CN108633187B - Method for preparing base material with metal pattern - Google Patents

Method for preparing base material with metal pattern Download PDF

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Publication number
CN108633187B
CN108633187B CN201710159058.4A CN201710159058A CN108633187B CN 108633187 B CN108633187 B CN 108633187B CN 201710159058 A CN201710159058 A CN 201710159058A CN 108633187 B CN108633187 B CN 108633187B
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photosensitive resin
resin composition
layer
base material
substrate
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CN108633187A (en
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何明展
徐茂峰
向首睿
苏赐祥
徐筱婷
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Zhen Ding Technology Co Ltd
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Zhen Ding Technology Co Ltd
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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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • 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
    • 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
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/05—Patterning and lithography; Masks; Details of resist
    • H05K2203/0502—Patterning and lithography
    • H05K2203/052—Magnetographic patterning
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/072—Electroless plating, e.g. finish plating or initial plating
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/0723—Electroplating, e.g. finish plating

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Electromagnetism (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Materials For Photolithography (AREA)

Abstract

A method of preparing a substrate having a metal pattern, comprising the steps of: providing a high molecular base material and a photosensitive resin composition and coating the photosensitive resin composition on one surface of the high molecular base material; forming a patterned photosensitive resin layer from the photosensitive resin composition by exposure and development; forming a seed crystal layer on the surface of the photosensitive resin layer far away from the high polymer base material in a chemical plating mode; and forming a metal layer on the surface of the seed crystal layer by electroplating to form the substrate with the metal pattern, wherein the seed crystal layer and the metal layer form the metal pattern.

Description

Method for preparing base material with metal pattern
Technical Field
The invention relates to a base material with a metal pattern, in particular to a preparation method of the base material with the metal pattern.
Background
In the future, electronic communication products are developed toward multi-function, thin and integrated, and people have more and more demands for flexible circuit boards with higher density and thinner circuits. The application of the polymer metallization technology in the manufacture of flexible circuit boards with higher density and thinner circuits is becoming wider and wider.
In the prior art, the polymer metallization process flow is as follows: degreasing, ring opening, catalyzing, reducing, nickel dissolving, copper plating and the like. The process flow is complex and complex.
In addition, the above process degreases and opens the polymer substrate to form hydroxyl and carboxyl. This causes degradation of the polymer substrate, thereby destroying the physical properties of the polymer substrate.
Disclosure of Invention
In view of the above, it is desirable to provide a method for preparing a substrate having a metal pattern, which can solve the above problems.
A method of preparing a substrate having a metal pattern, comprising the steps of:
providing a high molecular base material and a photosensitive resin composition and coating the photosensitive resin composition on one surface of the high molecular base material;
forming a patterned photosensitive resin layer from the photosensitive resin composition by exposure and development;
forming a seed crystal layer on the surface of the photosensitive resin layer far away from the high polymer base material in a chemical plating mode; and
and forming a metal layer on the surface of the seed crystal layer by electroplating, thereby forming the base material with the metal pattern.
Compared with the prior art, the preparation method of the base material with the metal pattern provided by the invention has the advantages that the photosensitive resin composition is coated on the surface of the high-molecular base material and is directly patterned, so that the photosensitive resin composition is directly combined with the high-molecular base material and is directly metallized in a chemical plating and electroplating mode, the surface treatment (degreasing and ring opening) of the high-molecular base material is not required, the process is simple, and the physical performance of the high-molecular base material is not damaged.
Drawings
FIG. 1 is a cross-sectional view of a polymer substrate coated with a photosensitive resin composition according to a preferred embodiment of the present invention.
FIG. 2 is a sectional view after pre-baking the photosensitive resin composition shown in FIG. 1 to form a photosensitive resin composition layer.
Fig. 3 is a sectional view of the photosensitive resin layer formed by forming the photosensitive resin composition layer shown in fig. 2.
Fig. 4 is a cross-sectional view of the photosensitive resin layer shown in fig. 3 after a seed layer is formed on the surface thereof.
Fig. 5 is a cross-sectional view of the substrate with a metal pattern formed by selectively plating a metal layer on the seed layer shown in fig. 4.
Description of the main elements
Substrate with metal pattern 100
Base material 10
Photosensitive resin composition 20
Photosensitive resin composition layer 21
Photosensitive resin layer 22
Seed layer 30
Metal layer 40
The following detailed description will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
In order to further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be made on the specific embodiments, structures, features and effects of the method for manufacturing the substrate with metal patterns and the flexible circuit board provided by the present invention with reference to the accompanying drawings 1-5 and the preferred embodiments.
Referring to fig. 1-5, a method for manufacturing a substrate 100 with a metal pattern according to a preferred embodiment of the present invention is provided, where the substrate 100 with a metal pattern may be a flexible circuit board (single-sided board, double-sided board, multi-layer board), an electromagnetic shielding film, or the like.
In the present embodiment, the substrate 100 with metal patterns is a flexible circuit board. The method for manufacturing the substrate 100 having a metal pattern will be further described below by taking a method for manufacturing a single-sided board in a flexible circuit board as an example.
The preparation method of the substrate 100 with the metal pattern comprises the following steps:
referring to fig. 1, a polymer substrate 10 and a photosensitive resin composition 20 are provided, and the photosensitive resin composition 20 is coated on a surface of the polymer substrate 10.
Wherein the thickness of the photosensitive resin composition 20 coated on the surface of the polymer substrate 10 is 1-5 um.
The material of the polymer substrate 10 is usually one or more of low dielectric loss and low dielectric constant polymer materials such as Polyethylene Terephthalate (PET), Polyethylene Naphthalate (PEN), Liquid Crystal Polymer (LCP), and the like.
The material of the polymer substrate 10 may also be Polyimide (PI). Although the polyimide itself does not contain carboxyl, the photosensitive resin composition 20 prepared in the present invention contains moisture, and when the photosensitive resin composition 20 is coated on the polymer substrate 10 of the polyimide, the polyimide is caused to open the ring to form carboxyl, and the physical properties of the polyimide are not destroyed, so the ring opening is not equivalent to the degreasing and ring opening surface treatment commonly used in the prior art.
In this embodiment, the material of the polymer substrate 10 is ethylene terephthalate, and the structural formula thereof is:
Figure GDA0002516345440000031
the photosensitive resin composition 20 is a photosensitive patterned coating containing carboxyl and oxazoline functional groups. Specifically, the photosensitive resin composition 20 comprises, by weight, 100 parts of epoxy acrylate, 10 to 50 parts of photosensitive monomer, 10 to 40 parts of photosensitive oligomer, 5 to 15 parts of photoinitiator, 1 to 5 parts of colorant, and 10 to 50 parts of oxazoline compound. Wherein the photosensitive resin composition does not include an epoxy resin. In this embodiment, the photosensitive resin composition further comprises an appropriate amount of solvent to adjust the viscosity of the photosensitive resin composition. Wherein the solvent may be butanone.
The number of the reactive functional groups of the epoxy acrylate is 2-4, and the reactive functional groups comprise benzene rings, carboxyl (-COOH) groups or hydroxyl (-OH) groups. In the embodiment, the molecular weight of the epoxy acrylate is 10000-40000 g/mole, and the acid value is 70-150 mgKOH/g.
The photosensitive monomer and the photosensitive oligomer both have a plurality of reactive functional groups, and are used for carrying out polymerization and crosslinking reaction with the epoxy acrylate when the photosensitive resin composition is irradiated by ultraviolet light.
In this embodiment, the number of reactive functional groups of the photosensitive monomer is not less than 3. The photosensitive monomer may be selected from one of polyethylene glycol diacrylate (PEGDA), 1, 6-hexanediol diacrylate (HDDA), ethoxybisphenol a diacrylate (BPA), trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), ethoxylated trimethylolpropane triacrylate [ TMP (eo) TA ], and propoxylated trimethylolpropane triacrylate [ TMP (3PO) TA ], and the like.
In this embodiment, the photosensitive oligomer may be an aliphatic urethane acrylate. The number of the reaction functional groups of the photosensitive oligomer is 2-4, and the molecular weight of the photosensitive oligomer is 3000-6000 g/mole.
The photoinitiator is used for absorbing ultraviolet light to form free radicals or cations when the photosensitive resin composition is irradiated by the ultraviolet light, and initiating polymerization and crosslinking reaction of the epoxy acrylate, the photosensitive monomer and the photosensitive oligomer.
The photoinitiator can be at least one selected from alpha-hydroxy ketone compounds, acyl phosphine oxides, alpha-amino ketone compounds, oxime ester compounds and the like. More specifically, the photoinitiator may be selected from at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, benzoin bismethyl ether, benzophenone, isopropylthioxanthone, and carbazolone ester.
The oxazoline compound (chemical formula is
Figure GDA0002516345440000051
) When the photosensitive resin composition is heated to a preset temperature higher than the normal temperature, the photosensitive resin composition will react with the carboxyl in the epoxy acrylate, and when the temperature is lower than the preset temperature (such as the normal temperature), the oxazoline compound is inactive, and the photosensitive resin composition does not include epoxy resin, thereby facilitating the storage of the photosensitive resin composition at the normal temperature. In this example, the molecular weight of the oxazoline compound is 7000 g/mole. Wherein the reaction formula of the oxazoline compound and the carboxyl is as follows:
Figure GDA0002516345440000052
the colorant is used for making the photosensitive resin composition to present a desired color, and may be selected from at least one of pigments and dyes.
The pigment may be at least one selected from inorganic pigments and organic pigments.
In this embodiment, the pigment may be selected from one of phthalocyanine blue, phthalocyanine green, crystal violet, permanent yellow, titanium dioxide, carbon black, iron oxide black, and aniline black.
The dye may be an organic dye, and more particularly, the dye may be at least one of a natural organic dye and a synthetic organic dye.
In this example, the dye may be selected from one of Kayase Red-B, Black-AN, Blue-N (chemical industry Standard), Neozapon Red 355, Orasol Black-X55, Oracet Yellow-144FE (chemical industry Standard), and the like, manufactured by Nippon chemical Co., Ltd.
In this embodiment, the photosensitive resin composition further includes 0.5 to 1 part by weight of triphenylphosphine.
Referring to fig. 2, the photosensitive resin composition 20 is pre-baked and semi-cured to form a photosensitive resin composition layer 21.
Wherein the pre-baking temperature is 80-120 ℃, and the pre-baking time is 20 minutes-1 hour.
In this example, the temperature of the prebaking was 80 ℃ and the prebaking time was 20 minutes.
Specifically, during the pre-baking process, a thermal curing reaction occurs between the carboxyl groups in the photosensitive resin composition 20 and the oxazoline compound, forming a chemically cross-linked network structure, thereby increasing the cross-linking density of the photosensitive resin composition. Meanwhile, the oxazoline compound in the photosensitive resin composition 20 and the carboxyl group in the polymer substrate 10 are also subjected to a thermal curing reaction, so that a chemically cross-linked network structure is formed between the polymer substrate 10 and the photosensitive resin composition layer 21, thereby enhancing the adhesion between the polymer substrate 10 and the photosensitive resin composition layer 21.
Third, referring to fig. 3, a desired pattern is formed in the photosensitive resin composition layer 21 by an exposure and development technique, and is thermally baked, thereby forming a patterned photosensitive resin layer 22.
In this embodiment, the exposure is performed with an exposure amount of 400mj/cm2。
In this example, a sodium bicarbonate solution with a mass concentration of 1% was used as the developer.
In this example, the temperature of the thermal baking was 150 ℃, and the time of the thermal baking was 1.5 hours.
Specifically, in the thermal baking process, the oxazoline compound in the photosensitive resin composition 20 and the carboxyl group in the photosensitive resin composition 20 and the polymer substrate 10 simultaneously undergo a further thermal curing reaction, so as to further form a chemically cross-linked network structure, further increase the cross-linking density between the photosensitive resin composition layer 21 and the polymer substrate 10, so that the photosensitive resin layer 22 has better alkali resistance and solder heat resistance, and the adhesion between the photosensitive resin layer 22 and the polymer substrate 10 is stronger.
In a fourth step, referring to fig. 4, a seed layer 30 is adsorbed on the surface of the patterned photosensitive resin layer 22 away from the polymer substrate 10, so as to facilitate electrical conduction during the subsequent electroplating.
The seed layer 30 is formed as follows:
first, palladium ions (Pd) are adsorbed on the surface of the patterned photosensitive resin layer 22 away from the polymer substrate 102+) In particular, the Pd2+And binds to carboxyl groups in the patterned photosensitive resin layer 22.
Secondly, Pd is reduced by reduction reaction2+Reducing the solution into Pd.
Then, a nickel layer is deposited on the Pd surface layer by electroless plating, thereby forming the seed layer 30.
Fifthly, a metal layer 40 is electroplated on the surface of the seed layer 30 away from the patterned photosensitive resin layer 22, thereby forming the substrate 100 with the metal pattern.
Specifically, in the present embodiment, the metal layer 40 is a copper layer, and the seed layer 30 and the metal layer 40 constitute a conductive circuit layer of the flexible circuit board.
For the double-sided board preparation method, the above steps may be repeated.
Specifically, in the second step: after or in the third step of forming the semi-cured photosensitive resin composition layer 21: after forming the photosensitive resin layer 22 or a fifth step: after the metal layer 40 is formed, the steps of the first to fifth steps are repeated.
In addition, since the metal layer 40 (conductive circuit) is formed by electroplating, the thickness of the metal layer 40 (conductive circuit) can be arbitrarily adjusted according to actual needs.
The preparation method of the substrate 100 with the metal pattern, 1) patterns the photosensitive resin composition 20 coated on the high molecular substrate 10, so that the high molecular substrate 10 does not need to be degreased and opened during the preparation process of the substrate 100 with the metal pattern, thereby simplifying the process and avoiding damaging the physical properties of the high molecular substrate; 2) the provided photosensitive resin composition 20 contains functional groups such as oxazoline, and during the preparation process, the carboxyl group in the polymer substrate 10 and the functional groups such as oxazoline in the photosensitive resin composition 20 undergo a thermal curing reaction, so that a chemically crosslinked network structure (covalent bond) is formed between the polymer substrate 10 and the photosensitive resin composition 20, thereby enhancing the adhesion between the polymer substrate 10 and the photosensitive resin layer 22; 3) the metal layer (conductive circuit layer) 40 is formed on the patterned photosensitive resin layer 22 by chemical plating and electroplating, so that the thickness of the metal layer 40 can be adjusted at will, and the thin circuit can be manufactured.
Although the present invention has been described with reference to the above preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

1. A method of preparing a substrate having a metal pattern, comprising the steps of:
providing a high molecular base material and a photosensitive resin composition and coating the photosensitive resin composition on one surface of the high molecular base material; the high molecular base material contains carboxyl, and the photosensitive resin composition contains carboxyl and oxazoline functional groups;
pre-baking the polymer substrate coated with the photosensitive resin composition to semi-cure the photosensitive resin composition so as to form a photosensitive resin composition layer; both the carboxyl group in the photosensitive resin composition and the oxazoline functional group and the carboxyl group in the high molecular base material have thermal curing reaction to form a chemically crosslinked network structure;
forming a patterned photosensitive resin layer on the photosensitive resin composition layer by exposure and development;
forming a seed crystal layer on the surface of the patterned photosensitive resin layer far away from the high polymer base material in a chemical plating mode; and
forming a metal layer on the surface of the seed crystal layer by electroplating to form the substrate with the metal pattern, wherein the seed crystal layer and the metal layer form the metal pattern.
2. The method of claim 1, wherein the polymeric substrate is at least one of polyethylene terephthalate, polyethylene naphthalate, and liquid crystal polymer.
3. The method of claim 1, wherein the polymeric substrate is polyimide.
4. The method of claim 1, wherein the photosensitive resin composition comprises, by weight, 100 parts of epoxy acrylate, 10 to 50 parts of photosensitive monomer, 10 to 40 parts of photosensitive oligomer, 5 to 15 parts of photoinitiator, 1 to 5 parts of colorant, and 10 to 50 parts of oxazoline compound; wherein the number of the reactive functional groups of the epoxy acrylate is 2-4, and the chemical formula of the oxazoline compound is as follows:
Figure FDA0002710157180000021
5. the method of claim 1, wherein the photosensitive resin composition further comprises 0.5 to 1 part by weight of triphenylphosphine.
6. The method of producing a substrate having a metal pattern according to claim 1, wherein an epoxy resin is not included in the photosensitive resin composition.
7. The method of claim 1, wherein after the step of forming the patterned photosensitive resin layer and before the step of forming the seed layer, the method further comprises: and carrying out thermal baking on the polymer substrate on which the patterned photosensitive resin layer is formed.
8. The method of claim 7, wherein the temperature of the thermal baking is 150 ℃ and the time of the thermal baking is 1.5 hours.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1755524A (en) * 2004-09-28 2006-04-05 山荣化学有限公司 Phototonus thermosetting resin composition and printing plug board coating with resist and its manufacturing method
CN100524021C (en) * 2003-03-07 2009-08-05 旭硝子株式会社 Photosensitive resin composition and coating film cured product thereof
CN105828587A (en) * 2015-01-06 2016-08-03 富葵精密组件(深圳)有限公司 Photosensitive ink and electromagnetic shielding structure employing same, circuit board, and electronic device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100524021C (en) * 2003-03-07 2009-08-05 旭硝子株式会社 Photosensitive resin composition and coating film cured product thereof
CN1755524A (en) * 2004-09-28 2006-04-05 山荣化学有限公司 Phototonus thermosetting resin composition and printing plug board coating with resist and its manufacturing method
CN105828587A (en) * 2015-01-06 2016-08-03 富葵精密组件(深圳)有限公司 Photosensitive ink and electromagnetic shielding structure employing same, circuit board, and electronic device

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