CN114574116B - Carrier resin film and preparation method and application thereof - Google Patents

Carrier resin film and preparation method and application thereof Download PDF

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Publication number
CN114574116B
CN114574116B CN202111576863.XA CN202111576863A CN114574116B CN 114574116 B CN114574116 B CN 114574116B CN 202111576863 A CN202111576863 A CN 202111576863A CN 114574116 B CN114574116 B CN 114574116B
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Prior art keywords
resin
film
carrier
base film
layer
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CN114574116A (en
Inventor
刘东亮
汪青
佘乃东
刘潜发
董晋超
张艳华
黄文琦
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/50—Adhesives in the form of films or foils characterised by a primer layer between the carrier and the adhesive
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2427/00—Presence of halogenated polymer
    • C09J2427/006—Presence of halogenated polymer in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a carrier resin film, a preparation method and application thereof, wherein the carrier resin film comprises a base film and a resin layer, the initial peeling strength of the resin layer and the base film is 0.40-1.0N/mm, the peeling strength of the resin layer and the base film is 0.20-0.8N/mm after the carrier resin film is subjected to heat treatment, and the heat treatment temperature is 170-190 ℃ and the time is 30-60min. The carrier resin film has good adhesion at normal temperature, high peel strength retention rate after high-temperature baking, and good laser drilling processability, and can be applied to printed circuit boards of multi-layer laminates, in particular to printed circuit boards of multi-layer laminates for manufacturing fine lines and micropores.

Description

Carrier resin film and preparation method and application thereof
Technical Field
The invention belongs to the technical field of carrier resin films, and relates to a carrier resin film, a preparation method and application thereof.
Background
Along with the trend of the electronic information products mainly oriented to the light, thin, short and small and multifunctional design in the future, the technical level of the printed circuit board serving as the main support of electronic components is also continuously improved so as to provide high-density wiring, thinness, micro-aperture, multidimensional three-dimensional and the like. Particularly, when the thickness of the dielectric layer is 30 μm or even 20 μm or less, the conventional glass cloth reinforced prepreg cannot meet the use requirement, and instead, a resin adhesive film is often used.
Resin adhesive films without reinforcing materials are developed and applied as new generation base materials because of thinner shapes, high-density wiring, micro-pore diameters, multi-dimensional stereo forming and the like, and meanwhile, fine circuits and laser micro-pores are generally manufactured by adopting a half additive method (SAP) because line width and line spacing below 25/25 mu m are difficult to manufacture by traditional etching technology. In the SAP process, after vacuum lamination of the resin adhesive film, the resin adhesive film needs to be baked and cured at the temperature of 170-190 ℃, and in the process, the film needs to be baked with a base film to protect the surface of the resin adhesive film and reduce pollution. However, after the conventional carrier resin film is baked at a high temperature, the peel strength of the resin layer and the base film is drastically reduced, thereby causing a problem of defective hole patterns easily occurring during laser drilling.
CN110684472a discloses a halogen-free flame-retardant epoxy resin adhesive film, which comprises the following components in parts by mass: 100 parts of bisphenol A epoxy resin, 50 parts of polyvinyl chloride resin, 2-8 parts of plasticizer, 1.2-3.6 parts of curing agent, 0.2-0.8 part of acidulant, 0.8-2.4 parts of halogen-free flame retardant, 0.4-0.8 part of antioxidant, 0.3-0.6 part of cross-linking agent and 1.2-3.6 parts of silane coupling agent; according to the invention, the halogen-free flame retardant HS-ACM is added, so that the flame retardance of the epoxy resin adhesive film is improved, the environment is protected, no pollution is caused, the HS-ACM is superfine nitrogen-phosphine white powder, the high-efficiency intumescent flame retardant is nontoxic, odorless and tasteless, the decomposition temperature is higher than 240 ℃, dehydration and charcoal formation are realized at high temperature, and nitrogen, carbon dioxide and water are released during combustion; according to the invention, by adding the acidulant, the curing acceleration effect can be achieved and the adhesive force of the adhesive film to metal can be increased. However, the epoxy resin film is not suitable for being applied to the field of printed wiring boards alone.
Therefore, in the art, it is desired to develop a carrier resin film which has good adhesion at normal temperature, high retention of peel strength after baking at high temperature, and good laser drilling processability, so as to be applied to a printed wiring board of a multi-layered laminate, particularly a printed wiring board of a multi-layered laminate for manufacturing fine lines and micro holes.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a carrier resin film and a preparation method and application thereof. The carrier resin film has good adhesion at normal temperature, high peel strength retention rate after high-temperature baking, and good laser drilling processability, and can be applied to printed circuit boards of multi-layer laminates, in particular to printed circuit boards of multi-layer laminates for manufacturing fine lines and micropores.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a carrier resin film comprising a base film and a resin layer, the resin layer having an initial peel strength from the base film of 0.40 to 1.0N/mm (e.g., 0.40N/mm, 0.50N/mm, 0.60N/mm, 0.70N/mm, 0.80N/mm, 0.90N/mm, or 1.0N/mm, etc.), the carrier resin film having a peel strength from the base film of 0.20 to 0.80N/mm (e.g., 0.20N/mm, 0.30N/mm, 0.40N/mm, 0.50N/mm, 0.60N/mm, 0.70N/mm, or 0.80N/mm, etc.) after heat treatment.
In the invention, by controlling the peeling strength of the resin layer and the base film before and after the heat treatment of the carrier resin film, the carrier resin film has good cohesiveness at normal temperature, high peeling strength retention rate after high-temperature baking, and better laser drilling processability, meets the processing requirements of subsequent copper deposition electroplating and the like, and is beneficial to improving the micropore quality.
Preferably, the temperature of the heat treatment is 170-190 ℃, e.g. 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, etc.
Preferably, the heat treatment is performed for 30-60min, such as 30min, 35min, 40min, 45min, 50min, 55min or 60min.
Preferably, the resin layer comprises 20-60 parts by weight (e.g., 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, etc.) of thermosetting resin, 40-80 parts by weight (e.g., 45 parts by weight, 50 parts by weight, 5 parts by weight5 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, or the like) of the surface-treated inorganic filler having a carbon amount per unit surface area of 0.20mg/m 2 -0.50mg/m 2 For example, it may be 0.25mg/m 2 、0.30mg/m 2 、0.35mg/m 2 、0.40mg/m 2 Or 0.45mg/m 2 . After the inorganic filler is subjected to surface treatment, the bonding force of the interface between the resin layer and the base film can be improved, and the principle is that: in the resin layer with high filler proportion, the filler with coupling groups on the surface has good dispersibility in thermosetting resin, and can avoid filler aggregation on the surface of the resin layer of the carrier resin film, thereby avoiding the occupation of the surface of the resin layer by the filler and reducing the effective contact between the resin and the base film; by controlling the carbon amount per unit surface area of the surface-treated inorganic filler, it is possible to prevent excessive surface treatment agent on the filler surface from migrating to the resin layer surface of the carrier resin film after baking at high temperature, and microscopic bubbles are formed between the resin layer and the base film.
In the present invention, the degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The carbon amount per unit surface area of the inorganic filler can be determined by: the surface-treated inorganic filler was subjected to a cleaning treatment using methyl ethyl ketone, and then measured. Specifically, 30g of methyl ethyl ketone was added to 15g of the inorganic filler surface-treated with the surface treatment agent, the mixture was ultrasonically cleaned at 25℃for 5 minutes, the supernatant was removed, and the solid content was dried, and then the carbon content per unit surface area of 0.3g of the inorganic filler was measured by using a carbon analyzer. As the carbon analyzer, EMIA-320V manufactured by horiba, inc. was used.
Preferably, the surface-treated surface-treating agent is selected from any one or a combination of at least two of a silane coupling agent, a silicone oligomer or a titanate coupling agent.
Preferably, the thermosetting resin comprises any one or a combination of at least two of epoxy resin, phenolic resin, cyanate ester, active ester, polyphenylene ether resin, maleimide resin, silicone resin, polybenzoxazole resin, polyimide resin, hydrocarbon resin or acrylate resin.
Preferably, the epoxy resin comprises one or a combination of at least two of bisphenol a type epoxy resin, bisphenol F type epoxy resin, phosphorous containing epoxy resin, MDI modified epoxy resin, phenolic epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene containing epoxy resin, or cycloaliphatic epoxy resin.
Preferably, the phenolic resin comprises one or a combination of at least two of bisphenol a type phenolic resin, phenol type phenolic resin, biphenyl type phenolic resin, dicyclopentadiene type phenolic resin or naphthol containing phenolic resin.
Preferably, the inorganic filler is selected from any one or a combination of at least two of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, boehmite, calcium carbonate, calcium silicate, or mica.
Preferably, the thickness of the resin layer is 5 to 150 μm, for example, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, or the like.
Preferably, the thickness of the base film is 10-100 μm, for example 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm, etc.
Preferably, the base film is selected from any one of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide (PI), polytetrafluoroethylene (PTFE), polybenzimidazole (PBI), polyether ether ketone (PEEK), polyphenylene sulfide (PPS), copper foil, aluminum foil, nickel foil, or alloy foil.
As a preferable technical scheme of the present invention, a release layer is further disposed between the base film and the resin layer, and it should be noted that the release layer corresponds to a portion of the base film, and when the release layer exists, the peel strength of the resin layer and the base film refers to the peel strength of the resin layer and the release layer.
Preferably, the release layer exhibits a minimum melt viscosity value of 10-9000 poise (e.g. 10 poise, 20 poise, 50 poise, 100 poise, 500 poise, 1000 poise, 2000 poise, 3000 poise, 4000 poise, 5000 poise, 6000 poise, 7000 poise, 8000 poise or 9000 poise, etc.), preferably 100-1000 poise, between 50-130 ℃.
In the invention, the lowest melt viscosity value of the release layer between 50 ℃ and 130 ℃ is 10-9000 poise, namely, after the release layer on the release film is scraped off, a An Dongpa MCR302 rheometer is used for testing the rheological curve of a release layer sample, the testing temperature range is set to be 20-160 ℃, the heating rate is 3 ℃/min, and after the testing is finished, the lowest melt viscosity value between 50 ℃ and 130 ℃ is read from the corresponding rheological curve (for example, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃ or 125 ℃ and the like), and the lowest melt viscosity value is between 10 poise and 9000 poise.
As the preferable technical scheme of the invention, a release layer is arranged between the base film and the resin layer, which is more beneficial to improving the retention rate of the peel strength of the carrier resin film after high-temperature baking, and has better laser drilling processability and other performances. Specifically, in the high-temperature baking process, the release layer of the base film can be softened or liquid peristaltic, small molecular substances generated by the resin layer can be absorbed, and overflowed through the release layer in a guiding way, so that the exhaust effect is achieved, and microscopic bubbles between the resin layer and the release layer after the carrier resin film is baked at high temperature can be avoided, so that the peeling strength is reduced.
Preferably, the thickness of the release layer is 1-10 μm, for example 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm, etc.
In the present invention, the release agent in the release layer is not particularly limited, and for example, the release agent includes any one or a combination of at least two of polyolefin resin, polyurethane resin, polyester resin, alkyd resin, cellulose resin, polyacrylate or polyvinyl acetal resin; the release agent can also comprise a cross-linking agent, wherein the cross-linking agent comprises any one or a combination of at least two of epoxy resin, phenolic resin, cyanate, active ester, amine cross-linking agent or anhydride cross-linking agent.
In a second aspect, the present invention provides a method for producing the carrier resin film according to the first aspect, the method comprising the steps of:
and (3) coating the raw material of the resin layer on the base film, and baking to obtain the carrier resin film.
As a preferable technical scheme of the invention, when a release layer is also arranged between the base film and the resin layer, the preparation method of the carrier resin film comprises the following steps:
and coating the raw material of the release layer on the base film, drying and curing, coating the raw material of the resin layer on the release surface of the release layer, and baking to obtain the carrier resin film.
Preferably, the base film is subjected to a surface treatment before the raw material of the resin layer is coated on the base film. When the release layer is arranged between the base film and the resin layer, the surface treatment is carried out on the base film, so that the binding force between the base film and the release layer can be improved, the release layer and each layer can be well bonded in the pressing and baking processes, and meanwhile, the release layer and the resin layer can be easily separated after baking and laser drilling.
Preferably, the surface treatment comprises a plasma roughening treatment.
Preferably, the baking temperature is 100-120deg.C, such as 100deg.C, 105deg.C, 110deg.C, 115deg.C or 120deg.C, etc., and the time is 3-5min, such as 3min, 4min or 5min, etc.
In a third aspect, the present invention provides the use of a carrier resin film according to the first aspect, said carrier resin film being applied to a printed wiring board.
Compared with the prior art, the invention has at least the following beneficial effects:
in the invention, by controlling the peeling strength of the resin layer and the base film before and after the heat treatment of the carrier resin film, the carrier resin film has good cohesiveness at normal temperature, high peeling strength retention rate (35% -83%) after high-temperature baking, and better laser drilling processability and operation processability.
Drawings
FIG. 1 is an SEM image of the surface of a resin layer after separating a base film by a carrier resin film obtained in example 1;
FIG. 2 is an SEM image of the surface of a resin layer after separating a base film by a carrier resin film obtained in comparative example 1;
fig. 3 is an SEM image of the surface of the resin layer after separating the base film from the carrier resin film obtained in comparative example 2.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
In this embodiment, there is provided a carrier resin film including a base film and a resin layer, the thickness of the resin layer being 40 μm, the thickness of the base film being 50 μm, the base film being made of Polytetrafluoroethylene (PTFE).
20 parts by weight of an epoxy resin (NC 3000H of Nippon Kagaku Co., ltd.) and 10 parts by weight of a phenol resin (SN-485 of Nitro iron chemical Co., ltd.) were dissolved with an appropriate amount of acetone and stirred for 2 hours or more, and then 70 parts by weight of silica (SC 2500-SQ of Nitro admatechs Co., ltd.) was added, and the surface treatment agent was KBM603 (N-2- (aminoethyl) -3-aminopropyl trimethoxysilane) of Sanyoshi chemical Co., ltd.) having a carbon content of 0.30mg/m per unit area 2 ) Stirring was continued for 4 hours or more, and the mixture was thoroughly and uniformly mixed to form a resin layer solution having a solid content of 65%.
The preparation method comprises the following steps:
and (3) carrying out plasma roughening treatment on the base film, coating the resin layer solution on the plasma roughening treatment surface of the base film, baking for 4min at 120 ℃, and removing the solvent to obtain the carrier resin film.
Example 2
In this embodiment, a carrier resin film is provided, where the carrier resin film includes a base film and a resin layer, a release layer is further disposed between the base film and the resin layer, the thickness of the release layer is 5 μm, the thickness of the resin layer is 40 μm, the thickness of the base film is 50 μm, and the base film is made of polyethylene terephthalate (PET).
20 parts by weight of an epoxy resin (NC 3000H of Nippon Kagaku Co., ltd.) and 10 parts by weight of a phenol resin (SN-485 of Nitro iron chemical Co., ltd.) were dissolved with an appropriate amount of acetone and stirred for 2 hours or more, and then 70 parts by weight of silica (SC 2500-SQ of Nitro admatechs Co., ltd.) was added, and the surface treatment agent was KBM603 (N-2- (aminoethyl) -3-aminopropyl trimethoxysilane) of Sanyoshi chemical Co., ltd.) having a carbon content of 0.30mg/m per unit area 2 ) Stirring was continued for 4 hours or more, and the mixture was thoroughly and uniformly mixed to form a resin layer solution having a solid content of 65%.
The release agent in the release layer consists of the following raw materials: 85 parts by weight of a polyacrylate resin (SG-790 of Nagase ChemteX Co., ltd., japan), 10 parts by weight of a bisphenol A type epoxy resin (EPON 1001 of Shell petrochemical industry), 5 parts by weight of a phenolic resin (PSM 4261 of Kagrong chemical Co., ltd.), and a solution having a solid content of 20% by weight was adjusted using butanone.
The preparation method comprises the following steps:
and (3) carrying out plasma roughening treatment on the base film, coating the raw material of the release layer on the base film, drying at 80 ℃, curing at 80 ℃ for 48 hours, and carrying out melt viscosity test on the release layer on the base film within the range of 20-160 ℃, wherein the melt viscosity value of the release layer at 103 ℃ is the lowest and is 800 poise.
Coating the release surface of the release layer with the resin layer solution, baking at 120 ℃ for 4min, and removing the solvent to obtain the carrier resin film.
Example 3
In this embodiment, a carrier resin film is provided, where the carrier resin film includes a base film and a resin layer, a release layer is further disposed between the base film and the resin layer, the thickness of the release layer is 10 μm, the thickness of the resin layer is 5 μm, the thickness of the base film is 10 μm, and the material of the base film is polyethylene naphthalate (PEN).
20 parts by weight of an epoxy resin (NC 3000H of Nippon Kagaku Co., ltd.) and 10 parts by weight of a phenol resin (SN-485 of Nitro iron chemical Co., ltd.) were dissolved with an appropriate amount of acetone and stirred for 2 hours or more, and then 70 parts by weight of silica (SC 2500-SQ of Nitro admatechs Co., ltd.) was added thereto, the carbon amount per unit area was 0.20mg/m 2 The surface treatment agent was KBM503, 3-methacryloxypropyl trimethoxysilane, from Xinyue chemical Co., ltd.) and was stirred for 4 hours or more, and then thoroughly mixed to form a resin layer solution having a solid content of 65%.
The release agent in the release layer consists of the following raw materials: 80 parts by weight of a polyvinyl butyral resin (BL-1 of SEKISUI Co., ltd., japan), 19.6 parts by weight of a bisphenol A type epoxy resin (EPON 1001 of Shell petrochemical industry), 0.4 part by weight of dicyandiamide, and a solution having a solid content of 30% by weight was adjusted with butanone.
The preparation method comprises the following steps:
coating the raw material of the release layer on the base film, drying at 90 ℃, curing at 100 ℃ for 30 hours, and carrying out melt viscosity test on the release layer on the base film within the range of 20-160 ℃, wherein the melt viscosity value of the release layer at 125 ℃ is the lowest and is 10 poise.
Coating the release surface of the release layer with the resin layer solution, baking at 120 ℃ for 4min, and removing the solvent to obtain the carrier resin film.
Example 4
In this embodiment, a carrier resin film is provided, where the carrier resin film includes a base film and a resin layer, a release layer is further disposed between the base film and the resin layer, the thickness of the release layer is 1 μm, the thickness of the resin layer is 150 μm, the thickness of the base film is 100 μm, and the base film is made of polyethylene terephthalate (PET).
20 parts by weight of an epoxy resin (NC 3000H of Nippon Kagaku Co., ltd.) and 10 parts by weight of a phenol resin (SN-485 of Nitro iron chemical Co., ltd.) were dissolved with an appropriate amount of acetone, and stirred for 2 hours or more, and then 70 parts by weight of silica (SC 2500-SQ of Nitro admatechs Co., ltd., surface treatment agent was Xinyue chemical Co., ltd.) was addedKBM503 (3-methacryloxypropyl trimethoxysilane) having a carbon content per unit area of 0.50mg/m 2 ) Stirring was continued for 4 hours or more, and the mixture was thoroughly and uniformly mixed to form a resin layer solution having a solid content of 65%.
The release agent in the release layer consists of the following raw materials: 50 parts by weight of a polyacrylate resin (SG-600 TEA from Nagase ChemteX Co., ltd., japan), 30 parts by weight of a bisphenol A type epoxy resin (EPON 1001 from Shell petrochemical industry), 20 parts by weight of a phenolic resin (PSM 4261 from Nippon chemical industry Co., ltd.), 1 part by weight of 2-methylimidazole, and a solution having a solids content of 20% by weight was adjusted using butanone.
The preparation method comprises the following steps:
coating the raw material of the release layer on the base film, drying at 100 ℃, curing at 170 ℃ for 1h, and carrying out melt viscosity test on the release layer on the base film within the range of 20-160 ℃, wherein the melt viscosity value of the release layer at 90 ℃ is the lowest and is 9000 poise.
Coating the release surface of the release layer with the resin layer solution, baking at 120 ℃ for 4min, and removing the solvent to obtain the carrier resin film.
Comparative example 1
The comparative example differs from example 1 only in that the carbon amount per unit area of silica is 0.15mg/m 2 。
Comparative example 2
The comparative example differs from example 1 only in that the carbon amount per unit area of silica is 0.55mg/m 2 。
Application examples 1-4, comparative application examples 1-2
The carrier resin films and the browned printed wiring boards provided in examples 1 to 4 and comparative examples 1 to 2 were subjected to a temperature of 6kgf/cm at 100 DEG C 2 Vacuum lamination for 60 seconds under the condition, baking for 60 minutes at 190 ℃, laser drilling after baking, separating a base film, performing desmear treatment, electroless copper plating to form a laminated printed wiring board with a circuit (examples 1-4 and comparative examples 1-2 correspond to application examples 1-4 and comparative application examples 1-2 in sequence), and performing performance test, wherein the test method is as follows:
(1) Minimum melt viscosity value: after scraping off the release layer on the base film, testing the rheological curve of the release layer sample by using a An Dongpa MCR302 rheometer, setting the testing temperature range to be 20-160 ℃ and the heating rate to be 3 ℃/min; after the test is completed, the lowest melt viscosity values occurring between 50 and 130 ℃ are read from the corresponding rheology curves.
(2) Thickness of release layer: the thickness of the base film was measured by a micrometer, which was H 1 Dipping acetone with a cotton swab to smear off the release layer at the measuring position, and measuring the thickness of the base film at the position by a micrometer, wherein the thickness is H 2 Then H 2 -H 1 The thickness of the release layer is the thickness of the release layer.
(3) Peel strength: the peel strength of the base film when peeled off the resin layer was measured with reference to the peel strength test method specified in IPC-TM-650.4.8.
(4) Laser drilling processability: testing the aperture size of the blind hole of the resin layer after laser drilling, and judging that the hole type quality of the laser blind hole is excellent when the ratio of the minimum aperture to the maximum aperture of the laser blind hole is larger than 0.8 and the ratio of the minimum diameter to the maximum diameter of the hole is larger than 0.9; when the ratio of the minimum aperture to the maximum aperture of the laser blind hole is larger than 0.7 and the ratio of the minimum diameter to the maximum diameter of the aperture is larger than 0.8, judging that the hole pattern quality of the laser blind hole is good; when the ratio of the minimum aperture to the maximum aperture of the laser blind hole is less than or equal to 0.7 or the ratio of the minimum diameter to the maximum diameter of the orifice is less than or equal to 0.8, the quality of the hole pattern of the laser blind hole is judged to be poor.
(5) Workability in handling: the carrier resin film is judged to be qualified if no falling-off exists in the film baking and laser drilling processes; otherwise, judging that the test paper is unqualified.
The results of the performance test are shown in Table 1.
TABLE 1
As can be seen from Table 1, the carrier resin films provided in examples 1 to 4 of the present invention have good adhesion at ordinary temperature, high retention of peel strength after baking at high temperature (35% -83%), and excellent laser drilling processability. Compared with the embodiment 1, the release layer is further arranged between the base film and the resin layer in the embodiments 2-4, and can guide and overflow small molecular substances generated by the resin layer in the high-temperature baking process, so that the peeling strength can be prevented from being reduced due to microscopic bubbles existing between the resin layer and the release layer after the carrier resin film is baked at a high temperature, and the peeling strength retention rate can reach 83 percent after the carrier resin film is baked at a high temperature.
Although the initial peel strength of the carrier resin film of comparative example 1 satisfies the requirements, the filler thereof is poorly dispersed in the thermosetting resin, so that the filler agglomeration occurs on the resin layer surface of the carrier resin film (as can be seen from a comparison of the SEM images of fig. 2 and 1), the resin layer surface is occupied by the filler to reduce the effective contact of the resin with the base film, resulting in easy falling-off of the carrier resin film in the film-carrying baking and laser drilling process, good laser drilling processability, and unsatisfactory handling processability. Although the initial peel strength of the carrier resin film of comparative example 2 was satisfactory, the surface treatment agent having too much filler surface migrated to the resin layer surface of the carrier resin film after baking at high temperature, microscopic bubbles (depressions in the SEM image of fig. 3) were formed between the resin layer and the base film, and the bonding force between the base film and the resin layer was also reduced, resulting in easy falling-off of the carrier resin film during the film-carrying baking and laser drilling process, poor laser drilling processability, and defective handling processability.
The applicant states that the present invention is illustrated by the above examples as well as the preparation method and application thereof, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be practiced depending on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (17)

1. The carrier resin film is characterized by comprising a base film and a resin layer, wherein the initial peeling strength of the resin layer and the base film is 0.40-1.0N/mm, and the peeling strength of the resin layer and the base film is 0.20-0.80N/mm after the carrier resin film is subjected to heat treatment;
the resin layer comprises 20-60 parts by weight of a thermosetting resin, 40-80 parts by weight of a surface-treated inorganic filler having a carbon content per unit surface area of 0.20mg/m 2 -0.50mg/m 2 ；
A release layer is arranged between the base film and the resin layer;
the release layer has a minimum melt viscosity value of 10-9000 poise at 50-130 ℃;
the release agent in the release layer comprises any one or a combination of at least two of polyolefin resin, polyurethane resin, polyester resin, alkyd resin, cellulose resin, polyacrylate or polyvinyl acetal resin.
2. The carrier resin film of claim 1 wherein the heat treatment is at a temperature of 170-190 ℃.
3. The carrier resin film according to claim 1, wherein the time of the heat treatment is 30 to 60 minutes.
4. The carrier resin film according to claim 1, wherein the surface-treated surface-treating agent is selected from any one or a combination of at least two of a silane coupling agent, a silicone oligomer, or a titanate coupling agent.
5. The carrier resin film of claim 1, wherein the thermosetting resin comprises any one or a combination of at least two of an epoxy resin, a phenolic resin, a cyanate ester, an active ester, a polyphenylene ether resin, a maleimide resin, a silicone resin, a polybenzoxazole resin, a polyimide resin, a hydrocarbon resin, or an acrylate resin.
6. The carrier resin film of claim 5, wherein the epoxy resin comprises one or a combination of at least two of bisphenol a type epoxy resin, bisphenol F type epoxy resin, phosphorous containing epoxy resin, MDI modified epoxy resin, phenolic epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene containing epoxy resin, or cycloaliphatic epoxy resin.
7. The carrier resin film of claim 5, wherein the phenolic resin comprises one or a combination of at least two of bisphenol a type phenolic resin, phenol type phenolic resin, biphenyl type phenolic resin, dicyclopentadiene type phenolic resin, or naphthol containing aldehyde resin.
8. The support resin film according to claim 1, wherein the inorganic filler is selected from any one or a combination of at least two of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, boehmite, calcium carbonate, calcium silicate, or mica.
9. The carrier resin film according to claim 1, wherein the resin layer has a thickness of 5 to 150 μm.
10. The carrier resin film according to claim 1, wherein the base film has a thickness of 10 to 100 μm.
11. The carrier resin film according to claim 1, wherein the base film is selected from any one of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polymethyl methacrylate, cyclic polyolefin, triacetyl cellulose, polyether sulfide, polyether ketone, polyimide, polytetrafluoroethylene, polybenzimidazole, polyether ether ketone, polyphenylene sulfide, copper foil, aluminum foil, nickel foil, or alloy foil.
12. The carrier resin film according to claim 1, wherein the thickness of the release layer is 1 to 10 μm.
13. The method for producing a carrier resin film according to any one of claims 1 to 12, characterized in that the method comprises the steps of:
and (3) coating the raw material of the resin layer on the base film, and baking to obtain the carrier resin film.
14. The method according to claim 13, wherein the base film is subjected to surface treatment before the raw material of the resin layer is coated on the base film.
15. The method of claim 14, wherein the surface treatment comprises a plasma roughening treatment.
16. The method according to claim 13, wherein the baking temperature is 100-120 ℃ for 3-5min.
17. Use of the carrier resin film according to any one of claims 1 to 12, wherein the carrier resin film is applied to a printed wiring board.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103650649A (en) * 2011-07-07 2014-03-19 日立化成株式会社 Adhesive film, multilayer printed wiring board using adhesive film, and method for manufacturing multilayer printed wiring board

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103650649A (en) * 2011-07-07 2014-03-19 日立化成株式会社 Adhesive film, multilayer printed wiring board using adhesive film, and method for manufacturing multilayer printed wiring board

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