CN111040678B - Halogen-free resin composition, reinforcing plate for flexible printed circuit containing halogen-free resin composition and application of reinforcing plate - Google Patents

Halogen-free resin composition, reinforcing plate for flexible printed circuit containing halogen-free resin composition and application of reinforcing plate Download PDF

Info

Publication number
CN111040678B
CN111040678B CN201911384831.2A CN201911384831A CN111040678B CN 111040678 B CN111040678 B CN 111040678B CN 201911384831 A CN201911384831 A CN 201911384831A CN 111040678 B CN111040678 B CN 111040678B
Authority
CN
China
Prior art keywords
resin composition
halogen
printed circuit
flexible printed
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911384831.2A
Other languages
Chinese (zh)
Other versions
CN111040678A (en
Inventor
左陈
茹敬宏
伍宏奎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shengyi Technology Co Ltd
Original Assignee
Shengyi Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shengyi Technology Co Ltd filed Critical Shengyi Technology Co Ltd
Priority to CN201911384831.2A priority Critical patent/CN111040678B/en
Publication of CN111040678A publication Critical patent/CN111040678A/en
Application granted granted Critical
Publication of CN111040678B publication Critical patent/CN111040678B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • 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
    • 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
    • C09J7/29—Laminated material
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • H05K1/0277—Bendability or stretchability details
    • H05K1/028—Bending or folding regions of flexible printed circuits
    • H05K1/0281—Reinforcement details thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate

Landscapes

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

Abstract

The invention provides a halogen-free resin composition, a reinforcing plate for a flexible printed circuit containing the same and application thereof, wherein the halogen-free resin composition comprises the following components in parts by weight: 50-60 parts of polyacrylate, 10-20 parts of epoxidized polybutadiene, 15-25 parts of copolyamide, 5-10 parts of amine curing agent and 10-20 parts of flame retardant; the components are compounded in a specific ratio in a synergistic manner, so that the resin composition forms a stable interpenetrating cross-linked network structure after being cured. The reinforcing plate for the flexible printed circuit prepared from the halogen-free resin composition has moderate touch adhesion, excellent storage stability, bonding strength, bonding property, heat resistance and flame retardance, and can fully meet the processing and application requirements of a reinforcing material in a flexible printed circuit board.

Description

Halogen-free resin composition, reinforcing plate for flexible printed circuit containing halogen-free resin composition and application of reinforcing plate
Technical Field
The invention belongs to the technical field of printed circuits, and particularly relates to a halogen-free resin composition, a flexible printed circuit reinforcing plate containing the halogen-free resin composition and application of the halogen-free resin composition.
Background
In recent years, consumer electronics are gradually becoming thinner and lighter and wearable, and flexible printed circuit boards have been widely used in consumer electronics due to their advantages of light weight and small thickness. The flexible printed circuit board adopts a polymer film as an insulating and supporting base material, has the characteristics of repeated flexing and bending, has good flexibility, but lacks rigidity, and is often difficult to support at the position needing welding or plugging because of insufficient rigidity. Therefore, it is usually necessary to reinforce a local portion of the flexible printed circuit board to increase the strength of the insertion portion for improving the workability.
The reinforcing material commonly used for the flexible printed circuit comprises a stainless steel sheet, an FR-4 insulating board, a polyimide reinforcing plate and the like, wherein the polyimide reinforcing plate has wider application prospect due to excellent heat resistance. Polyimide stiffening plates are divided into gum stiffening plates and non-gum stiffening plates, and the performance of the adhesive in the gum stiffening plates has important influence on the overall stability and usability of the stiffening plates, so that the problem of searching the adhesive suitable for the flexible printed circuit stiffening material is an ignorable problem in the field.
CN106867435A discloses a modified acrylate adhesive for a flexible printed circuit polyimide reinforcing plate and application thereof, wherein the adhesive comprises 100 parts of polyacrylate solution, 5-30 parts of rubber monomer, 4-10 parts of epoxy resin, 5-50 parts of bismaleimide-terminated polyimide resin and 1-50 parts of filler. The adhesive has higher peel strength, and can enhance the flexibility, heat resistance, water resistance, dimensional stability and insulativity of a reinforcing plate product. However, the adhesive adopts a rubber monomer as a toughening agent, has the defect of insufficient aging resistance, and is easy to have the problems of peeling strength reduction and the like during high-temperature pressing, so that the later application is influenced.
CN109337618A discloses an adhesive composition for a flexible circuit board, a preparation method and an application thereof, wherein the adhesive composition comprises epoxy resin and an acrylate copolymer, wherein the mass of the epoxy resin is 20-40% of that of the acrylate copolymer; the acrylate copolymer comprises n-butyl acrylate, styrene, acrylic acid, hydroxy phosphate ester, solvent and initiator. The adhesive composition is prepared into an adhesive film, can resist thermal shock through high-temperature soldering tin when being applied to bonding a flexible printed circuit board and a metal reinforcing plate, has stable peel strength in a high-temperature and high-humidity environment (the temperature is 85 ℃, the humidity is 85%), and the bonded reinforcing plate is not easy to fall off. However, the adhesive composition has poor flexibility and is difficult to adapt to later flexibility applications of flexible wiring boards.
CN101198671A discloses an adhesive and an adhesive sheet, wherein the adhesive comprises an acrylic resin having a carboxyl group and an acid value of 2mg KOH/g or more, an acrylic resin having a hydroxyl group and an acid value of 0.1mg KOH/g or less, an epoxy resin, and a curing agent or a curing catalyst. The adhesive has high punching and shearing processability and high heat resistance, can exert high adhesion on both polyimide films and polyester films, and can be bonded with base materials such as covering films, reinforcing plates and the like in flexible printed circuit boards to form adhesive sheets. However, the adhesive needs to be cured by heating, and the touch adhesion property of the adhesive cannot be suitable for preparing large-scale industrialized reinforcing materials.
Because the adhesive for the reinforcing plate in the prior art has the problems of short storage period, harsh storage condition, insufficient flame retardance, insufficient touch adhesion or overlarge touch adhesion, and unbalanced performances of flexibility, aging resistance and the like, the resin composition with good storage stability and heat resistance, high bonding strength, proper touch adhesion and flame retardance is developed to meet the application requirement of the reinforcing material for the flexible printed circuit, and the problem to be solved in the field is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a halogen-free resin composition, a reinforcing plate for a flexible printed circuit containing the halogen-free resin composition and an application of the reinforcing plate.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a halogen-free resin composition, which comprises the following components in parts by weight: 50-60 parts of polyacrylate, 10-20 parts of epoxidized polybutadiene, 15-25 parts of copolyamide, 5-10 parts of amine curing agent and 10-20 parts of flame retardant.
The halogen-free resin composition provided by the invention takes polyacrylate and epoxidized polybutadiene as main resins, the copolyamide, the amine curing agent and the flame retardant are matched and used, and the five components are compounded synergistically, so that the halogen-free resin composition is endowed with excellent storage stability, heat resistance, adhesiveness and flame retardance, and particularly has proper touch adhesiveness, the touch adhesiveness can ensure that the halogen-free resin composition can be bonded by lightly pressing in the using process, and meanwhile, the halogen-free resin composition can be peeled off without damaging the surface of an adherend if the bonding alignment is not correct. Wherein, the polyacrylate resin has the characteristics of long storage period, high stability and strong caking property; the epoxidized polybutadiene has better flexibility, and the crosslinking density of the halogen-free resin composition can be increased, so that a stable and compact crosslinking network is formed after the halogen-free resin composition is cured, and the heat resistance and the mechanical property of the bonding layer are improved; the co-polyamide used in combination can further improve the flexibility, thermal stability and adhesive property of the halogen-free resin composition; the amine curing agent reacts with an epoxy group in the system to realize the curing and bonding of the halogen-free resin composition; the flame retardant is uniformly dispersed in the system, and the halogen-free resin composition is endowed with excellent flame retardance.
The amount of polyacrylate in the halogen-free resin composition may be 51 parts by weight, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 57 parts by weight, 58 parts by weight or 59 parts by weight, and specific values therebetween, which are not exhaustive for the purpose of brevity and clarity.
The epoxidized polybutadiene content may be 11, 12, 13, 14, 15, 16, 17, 18, or 19 parts by weight, and specific values therebetween, not exhaustive of the invention including the specific values within the ranges, limited to space and for brevity.
The copolyamide may be present in an amount of 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight or 24 parts by weight, and specific values therebetween, not exhaustive of the specific values included in the ranges, limited to space and for the sake of brevity.
The amine-based curing agent may be present in an amount of 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, or 9.5 parts by weight, and specific values therebetween, not to limit the space and for the sake of brevity, the present invention is not exhaustive of the specific values included in the ranges.
The amount of the flame retardant may be 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, or 19 parts by weight, and specific points therebetween, which are included in the range are not exhaustive for the invention and for the sake of brevity.
In the halogen-free resin composition provided by the invention, the five components are cooperated with each other within the content range, so that the composition is endowed with excellent heat resistance, bonding strength, storage stability, flame retardance and proper touch viscosity. If the content of the epoxidized polybutadiene is less than the above range, the tack, cohesive strength and flexibility of the composition are lowered, the halogen-free resin composition forms a tack layer having poor heat resistance and adhesion, and if the content of the epoxidized polybutadiene is more than the above range, the reactivity of the composition is too high, the storage stability is low, the pot life is short, and the tack is too large.
Preferably, the polyacrylate comprises a carboxyl-containing polyacrylate and/or an epoxy-containing polyacrylate.
As a preferable technical scheme of the invention, the polyacrylate is one or a combination of two of carboxyl-containing polyacrylate or epoxy-containing polyacrylate, functional groups carboxyl or epoxy group in the main resin polyacrylate can react with epoxy group in epoxidized polybutadiene and amino group in amine curing agent to form stable chemical bond, on one hand, the crosslinking density and cohesive strength of the halogen-free resin composition are increased, the heat resistance and cohesiveness of the halogen-free resin composition are improved, on the other hand, the compatibility among the components in the composition is effectively increased, and the phase separation is avoided.
Preferably, the glass transition temperature of the polyacrylate is from-10 ℃ to 20 ℃, such as-9 ℃, -7 ℃, -5 ℃, -3 ℃, -1 ℃, 0 ℃, 2 ℃,4 ℃, 6 ℃, 8 ℃, 10 ℃, 12 ℃, 14 ℃, 16 ℃, 18 ℃ or 19 ℃, and the specific values therebetween are limited to space and for the sake of brevity and are not exhaustive of the specific values included in the ranges.
Preferably, the weight average molecular weight of the polyacrylate is 300000 to 900000, such as 350000, 400000, 450000, 500000, 550000, 600000, 650000, 700000, 750000, 800000, 850000, or 880000, and the specific values therebetween are limited to space and for the sake of brevity and clarity, and the present invention is not exhaustive.
The polyacrylate of the present invention can be obtained by the prior art, and illustratively, the polyacrylate can be selected from any one or a combination of at least two of SG-P3, SG-708-6 or PMS-12-81 manufactured by NAGASE ChemteX, Japan.
Preferably, the epoxidized polybutadiene has a number average molecular weight of 2500 to 6000g/mol, such as 2600g/mol, 2800g/mol, 3000g/mol, 3200g/mol, 3500g/mol, 3800g/mol, 4000g/mol, 4200g/mol, 4500g/mol, 4800g/mol, 5000g/mol, 5200g/mol, 5500g/mol, 5700g/mol or 5900g/mol, and the specific values therebetween are limited in space and for the sake of brevity and are not exhaustive, and the invention is not intended to include the specific values included in the ranges.
Preferably, the epoxy equivalent of the epoxidized polybutadiene is 120-170 g/eq (g/eq), such as 122g/eq, 125g/eq, 128g/eq, 130g/eq, 133g/eq, 135g/eq, 138g/eq, 140g/eq, 142g/eq, 145g/eq, 148g/eq, 150g/eq, 152g/eq, 155g/eq, 157g/eq, 160g/eq, 162g/eq, 165g/eq, 167g/eq, or 169g/eq, and the specific point values between the above point values, limited in space and for the sake of brevity, are not exhaustive of the specific point values included in the range.
The epoxidized polybutadiene of the present invention can be obtained by the prior art, and illustratively, the epoxidized polybutadiene may be selected from any one of or a combination of at least two of L680, L681 and L682 produced by Synthomer, uk.
Preferably, the copolyamide has a glass transition temperature of 20-40 ℃, for example 21 ℃, 23 ℃, 25 ℃, 27 ℃, 28 ℃, 30 ℃, 31 ℃, 33 ℃, 35 ℃, 37 ℃ or 39 ℃, and specific values therebetween, are not exhaustive for the purpose of space and brevity, and the invention is not intended to be limited to the specific values included in the ranges.
Preferably, the amine number of the copolyamide is 3-5 mg KOH/g, such as 3.1mg KOH/g, 3.2mg KOH/g, 3.4mg KOH/g, 3.6mg KOH/g, 3.7mg KOH/g, 3.9mg KOH/g, 4mg KOH/g, 4.1mg KOH/g, 4.3mg KOH/g, 4.5mg KOH/g, 4.6mg KOH/g, 4.7mg KOH/g, 4.8mg KOH/g or 4.9mg KOH/g, and the specific values therebetween are not exhaustive and for the sake of brevity.
The copolyamide according to the invention is obtainable by the prior art and may be exemplified by the copolyamide chosen from M1276F and/or M995F, manufactured by arkema, france.
Preferably, the amine curing agent is selected from any one of dicyandiamide, 4 '-diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone or diphenyl methane diamine or a combination of at least two thereof.
Preferably, the flame retardant is a phosphorus-containing flame retardant.
The phosphorus-containing flame retardant may be obtained by the prior art, and may be exemplified by any one or a combination of at least two selected from SPB-100 of Otsuka chemical Co., Ltd., Germany, OP-935 of Clariana, Germany, OP-930 of Clariana, or SP-703H of four national chemical Co., Ltd.
On the other hand, the invention provides a resin glue solution, which is obtained by dissolving or dispersing the halogen-free resin composition in a solvent.
Preferably, the solvent is selected from any one of acetone, butanone, toluene, ethanol, isopropanol, cyclohexanone, ethylene glycol methyl ether, propylene glycol methyl ether acetate or ethyl acetate or a combination of at least two of the above.
Preferably, the resin cement has a solid content of 40-60%, for example 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58% or 59%, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the ranges.
In another aspect, the present invention provides a reinforcing plate for a flexible printed circuit, the reinforcing plate comprising a base film and a resin layer on the base film, wherein a protective layer is provided on a surface of the resin layer.
The resin layer is a coating layer of the halogen-free resin composition.
Preferably, the base film is a single-layer polyimide film or a multi-layer polyimide film; the multilayer polyimide film is formed by bonding single-layer polyimide films through an adhesive.
Preferably, the thickness of the base film is 50 to 200 μm, such as 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, or 190 μm, and specific values therebetween, and the invention is not exhaustive for the specific values included in the range in consideration of space and conciseness.
Preferably, the resin layer has a thickness of 20 to 50 μm, such as 22 μm, 24 μm, 26 μm, 28 μm, 30 μm, 32 μm, 34 μm, 36 μm, 38 μm, 40 μm, 42 μm, 44 μm, 46 μm, 48 μm or 49 μm, and specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the range for brevity and conciseness.
Preferably, the protective layer is release paper or release film.
Illustratively, the method for preparing the stiffening plate for the flexible printed circuit comprises the following steps: mixing and dispersing the halogen-free resin composition and a solvent to obtain a resin glue solution; and coating resin glue solution on the base film, drying, compounding with the protective layer, and rolling to obtain the reinforcing plate for the flexible printed circuit.
Preferably, the dispersion is carried out in a ball mill, a pot mill or a sand mill;
preferably, the drying temperature is 80-160 ℃, such as 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃ or 155 ℃.
Preferably, the drying time is 2-8 min, such as 2.5min, 3min, 3.5min, 4min, 4.5min, 5min, 5.5min, 6min, 6.5min, 7min or 7.5 min.
Preferably, the temperature of the compounding is 70 to 90 ℃, such as 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃ or 89 ℃ and the like.
In another aspect, the present invention provides a flexible printed circuit board including the reinforcing plate for a flexible printed circuit as described above.
Compared with the prior art, the invention has the following beneficial effects:
the halogen-free resin composition provided by the invention takes polyacrylate and epoxidized polybutadiene as main body resins, copolyamide, amine curing agent and flame retardant are matched and compounded in a specific proportion, and an interpenetrating cross-linked network structure is formed after the resin composition is cured through multiple chemical reactions among the components, so that the halogen-free resin composition is endowed with excellent compatibility, storage stability, heat resistance, bonding strength, flame retardance and proper touch viscosity. The reinforcing plate for the flexible printed circuit, which is prepared by using the halogen-free resin composition, has moderate touch adhesion of 0.32-0.48N/25 mm, can realize bonding under light pressing, and can be peeled off when the bonding alignment is not correct without damaging the surface of an adherend; the peel strength of the reinforcing plate for the flexible printed circuit reaches 1.83-1.95N/mm, the reinforcing plate is stably stored for more than 1 year in an environment with the temperature of 25 ℃ and the relative humidity of 50%, the phenomenon of layered foaming is avoided after 3 times of tin immersion in a tin furnace at the temperature of 300 ℃, the flame retardance reaches V-0 level, and the reinforcing plate has excellent storage stability, bonding strength, heat resistance and flame retardance and can fully meet the processing and application requirements of a reinforcing material in a flexible printed circuit board.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The experimental materials used in the examples and comparative examples of the present invention were as follows:
(1) polyacrylate: SG-P3 (functional group is epoxy group, weight average molecular weight is 850000, T) from NAGASE ChemteX, Japang12 ℃ C.), SG-708-6 (functional group is carboxyl, weight average molecular weight is 700000, TgAt 4 deg.C or PMS-12-81 (functional group is epoxy group, weight average molecular weight is 500000, TgAt 16 ℃ C.).
(2) Epoxidized polybutadiene: l680 (number average molecular weight of 2900g/mol, epoxy equivalent of 157g/eq), L681 (number average molecular weight of 2950g/mol, epoxy equivalent of 136g/eq) or L682 (number average molecular weight of 5600g/mol, epoxy equivalent of 151g/eq) from Synthomer, UK.
(3) Copolyamide: M1276F (T) from Akema, FrancegAt 32 ℃ and an amine number of 3.3mg KOH/g) or M995F (T)gAt 25 ℃ and an amine number of 4.8mg KOH/g).
(4) Flame retardant: a phosphorus-containing flame retardant, SPB-100 available from Otsuka chemical Co., Ltd., OP-935 or OP-930 available from Laine, Germany.
(5) Base film: the polyimide composite films were divided into 3 kinds by thickness, 50 μm, 75 μm and 200 μm, respectively.
(6) Protective layer: a release film or release paper.
Example 1
The halogen-free resin composition comprises the following components in parts by weight: 50 parts of polyacrylate SG-P3, 10 parts of epoxidized polybutadiene L680, 15 parts of copolyamide M1276F, 5 parts of dicyandiamide and 10 parts of flame retardant SPB-100.
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method comprises the following steps:
(1) mixing the halogen-free resin composition with butanone, and uniformly dispersing the halogen-free resin composition with the butanone by using a ball mill to obtain uniformly dispersed resin glue solution with the solid content of 40 percent;
(2) coating the resin glue solution obtained in the step (1) on the surface of a polyimide composite film with the thickness of 50 microns by using a coating machine, wherein the coating thickness is 25 microns; drying at 85 deg.C for 3min to form partially cured resin layer on the surface of the polyimide composite film; and then compounding the reinforcing plate with release paper at 70 ℃, and rolling to obtain the reinforcing plate for the flexible printed circuit.
Example 2
The halogen-free resin composition comprises the following components in parts by weight: 55 parts by weight of polyacrylate SG-708-6, 15 parts by weight of epoxidized polybutadiene L681, 18 parts by weight of copolyamide M995F, 8 parts by weight of 4,4' -diaminodiphenyl sulfone and 15 parts by weight of flame retardant OP-935.
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method comprises the following steps:
(1) mixing the halogen-free resin composition with toluene, and uniformly dispersing the mixture by using a tank mill to obtain uniformly dispersed resin glue solution with the solid content of 50 percent;
(2) coating the resin glue solution obtained in the step (1) on the surface of a polyimide composite film with the thickness of 75 microns by using a coating machine, wherein the coating thickness is 50 microns; drying at 130 deg.C for 5min to form partially cured resin layer on the surface of the polyimide composite film; and then compounding the reinforcing plate with a release film at 80 ℃, and rolling to obtain the reinforcing plate for the flexible printed circuit.
Example 3
The halogen-free resin composition comprises the following components in parts by weight: 60 parts by weight of polyacrylate PMS-12-81, 20 parts by weight of epoxidized polybutadiene L682, 25 parts by weight of copolyamide M995F, 10 parts by weight of diphenylmethane diamine and 20 parts by weight of flame retardant OP-930.
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method comprises the following steps:
(1) mixing the halogen-free resin composition with cyclohexanone, and uniformly dispersing the mixture by using a sand mill to obtain uniformly dispersed resin glue solution with the solid content of 60 percent;
(2) coating the resin glue solution obtained in the step (1) on the surface of a polyimide composite film with the thickness of 200 microns by using a coating machine, wherein the coating thickness is 25 microns; drying at 160 deg.C for 8min to form partially cured resin layer on the surface of the polyimide composite film; and then compounding the reinforcing plate with a release film at 90 ℃, and rolling to obtain the reinforcing plate for the flexible printed circuit.
Example 4
A halogen-free resin composition whose composition differs from that of example 2 in that polyacrylate SG-708-6 was replaced with polyacrylate SG-790 (available from NAGASE ChemteX, with a weight-average molecular weight of 500000 and hydroxyl group as a functional group) of equal mass.
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method is the same as that in example 2, so that the reinforcing plate for the flexible printed circuit is obtained.
Example 5
A halogen-free resin composition differing from example 2 in composition in that epoxidized polybutadiene L681 was replaced with an equal mass of epoxidized polybutadiene PB3600 (EPOLEAD PB3600 from Daicel corporation, Japan, number average molecular weight 5400g/mol, epoxy equivalent weight 193 g/eq).
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method is the same as that in example 2, so that the reinforcing plate for the flexible printed circuit is obtained.
Example 6
A halogen-free resin composition whose composition differs from that of example 2 in that copolyamide M995F was replaced by an equal mass of copolyamide PA9801 (Shanghai Tianyang PA9801, amine number 9mg KOH/g).
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method is the same as that in example 2, so that the reinforcing plate for the flexible printed circuit is obtained.
Example 7
A halogen-free resin composition whose composition differs from that of example 2 in that copolyamide M995F was replaced by an equal mass of copolyamide PA6150 (Shanghai Tianyang PA6150, amine number 2mg KOH/g).
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method is the same as that in example 2, so that the reinforcing plate for the flexible printed circuit is obtained.
Comparative example 1
A halogen-free resin composition whose composition is different from that of example 2 in that it does not contain epoxidized polybutadiene.
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method is the same as that in example 2, so that the reinforcing plate for the flexible printed circuit is obtained.
Comparative example 2
A halogen-free resin composition whose composition differs from that of example 2 in that it does not contain a copolyamide.
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method is the same as that in example 2, so that the reinforcing plate for the flexible printed circuit is obtained.
Comparative example 3
A halogen-free resin composition whose composition is different from that of example 2 in that the content of epoxidized polybutadiene L681 is 7 parts by weight.
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method is the same as that in example 2, so that the reinforcing plate for the flexible printed circuit is obtained.
Comparative example 4
A halogen-free resin composition whose composition is different from that of example 2 in that the content of epoxidized polybutadiene L681 is 25 parts by weight.
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method is the same as that in example 2, so that the reinforcing plate for the flexible printed circuit is obtained.
Comparative example 5
A halogen-free resin composition whose composition differs from that of example 2 in that the content of copolyamide M995F was 10 parts by weight.
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method is the same as that in example 2, so that the reinforcing plate for the flexible printed circuit is obtained.
Comparative example 6
A halogen-free resin composition whose composition differs from that of example 2 in that the content of copolyamide M995F was 30 parts by weight.
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method is the same as that in example 2, so that the reinforcing plate for the flexible printed circuit is obtained.
Comparative example 7
A halogen-free resin composition whose composition differs from that of example 2 in that epoxidized polybutadiene L681 is replaced with an equal-mass alicyclic epoxy resin (JE-8421, epoxy equivalent 137g/eq, Ex. Dynah Material Co., Ltd.).
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method is the same as that in example 2, so that the reinforcing plate for the flexible printed circuit is obtained.
Comparative example 8
A halogen-free resin composition whose composition differs from that of example 2 in that copolyamide M995F was replaced by an equal mass of non-copolyamide (TF-118 from Jinan Co., Ltd., amine value 5 mgKOH/g).
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method is the same as that in example 2, so that the reinforcing plate for the flexible printed circuit is obtained.
Comparative example 9
A halogen-free resin composition differing from example 2 in that epoxidized polybutadiene L681 was replaced with polybutadiene of equal mass (P4-150P, number average molecular weight 3200g/mol, from Synthomer, UK).
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method is the same as that in example 2, so that the reinforcing plate for the flexible printed circuit is obtained.
Comparative example 10
A halogen-free resin composition differing from example 2 in composition in that epoxidized polybutadiene L681 was replaced with maleic anhydride-modified polybutadiene (AL-15 MA, acid value 74mgKOH/g, manufactured by Synthomer, UK) of equal mass.
The halogen-free resin composition is used for preparing a reinforcing plate for a flexible printed circuit, and the specific method is the same as that in example 2, so that the reinforcing plate for the flexible printed circuit is obtained.
And (3) performance testing:
(1) touch viscosity: the reinforcing plate for the flexible printed circuit is cut into a strip-shaped sample with the width of 25mm, then the adhesive surface (namely a resin layer) is attached to the surface of the polyimide film, a 2kg roller is used for rolling back and forth for 3 times, then a tension meter is used for peeling off at 180 degrees, the peeling force is tested, and the size of the touch adhesion is characterized. The contact viscosity can meet the processing requirements of the printed circuit board when being within the range of 0.3-0.5N/25 mm; if the touch adhesion is less than 0.3N/25mm, the adhesive is easy to fall off after bonding; if the tack is more than 0.5N/25mm, peeling after bonding becomes difficult and adhesive remains.
(2) Heat resistance: the glue surface (resin layer) of the reinforcing plate for the flexible printed circuit and the polyimide film are pressed at 180 ℃, then are placed in a 160 ℃ oven for curing for 1h, and then are dipped in tin for 3 times in a 300 ℃ tin furnace, and whether layering and foaming exist is observed for 10s each time.
(3) Peel strength: the adhesive surface (resin layer) of the reinforcing plate for the flexible printed circuit and the polyimide film are pressed at 180 ℃ and then are placed in a 160 ℃ oven for curing for 1h, and the test is carried out according to the method specified in the standard IPC-TM-6502.4.9.
(4) Storage stability: storing the reinforcing plate for the flexible printed circuit for 1 year in an environment with the temperature of 25 ℃ and the humidity of 50% RH, comparing the touch adhesion and the peel strength before and after the storage, and if the touch adhesion and the peel strength decay after the storage for 1 year is less than 10%, determining that the flexible printed circuit is qualified; otherwise, it is not qualified.
(5) Flame retardancy: the test was carried out according to the UL94 method.
The properties of the reinforcing plates for flexible printed circuits obtained in examples 1 to 7 and comparative examples 1 to 10 were measured according to the above-described property measurement method, and the measurement results are shown in table 1.
TABLE 1
Figure BDA0002343277210000151
Figure BDA0002343277210000161
As can be seen from the data in table 1, the halogen-free resin composition provided in embodiments 1 to 3 of the present invention is used for preparing a stiffener for a flexible printed circuit, and the obtained stiffener for a flexible printed circuit has excellent flame retardancy, heat resistance and storage stability, has high peel strength and moderate touch adhesion, has a touch adhesion test value of 0.32 to 0.48N/25mm, can realize bonding under light pressure, can be peeled off when the bonding is misaligned without damaging the surface of an adherend, has a peel strength of 1.83 to 1.95N/mm, can be stably stored for more than 1 year in an environment with a relative humidity of 50% at 25 ℃, and has no delamination when the bonding layer is subjected to tin immersion for 3 times in a tin furnace at 300 ℃, and has a flame retardancy of V-0 grade.
In the halogen-free resin composition provided by the invention, carboxyl or epoxy functional groups in the main resin polyacrylate can react with the epoxidized polybutadiene and the amine curing agent, so that the crosslinking density and the cohesive strength of the composition are improved, and the heat resistance and the bonding property of the composition are improved. If the main resin in the halogen-free resin composition does not contain the above functional group (example 4), the heat resistance and peel strength of the reinforcing sheet for a flexible printed circuit including the same are lowered, and the touch adhesion is not satisfactory.
In the halogen-free resin composition, when the epoxy equivalent of the epoxidized polybutadiene is 120 to 170g/eq, the composition can be endowed with proper crosslinking density and cohesive strength, and when the epoxy equivalent is too high (example 5), the heat resistance and the peel strength of the reinforcing plate for the flexible printed circuit are reduced.
In the halogen-free resin composition, when the amine value of the copolyamide is 3-5 mg KOH/g, the bonding property and the touch adhesion property of the reinforcing plate for the flexible printed circuit containing the copolyamide can be effectively improved. When the amine value of the copolyamide is too high (example 6), the tack and peel strength of a reinforcing sheet for a flexible printed circuit comprising the same are lowered, and the storability is deteriorated; when the amine value of the copolyamide is too low (example 7), the peel strength and heat resistance of a reinforcing sheet for a flexible printed circuit comprising the same are lowered.
In the halogen-free resin composition provided by the invention, polyacrylate and epoxidized polybutadiene are used as main resin, copolyamide, amine curing agent and flame retardant are matched, and the five components are compounded synergistically according to a specific mass ratio, so that the application requirement of the halogen-free resin composition in a reinforcing plate for a flexible printed circuit can be met. If epoxidized polybutadiene or copolyamide is absent from the composition (comparative examples 1 and 2) or if the amount of epoxidized polybutadiene and copolyamide is outside the range of the compounding ratio of the present invention (comparative examples 3 to 6), the peel strength, heat resistance, storage stability and touch adhesion of a reinforcing sheet for flexible printed circuits comprising the same are adversely affected to various degrees. Further, if an epoxy resin containing no butadiene structural unit (comparative example 7), a copolyamide defined in the present invention replaced with a non-copolyamide (comparative example 8), a polybutadiene containing no epoxy group (comparative example 9) or a maleated polybutadiene (comparative example 10) were used in place of the epoxidized polybutadiene described in the present invention, the resulting halogen-free resin composition could not satisfy the requirements of a reinforcing sheet for flexible printed circuits in terms of heat resistance, storage stability, peel strength, and the like.
The applicant states that the present invention is illustrated by the above examples of the halogen-free resin composition of the present invention, the reinforcing plate for flexible printed circuit comprising the same and the application thereof, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention is implemented only by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (18)

1. The halogen-free resin composition is characterized by comprising the following components in parts by weight: 50-60 parts of polyacrylate, 10-20 parts of epoxidized polybutadiene, 15-25 parts of copolyamide, 5-10 parts of amine curing agent and 10-20 parts of flame retardant; the polyacrylate comprises carboxyl-containing polyacrylate and/or epoxy-containing polyacrylate.
2. The halogen-free resin composition according to claim 1, wherein the glass transition temperature of the polyacrylate is-10 to 20 ℃.
3. The halogen-free resin composition according to claim 1, wherein the weight average molecular weight of the polyacrylate is 300000 to 900000.
4. The halogen-free resin composition according to claim 1, wherein the epoxidized polybutadiene has a number average molecular weight of 2500 to 6000 g/mol.
5. The halogen-free resin composition according to claim 1, wherein the epoxy equivalent of the epoxidized polybutadiene is 120 to 170 g/eq.
6. The halogen-free resin composition according to claim 1, wherein the glass transition temperature of the copolyamide is 20-40 ℃.
7. The halogen-free resin composition according to claim 1, wherein the amine value of the copolyamide is 3 to 5mg KOH/g.
8. Halogen-free resin composition according to claim 1, characterized in that the amine curing agent is selected from any one or a combination of at least two of dicyandiamide, 4 '-diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone or diphenylmethanediamine.
9. The halogen-free resin composition according to claim 1, wherein the flame retardant is a phosphorus-containing flame retardant.
10. A resin glue solution, which is obtained by dissolving or dispersing the halogen-free resin composition according to any one of claims 1 to 9 in a solvent.
11. The resin cement as claimed in claim 10, wherein the solvent is selected from any one or a combination of at least two of acetone, butanone, toluene, ethanol, isopropanol, cyclohexanone, ethylene glycol methyl ether, propylene glycol methyl ether acetate or ethyl acetate.
12. The resin cement as claimed in claim 10, wherein the solid content of the resin cement is 40-60%.
13. A stiffening plate for a flexible printed circuit is characterized by comprising a base film and a resin layer positioned on the base film, wherein the surface of the resin layer is provided with a protective layer;
the resin layer is a coating layer of the halogen-free resin composition according to any one of claims 1 to 9.
14. The stiffening plate for a flexible printed circuit according to claim 13, wherein the base film is a single-layer polyimide film or a multi-layer polyimide film.
15. The reinforcing plate for a flexible printed circuit according to claim 13, wherein the thickness of the base film is 50 to 200 μm.
16. The reinforcing plate for a flexible printed circuit according to claim 13, wherein the thickness of the resin layer is 20 to 50 μm.
17. The stiffening plate for a flexible printed circuit according to claim 13, wherein the protective layer is a release paper or a release film.
18. A flexible printed circuit board comprising the reinforcing plate for a flexible printed circuit according to any one of claims 13 to 17.
CN201911384831.2A 2019-12-28 2019-12-28 Halogen-free resin composition, reinforcing plate for flexible printed circuit containing halogen-free resin composition and application of reinforcing plate Active CN111040678B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911384831.2A CN111040678B (en) 2019-12-28 2019-12-28 Halogen-free resin composition, reinforcing plate for flexible printed circuit containing halogen-free resin composition and application of reinforcing plate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911384831.2A CN111040678B (en) 2019-12-28 2019-12-28 Halogen-free resin composition, reinforcing plate for flexible printed circuit containing halogen-free resin composition and application of reinforcing plate

Publications (2)

Publication Number Publication Date
CN111040678A CN111040678A (en) 2020-04-21
CN111040678B true CN111040678B (en) 2021-10-19

Family

ID=70240763

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911384831.2A Active CN111040678B (en) 2019-12-28 2019-12-28 Halogen-free resin composition, reinforcing plate for flexible printed circuit containing halogen-free resin composition and application of reinforcing plate

Country Status (1)

Country Link
CN (1) CN111040678B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1670107A (en) * 2004-03-05 2005-09-21 信越化学工业株式会社 Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same
WO2008043658A1 (en) * 2006-10-06 2008-04-17 Tesa Ag Heat-activable adhesive tape particularly for bonding electronic components and conductor tracks
CN103619960A (en) * 2011-06-17 2014-03-05 太阳油墨制造株式会社 Flame-retardant curable resin composition, dry film using same, and printed wiring board
CN103923585A (en) * 2014-04-03 2014-07-16 新纶科技（常州）有限公司 Conductive adhesive composition and conductive adhesive membrane
CN109705387A (en) * 2018-12-27 2019-05-03 广东生益科技股份有限公司 A kind of halogen-free resin composition, flexible printed-circuit board cover film and flexible printed-circuit board comprising it

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1670107A (en) * 2004-03-05 2005-09-21 信越化学工业株式会社 Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same
WO2008043658A1 (en) * 2006-10-06 2008-04-17 Tesa Ag Heat-activable adhesive tape particularly for bonding electronic components and conductor tracks
CN103619960A (en) * 2011-06-17 2014-03-05 太阳油墨制造株式会社 Flame-retardant curable resin composition, dry film using same, and printed wiring board
CN103923585A (en) * 2014-04-03 2014-07-16 新纶科技（常州）有限公司 Conductive adhesive composition and conductive adhesive membrane
CN109705387A (en) * 2018-12-27 2019-05-03 广东生益科技股份有限公司 A kind of halogen-free resin composition, flexible printed-circuit board cover film and flexible printed-circuit board comprising it

Also Published As

Publication number Publication date
CN111040678A (en) 2020-04-21

Similar Documents

Publication Publication Date Title
CN111196066B (en) Adhesive composition and adhesive layer-equipped laminate using same
CN102127290B (en) Epoxy resin composition and flexible copper-clad plate prepared from same
CN101747854B (en) Adhesive combination, covering film and flexible circuit board
US20080113184A1 (en) Adhesive sheet
JP2008088302A (en) Flame-retardant adhesive composition, adhesive sheet using it, cover-lay film and flexible copper-clad laminate plate
JP6831356B2 (en) Halogen-free resin composition and adhesive film, cover film, copper-clad plate produced by it
JP2008291171A (en) Flame-retardant adhesive composition and cover-lay film using the same
CN104629342A (en) Resin composition and covering film prepared from resin composition
CN107922813B (en) Adhesive compositions and articles made therefrom
CN114015371B (en) Insulating adhesive tape
CN102093667B (en) Epoxy resin composite and covering film prepared from same
US20060069201A1 (en) Acrylic flame retardant adhesive composition and acrylic flame retardant adhesive sheet
JP5771186B2 (en) Film composition, and adhesive film and coverlay film thereby
KR100730985B1 (en) Adhesive composition for coverlay film
CN111040387B (en) Halogen-free resin composition and flexible copper clad laminate comprising same
CN111040678B (en) Halogen-free resin composition, reinforcing plate for flexible printed circuit containing halogen-free resin composition and application of reinforcing plate
CN108676475B (en) Halogen-free resin composition, covering film for flexible printed circuit board, flexible copper clad laminate and preparation method thereof
JP2010155975A (en) Polyimide resin, method for producing the same, adhesive composition using the same, adhesive sheet, printing ink composition, and printed circuit board
CN116515239A (en) Resin composition and cover film
JP2010018676A (en) Flame-retardant adhesive composition and adhesion sheet using the same, coverlay film, and flexible copper-clad laminate
WO2023282318A1 (en) Adhesive composition, adhesive sheet, electromagnetic-wave shielding material, laminate, and printed wiring board
JP4238172B2 (en) Flame retardant resin composition and metal-clad laminate for flexible printed wiring board using the flame retardant resin composition
JPWO2010041644A1 (en) Polyamideimide resin, adhesive composition using the resin, printed circuit board ink using the adhesive composition, coverlay film, adhesive sheet, and printed circuit board
JP6716676B2 (en) Resin composition, adhesive tape, method for producing resin composition and method for producing adhesive tape
CN114292493B (en) Resin composition and use thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant