer obtained in the step 1), the photoreaction monomer composition, the first photoinitiator, the second photoinitiator and the auxiliary agent into a container, and uniformly mixing to obtain a photosensitive resin glue solution;
3) Preparing a photosensitive dry film: coating the photosensitive resin glue solution obtained in the step 2) on PET, irradiating under 273nm light, and rolling to obtain the PCB photosensitive dry film.
According to the invention, acrylic resin oligomer, a photoreaction monomer reacting under different energies, a low-energy photoinitiator, a high-energy photoinitiator and an auxiliary agent are prepared into photosensitive resin glue solution, the photosensitive resin glue solution is coated on PET, the existing thermosetting coating process is replaced by a UV curing coating process, a PCB dry film is obtained by low-energy UV irradiation curing, and a client transfers a required negative film pattern to a PCB plate after high-energy UV irradiation.
The method of the invention does not discharge VOC gas in the production process, and is environment-friendly, economical and efficient.
As a preferable scheme of the invention, in the step 1), the hydroxyl acrylate monomer, the initiator and the relative molecular mass control agent are sequentially as follows: 10-15 parts of hydroxyl acrylate monomer, 8-15 parts of acrylate monomer, 0.05-0.2 part of initiator and 1-1.5 parts of relative molecular mass control agent.
In a preferred embodiment of the present invention, the initiator is azobisisobutyronitrile, and the relative molecular mass controller is dodecanethiol.
As a preferable scheme of the invention, in the step 1), the reaction is firstly carried out for 35-45min at 78-82 ℃, then the temperature is reduced to 65-75 ℃, and the reaction is carried out for 90-150min.
As a preferable scheme of the invention, in the step 2), the photoreactive monomer composition is a composition of EOEOEOEA, IBOA and LA with the mass ratio of 4-6:2-4:1-3.
In a preferred embodiment of the present invention, in step 2), the first photoinitiator is UV1173, and the second photoinitiator is UV819.
As a preferable scheme of the present invention, in step 2), the acrylic resin oligomer, the photoreactive monomer composition, the first photoinitiator, the second photoinitiator and the auxiliary agent are sequentially, in parts by weight: 75-85 parts of acrylic resin oligomer, 15-25 parts of photoreaction monomer composition, 0.1-0.8 part of first photoinitiator, 0.1-0.5 part of second photoinitiator and 0.8-1.2 parts of auxiliary agent.
As a preferable embodiment of the present invention, in the step 2), the assistant is a composition of a leveling agent, OP powder and PS powder.
Compared with the prior art, the invention has the following beneficial effects:
1) The preparation method has simple steps, and the prepared PCB dry film has good performance;
2) The preparation method provided by the invention adopts a UV curing mode, does not consume a large amount of organic solvent, does not need the heat of an oven, does not have the emission of VOC gas, and is economic and environment-friendly.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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 raw materials used in the present invention are all commercially available.
Example 1
The embodiment provides a preparation method of a UV curing PCB dry film for copper-clad plate photoetching, which comprises the following steps:
1) Synthesis of acrylic resin oligomer:
a mixture of hydroxyl acrylate monomer, initiator and relative molecular mass control agent is added into a four-neck flask provided with a stirrer, a condenser pipe, a constant pressure funnel and a nitrogen pipe. First, 10g of methyl methacrylate, 13g of hydroxypropyl acrylate, 3g of methacrylic acid, 0.1g of azobisisobutyronitrile, and 1.1g of dodecanethiol were mixed in a beaker at room temperature to form a transparent solution. Secondly, reacting for 40min at the temperature of a constant-temperature water bath kettle of 80 ℃, and finally reducing the temperature to 70 ℃ for 2h. And (3) regulating the mass ratio of the hydroxyl acrylate monomer to the acrylate monomer, and the mass of the initiator and the relative molecular mass control agent to obtain the hydroxyl acrylate resin with different relative molecular masses.
2) Preparing photosensitive resin glue solution:
weighing 80g of acrylic resin oligomer, and mixing according to the mass ratio EOEOEOEA: IBOA: LA =5, 20g of the photoreactive monomer composition, 0.5g of the photoinitiator 1173,0.2g of the photoinitiator 819,1g of the leveling agent 6501,0.05g of the OP powder, and 0.05g of the PS powder were weighed, poured into a four-neck flask, and mixed and stirred uniformly to obtain a photosensitive resin paste solution.
3) Preparing a photosensitive dry film:
coating the photosensitive resin glue solution obtained in the step 2) on PET, and selecting the wavelength of light with the wavelength of 273nm or less by using a filter for irradiation. Time determination of the irradiation: exposing with a 41-step energy ruler, developing at the optimal developing speed, and selecting the exposure energy with 20 steps as the optimal exposure energy; and testing the gel rate of the adhesive film, namely, rolling the adhesive film to obtain the PCB dry film, wherein the gel rate is about 30%.
Example 2
The embodiment provides a preparation method of a UV curing PCB dry film for copper-clad plate photoetching, which comprises the following steps:
1) Synthesis of acrylic resin oligomer:
a mixture of hydroxyl acrylate monomer, initiator and relative molecular mass control agent is added into a four-neck flask provided with a stirrer, a condenser pipe, a constant pressure funnel and a nitrogen pipe. First, 11g of methyl methacrylate, 10g of hydroxypropyl acrylate, 2g of methacrylic acid, 0.05g of azobisisobutyronitrile, and 1.5g of dodecanethiol were mixed in a beaker at room temperature to form a transparent solution. Secondly, reacting for 35min at the temperature of the constant-temperature water bath kettle of 78 ℃, and finally reducing the temperature to 65 ℃ for reacting for 2.5h. And (3) regulating the mass ratio of the hydroxyl acrylate monomer to the acrylate monomer, and the mass of the initiator and the relative molecular mass control agent to obtain the hydroxyl acrylate resin with different relative molecular masses.
2) Preparing photosensitive resin glue solution:
weighing 75g of acrylic resin oligomer, and mixing according to the mass ratio EOEOEOEA: IBOA: LA = 4.
3) Preparing a photosensitive dry film:
coating the photosensitive resin glue solution obtained in the step 2) on PET, and selecting the wavelength of light with the wavelength of 273nm or less by using a filter for irradiation. Time determination of the irradiation: exposing by using a 41-step energy ruler, developing at the optimal developing speed, and selecting the exposure energy with 20 light steps as the optimal exposure energy; and testing the gel rate of the adhesive film, namely, rolling the adhesive film to obtain the PCB dry film, wherein the gel rate is about 30%.
Example 3
The embodiment provides a preparation method of a UV curing PCB dry film for copper-clad plate photoetching, which comprises the following steps:
1) Synthesis of acrylic resin oligomer:
a mixture of hydroxyl acrylate monomer, initiator and relative molecular mass control agent is added into a four-neck flask provided with a stirrer, a condenser pipe, a constant pressure funnel and a nitrogen pipe. First, 10g of methyl methacrylate, 15g of hydroxypropyl acrylate, 4g of methacrylic acid, 0.2g of azobisisobutyronitrile, and 1g of dodecanethiol were mixed in a beaker at room temperature to form a transparent solution. Secondly, reacting for 45min at the temperature of the constant-temperature water bath kettle of 82 ℃, and finally reducing the temperature to 75 ℃ for reacting for 1.5h. And (3) regulating the mass ratio of the hydroxyl acrylate monomer to the acrylate monomer, and the mass of the initiator and the relative molecular mass control agent to obtain the hydroxyl acrylate resin with different relative molecular masses.
2) Preparing photosensitive resin glue solution:
weighing 80g of acrylic resin oligomer, and mixing according to the mass ratio EOEOEOEA: IBOA: LA =6, and 25g of the total photoreactive monomer composition, 0.8g of the photoinitiator 1173, 0.1g of the photoinitiator 819,1.07g of the leveling agent 6501,0.08g of the OP powder, and 0.07g of the PS powder were weighed, poured into a four-necked flask, and mixed and stirred uniformly to obtain a photosensitive resin paste solution.
3) Preparing a photosensitive dry film:
coating the photosensitive resin glue solution obtained in the step 2) on PET, and selecting the wavelength of light with the wavelength of less than 273nm by using a filter for irradiation. Time determination of the irradiation: exposing by using a 41-step energy ruler, developing at the optimal developing speed, and selecting the exposure energy with 20 light steps as the optimal exposure energy; and testing the gel rate of the adhesive film, namely, rolling the adhesive film to obtain the PCB dry film, wherein the gel rate is about 30%.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (8)
1. A preparation method of a UV curing PCB dry film for copper-clad plate photoetching is characterized by comprising the following steps:
1) Synthesis of acrylic resin oligomer: adding a mixture of a hydroxyl acrylate monomer, an initiator and a relative molecular mass control agent into a container, reacting for a period of time under the water bath condition, and then cooling to react to obtain an acrylic resin oligomer;
2) Preparing photosensitive resin glue solution: adding the acrylic resin oligomer obtained in the step 1), the photoreaction monomer composition, the first photoinitiator, the second photoinitiator and the auxiliary agent into a container, and uniformly mixing to obtain a photosensitive resin glue solution;
3) Preparing a photosensitive dry film: coating the photosensitive resin glue solution obtained in the step 2) on PET, irradiating under 273nm light, and rolling to obtain the PCB photosensitive dry film.
2. The method for preparing the UV-cured PCB dry film for copper-clad plate lithography according to claim 1, wherein in step 1), the hydroxyl acrylate monomer, the initiator and the relative molecular mass control agent are sequentially as follows in parts by weight: 10-15 parts of hydroxyl acrylate monomer, 8-15 parts of acrylate monomer, 0.05-0.2 part of initiator and 1-1.5 parts of relative molecular mass control agent.
3. The method for preparing the UV-cured PCB dry film for the photoetching of the copper-clad plate according to claim 1 or 2, wherein the initiator is azobisisobutyronitrile, and the relative molecular mass control agent is dodecyl mercaptan.
4. The method for preparing the UV-cured PCB dry film for copper-clad plate lithography according to claim 1, wherein in the step 1), the reaction is carried out for 35-45min at 78-82 ℃, and then the temperature is reduced to 65-75 ℃ for 90-150min.
5. The method for preparing the UV-curable PCB dry film for copper clad laminate lithography according to claim 1, wherein in the step 2), the photoreactive monomer composition is a composition of EOEOEA, IBOA and LA with a mass ratio of 4-6:2-4:1-3.
6. The method for preparing the UV-curable PCB dry film for copper-clad plate lithography according to claim 1, wherein in the step 2), the first photoinitiator is UV1173, and the second photoinitiator is UV819.
7. The method for preparing the UV-cured PCB dry film for copper-clad plate lithography according to claim 1, wherein in the step 2), the acrylic resin oligomer, the photoreaction monomer composition, the first photoinitiator, the second photoinitiator and the auxiliary agent are sequentially as follows in parts by weight: 75-85 parts of acrylic resin oligomer, 15-25 parts of photoreaction monomer composition, 0.1-0.8 part of first photoinitiator, 0.1-0.5 part of second photoinitiator and 0.8-1.2 parts of auxiliary agent.
8. The method for preparing the UV-cured PCB dry film for copper-clad plate lithography according to claim 1, wherein in the step 2), the auxiliary agent is a composition of a leveling agent, OP powder and PS powder.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210947553.2A CN115368609A (en) | 2022-08-09 | 2022-08-09 | Preparation method of UV (ultraviolet) cured PCB (printed Circuit Board) dry film for copper-clad plate photoetching |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210947553.2A CN115368609A (en) | 2022-08-09 | 2022-08-09 | Preparation method of UV (ultraviolet) cured PCB (printed Circuit Board) dry film for copper-clad plate photoetching |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0640875A1 (en) * | 1993-08-27 | 1995-03-01 | E.I. Du Pont De Nemours And Company | Aqueous developable flexographic printing plate |
| CN105849640A (en) * | 2013-12-24 | 2016-08-10 | 可隆工业株式会社 | Photosensitive resin composition for dry film photoresist |
| CN110488570A (en) * | 2019-08-29 | 2019-11-22 | 浙江福斯特新材料研究院有限公司 | A kind of photosensitive polymer combination and application thereof |
| CN114350202A (en) * | 2022-01-21 | 2022-04-15 | 东莞市蓝邦电子五金材料有限公司 | Water-soluble photosensitive ink and preparation method and construction method thereof |
| CN114859656A (en) * | 2022-05-17 | 2022-08-05 | 杭州福斯特电子材料有限公司 | Photosensitive resin composition and dry film anti-corrosion laminated body thereof |
-
2022
- 2022-08-09 CN CN202210947553.2A patent/CN115368609A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0640875A1 (en) * | 1993-08-27 | 1995-03-01 | E.I. Du Pont De Nemours And Company | Aqueous developable flexographic printing plate |
| CN105849640A (en) * | 2013-12-24 | 2016-08-10 | 可隆工业株式会社 | Photosensitive resin composition for dry film photoresist |
| CN110488570A (en) * | 2019-08-29 | 2019-11-22 | 浙江福斯特新材料研究院有限公司 | A kind of photosensitive polymer combination and application thereof |
| CN114350202A (en) * | 2022-01-21 | 2022-04-15 | 东莞市蓝邦电子五金材料有限公司 | Water-soluble photosensitive ink and preparation method and construction method thereof |
| CN114859656A (en) * | 2022-05-17 | 2022-08-05 | 杭州福斯特电子材料有限公司 | Photosensitive resin composition and dry film anti-corrosion laminated body thereof |
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