CN111040387B - Halogen-free resin composition and flexible copper clad laminate comprising same - Google Patents

Halogen-free resin composition and flexible copper clad laminate comprising same Download PDF

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Publication number
CN111040387B
CN111040387B CN201911383764.2A CN201911383764A CN111040387B CN 111040387 B CN111040387 B CN 111040387B CN 201911383764 A CN201911383764 A CN 201911383764A CN 111040387 B CN111040387 B CN 111040387B
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halogen
parts
resin composition
clad laminate
copper clad
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CN111040387A (en
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左陈
茹敬宏
伍宏奎
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/08—Epoxidised polymerised polyenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/08—Epoxidised polymerised polyenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention provides a halogen-free resin composition and a flexible copper clad laminate containing the same, wherein the halogen-free resin composition comprises the following components: 20-30 parts of epoxidized polybutadiene, 18-25 parts of multifunctional epoxy resin, 10-20 parts of carboxyl-containing saturated polyester resin, 5-10 parts of polyester polyol, 20-30 parts of curing agent and 15-25 parts of flame retardant; the multiple chemical reactions among the components can realize medium-temperature rapid curing of the system, and a compact and stable interpenetrating crosslinked network is formed after curing, so that the halogen-free resin composition has a long pot life, proper touch viscosity, extremely low hygroscopicity and excellent bonding stability, and is suitable for a roll-to-roll preparation process of a flexible copper clad laminate. The flexible copper clad laminate containing the halogen-free resin composition has excellent peel strength, heat resistance, secondary appearance and chemical resistance, and can meet the requirements of stability and reliability of flexible printed circuits.

Description

Halogen-free resin composition and flexible copper clad laminate comprising same
Technical Field
The invention belongs to the technical field of copper-clad plates, and particularly relates to a halogen-free resin composition and a flexible copper-clad plate containing the same.
Background
In recent years, electronic products are developing towards light, thin, short, small and wearable products, and the development trend effectively drives upgrading and updating of circuit boards. The flexible printed circuit board is very suitable for three-dimensional space installation, can ensure that the wiring is more reasonable, the structure is more compact, and the installation space is saved, so the flexible printed circuit board is widely applied to portable electronic equipment such as mobile phones, digital cameras, notebook computers and the like, and the fields such as flat televisions, automotive electronics, instruments and meters, medical instruments, aerospace, war industry and the like. The flexible copper clad laminate is a component of the flexible printed circuit, and the structural performance of the flexible copper clad laminate is directly related to the preparation and application of the flexible printed circuit, so the flexible copper clad laminate has important research value.
The flexible copper clad laminate of the adhesive type is a copper clad laminate which realizes the connection of a base film and a copper foil through an adhesive, has very wide application and plays an important role in the flexible copper clad laminate. In the copper-clad plate, the performance of the adhesive is important for the later processing property and usability of the flexible copper-clad plate, and based on the performance, the finding of the adhesive suitable for the copper-clad plate is a critical problem.
CN103540103A discloses an epoxy resin composition and a method for preparing adhesive using the same, wherein the composition is composed of the following components: 100-110 parts of epoxy resin, 1.9-2.4 parts of dicyandiamide, 0.04-0.07 part of dimethyl imidazole and 22-25 parts of N, N-dimethylformamide. The composition adopts N, N-dimethylformamide as a solvent, so that the composition has proper viscosity and gel time; the adhesive prepared by the composition has good cohesiveness, good heat resistance, toughness and machining performance after curing, high glass transition temperature and low hygroscopicity, and is suitable for producing copper clad plates.
CN1529546A discloses a method for preparing a cover film for a flexible circuit board, which specifically comprises: coating a resin glue solution comprising 20-30 parts of brominated epoxy resin, 16-20 parts of bisphenol A epoxy resin, 8-12 parts of novolac epoxy resin, 14-9 parts of Hytrel thermoplastic elastomer, 8-14 parts of thermoplastic carboxyl nitrile rubber, 4 parts of arylamine curing agent and 8 parts of modified dicyandiamide curing agent on a polyimide film, drying for 15min at 80-90 ℃ to form a coating with the thickness of 15-20 microns, and isolating by using polyester or other release paper to prepare a cover film. The cover film is used for a flexible circuit board, and has high bonding strength and good heat resistance.
CN102391808A discloses a preparation method of a medium temperature curing epoxy adhesive and an application thereof in a flexible polyester copper clad laminate, wherein the adhesive comprises: liquid epoxy CYD-128, solid epoxy CYD-014, liquid carboxyl nitrile rubber CTBN, solid carboxyl nitrile rubber 1072, modified dicyandiamide curing agent and one or more inorganic fillers; the adhesive is used for bonding a copper foil and a polyester film, and can be cured at the temperature of 120-130 ℃, so that the prepared flexible polyester copper clad laminate substrate has the peel strength of more than 1.0N/mm.
In the existing adhesive type flexible copper clad laminate, an epoxy system toughened by nitrile rubber is generally used as an adhesive, in order to obtain better heat resistance and a better pot life, aromatic amine or dicyandiamide is generally used as a curing agent, and the adhesive has a longer pot life but can be cured in an environment of more than 120 ℃. Because the flexible copper clad laminate is mostly produced in a roll-to-roll mode, high-temperature curing can cause uneven heating inside and outside the roll of the roll-shaped flexible copper clad laminate, potential performance hazards exist, large-roll production cannot be carried out, and the production efficiency and the product percent of pass are seriously influenced.
Therefore, it is a research focus in the field to develop an adhesive with relatively low curing temperature, heat resistance and a pot life to meet the requirements of production process and performance of a flexible copper clad laminate.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a halogen-free resin composition and a flexible copper clad laminate containing the same, wherein the halogen-free resin composition is endowed with the characteristics of low curing temperature, good heat resistance and high peel strength through screening and compounding of all components, and can be adapted to the roll-to-roll production process of the flexible copper clad laminate; the flexible copper clad laminate containing the halogen-free resin composition has excellent heat resistance stability, peeling strength and chemical resistance, and can meet the requirements of the flexible printed circuit on stability and reliability.
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: 20-30 parts of epoxidized polybutadiene, 18-25 parts of multifunctional epoxy resin, 10-20 parts of carboxyl-containing saturated polyester resin, 5-10 parts of polyester polyol, 20-30 parts of curing agent and 15-25 parts of flame retardant.
The halogen-free resin composition provided by the invention takes epoxidized polybutadiene and multifunctional epoxy resin as main resins. Among them, epoxidized polybutadiene has excellent flexibility and reactivity; the multifunctional epoxy resin can effectively increase the crosslinking density and the cohesive strength of the cured composition, and greatly contributes to the improvement of the heat resistance and the cohesiveness of the halogen-free resin composition. The halogen-free resin composition takes the carboxyl-containing saturated polyester resin as the toughening agent, the carboxyl-containing saturated polyester resin has good flexibility, and the carboxyl-containing saturated polyester resin is uniformly dispersed in a composition system to form a sea-island structure, so that the toughening of the composition is realized, and the carboxyl functional group of the composition can react with the epoxy group in the main resin, so that the crosslinking density and the compatibility of the halogen-free resin composition can be further improved. The halogen-free resin composition provided by the invention also comprises polyester polyol, and on one hand, the polyester polyol can react with residual carboxyl in a system to reduce the carboxyl content in the cured system, so that the hygroscopicity is reduced, and the risk of layering and board explosion in the subsequent circuit board processing process is reduced; on the other hand, the polyester polyol has small molecular weight and large apparent viscosity, and the introduction of the polyester polyol can improve the touch adhesion of the halogen-free resin composition and avoid the generation of micro bubbles after the copper foil is rolled in the production of the flexible copper clad laminate, thereby improving the reliability of the flexible copper clad laminate.
The halogen-free resin composition provided by the invention has the advantages that the curing temperature of the composition is reduced by compounding various components, a stable interpenetrating cross-linked network structure is formed after curing, the composition has high cohesive strength, thermal stability, cohesiveness, flame retardance and proper touch adhesiveness, and is suitable for a roll-to-roll production process of a flexible copper clad laminate, so that the obtained flexible copper clad laminate has excellent heat resistance, peel strength and reliability.
The amount of epoxidized polybutadiene in the halogen-free resin composition may be 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, or 29 parts by weight, and specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the ranges for brevity and clarity.
The multifunctional epoxy resin may be included in an amount of 18.5 parts by weight, 19 parts by weight, 19.5 parts by weight, 20 parts by weight, 20.5 parts by weight, 21 parts by weight, 21.5 parts by weight, 22 parts by weight, 22.5 parts by weight, 23 parts by weight, 23.5 parts by weight, 24 parts by weight, or 24.5 parts by weight, and specific point values therebetween are not exhaustive, and specific point values included in the range are not enumerated herein for the sake of brevity and conciseness.
The content of the carboxyl group-containing saturated polyester resin 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, and the present invention is not exhaustive in the specific points included in the range for brevity and conciseness.
The polyester polyol 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 points therebetween, limited to space and for the sake of brevity, are not exhaustive and are not intended to include specific points within the recited ranges.
The curing agent may be present in an amount of 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, or 29 parts by weight, and specific points therebetween are not exhaustive for the purpose of brevity and clarity.
The flame retardant may be used 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 points therebetween are not exhaustive for the purpose of brevity and clarity.
In the halogen-free resin composition provided by the invention, the components are compounded in a synergistic manner within the content range, the curing temperature is not higher than 100 ℃, medium-temperature curing is realized, and the obtained halogen-free resin composition forms an interpenetrating compact cross-linked network structure after curing, so that the composition is endowed with high thermal stability, cohesiveness, flexibility and higher touch viscosity. The content of any component in the composition outside the above-defined range affects the overall properties of the halogen-free resin composition. The epoxidized polybutadiene with too high content can cause the heat resistance and aging resistance of the composition to be poor, and the epoxidized polybutadiene with too low content can cause the flexibility and crosslinking density of the composition to be insufficient, thereby affecting the peel strength and chemical resistance of the halogen-free resin composition. The high content of the polyester polyol can reduce the crosslinking density and the heat resistance of a system, and the low dosage of the polyester polyol can cause the insufficient touch adhesion of the composition, so that microbubbles are generated after the copper foil is rolled in the process of preparing the flexible copper clad laminate, and the reliability of the flexible copper clad laminate is influenced.
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 multifunctional epoxy resin has a functionality > 2, e.g., a functionality of 3 or 4, etc.
Preferably, the multifunctional epoxy resin is selected from any one of phenol type novolac epoxy resin, bisphenol a type novolac epoxy resin, o-cresol novolac epoxy resin or tetraphenol ethane tetraglycidyl ether epoxy resin or a combination of at least two thereof.
Preferably, the multifunctional epoxy resin has an epoxy equivalent weight of 150 to 220 grams per equivalent (g/eq), such as 155g/eq, 160g/eq, 165g/eq, 170g/eq, 175g/eq, 180g/eq, 185g/eq, 190g/eq, 195g/eq, 200g/eq, 210g/eq, or 215g/eq, and the specific point values between the above point values, limited to space and for the sake of brevity, are not exhaustive and the invention is not intended to include the specific point values included in the ranges.
Preferably, the acid value of the carboxyl group-containing saturated polyester resin is 10 to 25mg KOH/g, such as 12mg KOH/g, 14mg KOH/g, 16mg KOH/g, 18mg KOH/g, 20mg KOH/g, 22mg KOH/g or 24mg KOH/g, and the 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 carboxyl group-containing saturated polyester resin has a number average molecular weight of 5000 to 20000g/mol, such as 6000g/mol, 7000g/mol, 8000g/mol, 9000g/mol, 10000g/mol, 11000g/mol, 12000g/mol, 14000g/mol, 16000g/mol, 18000g/mol or 19000g/mol, and specific points therebetween are not limited to space and for the sake of brevity, and the present invention does not provide an exhaustive list of specific points included in the range.
Preferably, the glass transition temperature of the carboxyl group-containing saturated polyester resin is-10 to 50 ℃, such as-8 ℃, -5 ℃, -2 ℃, 0 ℃, 3 ℃, 5 ℃, 8 ℃, 10 ℃, 13 ℃, 15 ℃, 18 ℃, 20 ℃, 23 ℃, 25 ℃, 28 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃, 42 ℃, 45 ℃ or 48 ℃, and specific values therebetween, are limited to space and for the sake of brevity, and the present invention does not exhaustively enumerate specific values encompassed by the range.
In a preferred embodiment of the present invention, the carboxyl group-containing saturated polyester resin has an acid value of 10 to 25mgKOH/g, a number average molecular weight of 5000 to 20000g/mol, and TgThe temperature is-10 to 50 ℃, and the toughening agent can be uniformly dispersed in the composition to form a sea-island structure and has a toughening effect on a system. The carboxyl functional group in the carboxyl-containing saturated polyester resin can react with the main resin, the polyester polyol and the curing agent to form a stable chemical crosslinking network, so that the flexibility, the heat resistance and the compatibility of the composition are further improved. If the acid value of the carboxyl group-containing saturated polyester resin is less than the above-defined range, the reactivity is extremely low and no chemical reaction occurs, resulting in a decrease in the heat resistance and compatibility of the system; if the acid value is higher than the limited range, the composition contains excessive unblocked carboxyl, so that the hygroscopicity of the composition is strong, and the reliability and the heat resistance of the flexible copper-clad plate are influenced.
The carboxyl group-containing saturated polyester resin of the present invention can be obtained by the prior art, and illustratively, the carboxyl group-containing saturated polyester resin may be selected from BX-39SS manufactured by toyobo co.
Preferably, the polyester polyol has a number average molecular weight of 2000 to 3000g/mol, such as 2100g/mol, 2200g/mol, 2300g/mol, 2400g/mol, 2500g/mol, 2600g/mol, 2700g/mol, 2800g/mol or 2900g/mol, and the specific values therebetween are not exhaustive, and for the sake of brevity and brevity, the present invention is not intended to be exhaustive of the specific values included in the ranges.
Preferably, the hydroxyl value of the polyester polyol is 30-60 mg KOH/g, such as 32mg KOH/g, 34mg KOH/g, 36mg KOH/g, 38mg KOH/g, 40mg KOH/g, 42mg KOH/g, 44mg KOH/g, 46mg KOH/g, 48mg KOH/g, 50mg KOH/g, 52mg KOH/g, 54mg KOH/g, 56mg KOH/g, 58mg KOH/g or 59mg KOH/g, and the specific values therebetween are limited to space and for brevity, and the invention is not exhaustive.
The polyester polyol of the present invention can be obtained by the prior art, and illustratively, the polyester polyol can be selected from XCP-2000M and/or XCP-3000M produced by asahi chemistry.
Preferably, the curing agent is an amine curing agent.
Preferably, the curing temperature of the curing agent is 50 to 100 ℃, for example, 52 ℃, 55 ℃, 58 ℃, 60 ℃, 62 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃, 78 ℃, 80 ℃, 82 ℃, 85 ℃, 88 ℃, 90 ℃, 92 ℃, 95 ℃, 97 ℃ or 99 ℃, and the specific values therebetween are limited by the space and the conciseness, and the invention is not exhaustive.
Preferably, the curing agent is a polyetheramine curing agent and/or a polyamide curing agent.
The polyetheramine curing agent and/or polyamide curing agent of the present invention may be obtained by the prior art, and may be exemplified by any one or a combination of at least two of Baxxodur EC301, Baxxodur EC302, or Baxxodur EC310, which are available from BASF corporation, and may be selected from Versamid 125 and/or Versamid 140, which are available from Gabriel corporation.
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 20-30%, such as 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28% or 29%, 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.
The solid content of the resin glue solution is preferably 20-30%, and if the solid content is too high, the resin glue solution is easy to gel and the operation time is shortened; if the solid content is too low, the resin adhesive is easy to flow during operation, and surface defects are generated.
In another aspect, the invention provides a flexible copper clad laminate, which comprises a base film and a resin layer positioned on one or two surfaces of the base film, wherein the surface of the resin layer is provided with a copper foil.
The resin layer is a coating layer of the halogen-free resin composition.
Preferably, the base film is a polyimide insulating film.
Preferably, the base film has a thickness of 10 to 75 μm, such as 12 μm, 15 μm, 18 μm, 20 μm, 23 μm, 25 μm, 27 μm, 30 μm, 33 μm, 35 μm, 38 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 72 μm, or 74 μm, and specific values therebetween are limited in space and for the sake of brevity, and the present invention is not exhaustive of the specific values included in the ranges.
Preferably, the thickness of the resin layer is 10 to 35 μm, such as 12 μm, 15 μm, 17 μm, 20 μm, 22 μm, 25 μm, 28 μm, 30 μm, 32 μm or 34 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 copper foil is a rolled copper foil or an electrolytic copper foil.
Preferably, the copper foil has a thickness of 12 to 50 μm, such as 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, 28 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm or 48 μm, and specific values therebetween, and the invention is not exhaustive for reasons of space and simplicity.
Illustratively, the preparation method of the flexible copper clad laminate comprises the following steps: coating the resin glue solution of the resin composition on one side or two sides of the base film, and drying; and then pressing copper foil on the surface of the resin composition, and curing to obtain the flexible copper clad laminate.
Preferably, the drying temperature is 80-120 deg.C, such as 82 deg.C, 85 deg.C, 88 deg.C, 90 deg.C, 92 deg.C, 95 deg.C, 98 deg.C, 100 deg.C, 102 deg.C, 105 deg.C, 108 deg.C, 110 deg.C, 113 deg.C, 115 deg.C, 117 deg.C or 119 deg.C.
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 method of pressing is roll lamination.
Preferably, the temperature of the pressing is 60-90 ℃, such as 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃ or 89 ℃.
Preferably, the curing temperature is 50-100 ℃, such as 52 ℃, 55 ℃, 58 ℃, 60 ℃, 62 ℃, 65 ℃, 67 ℃, 70 ℃, 72 ℃, 75 ℃, 78 ℃, 80 ℃, 82 ℃, 85 ℃, 88 ℃, 90 ℃, 92 ℃, 95 ℃, 97 ℃ or 99 ℃ and the like.
Preferably, the curing time is 5 to 10 hours, such as 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, or 9.5 hours.
Compared with the prior art, the invention has the following beneficial effects:
the halogen-free resin composition provided by the invention takes epoxidized polybutadiene and multifunctional epoxy resin as main body resin, carboxyl-containing saturated polyester resin as a toughening agent, polyester polyol, a curing agent and a flame retardant are matched for use, the medium-temperature rapid curing of a system is realized through multiple chemical reactions among the components, the curing temperature is 50-100 ℃, and a compact and stable interpenetrating cross-linked network is formed after the curing, so that the halogen-free resin composition has the advantages of longer pot life, higher touch viscosity, extremely low hygroscopicity, excellent flexibility, compatibility, cohesiveness, heat resistance and flame retardance, and is suitable for the roll-to-roll preparation process of the flexible copper clad laminate. The flexible copper clad laminate containing the halogen-free resin composition has the peel strength of 1.3-1.5N/mm, the ultimate dip soldering temperature of 350 ℃ and the chemical resistance of 93-95%, has good secondary appearance of an adhesive layer, is bubble-free, has excellent peel strength, heat resistance, chemical resistance and reliability, and can meet the requirements of stability and reliability of a flexible printed circuit.
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) 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.
(2) Multifunctional epoxy resin: phenol type novolac epoxy resin (KEP-1131, having an epoxy equivalent of 175g/eq, available from Kolon Chemical Co.), bisphenol A type novolac epoxy resin (KEB-3165, having an epoxy equivalent of 213g/eq, available from Kolon Chemical Co.), or tetraphenolethane tetraglycidyl ether epoxy resin (EPON 1031-A-70, having an epoxy equivalent of 212g/eq, available from Hexion Co.).
(3) Carboxyl group-containing saturated polyester resin: BX-39SS (acid value: 17mg KOH/g, number average molecular weight: 16000g/mol, glass transition temperature: 15 ℃) or H204 (acid value: 25mg KOH/g, number average molecular weight: 5400g/mol, glass transition temperature: 32 ℃) from hyperbranched resins technologies.
(4) Polyester polyol: XCP-2000M (hydroxyl number 56mg KOH/g, number average molecular weight 2000g/mol) or XCP-3000M (hydroxyl number 36mg KOH/g, number average molecular weight 3000g/mol) of Asahi Sichuan chemical.
(5) Curing agent: the polyether amine curing agent is Baxxodur EC301 from BASF, and the polyamide curing agent is Versamid 125 or Versamid 140 from Gabriel.
(6) Flame retardant: a phosphorus-containing flame retardant, SPB-100 available from Otsuka chemical Co., Ltd., OP-935 or OP-930 available from Laine, Germany.
(7) Base film: the polyimide films were divided into 3 kinds by thickness, 12.5 μm, 25 μm and 75 μm, respectively.
(8) Copper foil: 12 μm rolled copper foil, 35 μm electrolytic copper foil or 50 μm rolled copper foil.
Example 1
The halogen-free resin composition comprises the following components in parts by weight: 20 parts by weight of epoxidized polybutadiene L680, 18 parts by weight of phenol novolac epoxy resin, 10 parts by weight of carboxyl-containing saturated polyester resin BX-39SS, 5 parts by weight of polyester polyol XCP-2000M, 20 parts by weight of curing agent Baxxodur EC301 and 15 parts by weight of flame retardant SPB-100.
The halogen-free resin composition is used for preparing the flexible copper clad laminate, and the specific method comprises the following steps:
(1) mixing and uniformly dispersing the halogen-free resin composition and acetone to obtain a resin glue solution with a solid content of 20%;
(2) coating the resin glue solution obtained in the step (1) on two surfaces of a polyimide film with the thickness of 12.5 microns, wherein the glue coating thickness is 10 microns; drying at 80 deg.C for 2min, removing solvent and forming partially cured resin layer on the surface of the polyimide film; and then compounding with 12 mu m rolled copper foil at 60 ℃, and curing for 5 hours at 50 ℃ to obtain the flexible copper clad laminate.
Example 2
The halogen-free resin composition comprises the following components in parts by weight: 25 parts by weight of epoxidized polybutadiene L681, 20 parts by weight of bisphenol A type novolac epoxy resin, 15 parts by weight of carboxyl group-containing saturated polyester resin H204, 8 parts by weight of polyester polyol XCP-3000M, 25 parts by weight of curing agent Versamid 125 and 20 parts by weight of flame retardant OP-930.
The halogen-free resin composition is used for preparing the flexible copper clad laminate, and the specific method comprises the following steps:
(1) mixing the halogen-free resin composition with butanone and uniformly dispersing to obtain a resin glue solution with a solid content of 25%;
(2) coating the resin glue solution obtained in the step (1) on two surfaces of a polyimide film with the thickness of 25 micrometers, wherein the coating thickness is 20 micrometers; drying at 100 deg.C for 5min, removing solvent and forming partially cured resin layer on the surface of the polyimide film; then compounding with 35 mu m electrolytic copper foil at 80 ℃, and curing for 10 hours at 80 ℃ to obtain the flexible copper clad laminate.
Example 3
The halogen-free resin composition comprises the following components in parts by weight: 30 parts by weight of epoxidized polybutadiene L682, 25 parts by weight of tetraphenolethane tetraglycidyl ether epoxy resin, 20 parts by weight of carboxyl group-containing saturated polyester resin BX-39SS, 10 parts by weight of polyester polyol XCP-2000M, 30 parts by weight of curing agent Versamid 140 and 25 parts by weight of flame retardant OP-935.
The halogen-free resin composition is used for preparing the flexible copper clad laminate, and the specific method comprises the following steps:
(1) mixing and uniformly dispersing the halogen-free resin composition and toluene to obtain a resin glue solution with the solid content of 30%;
(2) coating the resin glue solution obtained in the step (1) on two surfaces of a polyimide film with the thickness of 75 microns, wherein the glue coating thickness is 35 microns; drying at 120 deg.C for 8min, removing solvent and forming partially cured resin layer on the surface of the polyimide film; and then compounding with a 50-micron rolled copper foil at 90 ℃, and curing for 6 hours at 100 ℃ to obtain the flexible copper clad laminate.
Example 4
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, epoxy equivalent of 193 g/eq).
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Example 5
A halogen-free resin composition whose composition differs from that of example 2 in that the carboxyl group-containing saturated polyester resin H204 was replaced with an equal mass of carboxyl group-containing saturated polyester resin DYNAPOL 013402 (DYNAPOL 013402 from Evonik corporation, acid value 8mg KOH/g).
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Example 6
A halogen-free resin composition whose composition differs from that of example 2 in that the carboxyl group-containing saturated polyester resin H204 was replaced with an equal mass of carboxyl group-containing saturated polyester resin H104 (H104 from hyperbranched resins technologies, Inc., acid value 30mg KOH/g).
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Example 7
A halogen-free resin composition is characterized in that the components of the halogen-free resin composition are different from those of the embodiment 2, in that polyester polyol XCP-3000M is replaced by polyester polyol PA-3018 (PA-3018 of Shanghai Weika photoelectric new material, the hydroxyl value is 19mg KOH/g) with equal mass.
The halogen-free resin composition is used for preparing the flexible copper clad laminate, and the specific method is the same as that in the embodiment 2, so that the flexible copper clad laminate is obtained.
Example 8
A halogen-free resin composition whose composition differs from that of example 2 in that the polyester polyol XCP-3000M is replaced with an equal mass of polyester polyol XCP-706 (XCP-706, OH number 75mg KOH/g, available from Asahi Chuan chemical Co., Ltd.).
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Example 9
A halogen-free resin composition whose composition differs from that of example 2 in that a bisphenol A type novolac epoxy resin was replaced with an equal mass of a polyfunctional epoxy ERDM-404L (ERDM-404L, epoxy equivalent 118g/eq, manufactured by Shanghai Mass Splenders Co., Ltd.).
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Example 10
A halogen-free resin composition is characterized in that the components of the composition are different from those of example 2 in that bisphenol A type novolac epoxy resin is replaced by equal mass of multifunctional epoxy KDCP-200 (KDCP-200 of national chemical Co., Ltd., epoxy equivalent weight 275 g/eq).
The halogen-free resin composition is used for preparing the flexible copper clad laminate, and the specific method is the same as that in the embodiment 2, so that the flexible copper clad laminate 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 a bisphenol A type novolac epoxy resin.
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Comparative example 2
A halogen-free resin composition whose composition is different from that of example 2 in that polyester polyol is not contained.
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Comparative example 3
A halogen-free resin composition whose composition is different from that of example 2 in that it does not contain a carboxyl group-containing saturated polyester resin.
The halogen-free resin composition is used for preparing the flexible copper clad laminate, and the specific method is the same as that in the embodiment 2, so that the flexible copper clad laminate is obtained.
Comparative example 4
A halogen-free resin composition differing from example 2 in the composition that bisphenol A type novolac epoxy resin was replaced with bisphenol A epoxy resin NPEL-144 (NPEL-144 in south Asia, epoxy equivalent weight 215g/eq) of equal mass.
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Comparative example 5
A halogen-free resin composition whose composition differs from that of example 2 in that the polyester polyol XCP-3000M was replaced with an equal mass of polyether polyol EP-330N (EP-330N of the Guangzhou Venturi chemical industry, hydroxyl value: 34mg KOH/g).
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Comparative example 6
A halogen-free resin composition whose composition is different from that of example 2 in that the content of the bisphenol a type novolac epoxy resin is 14 parts by weight.
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Comparative example 7
A halogen-free resin composition whose composition is different from that of example 2 in that the content of the bisphenol a type novolac epoxy resin is 35 parts by weight.
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Comparative example 8
A halogen-free resin composition whose composition is different from that of example 2 in that the content of epoxidized polybutadiene L681 is 15 parts by weight.
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Comparative example 9
A halogen-free resin composition whose composition is different from that of example 2 in that the content of epoxidized polybutadiene L681 is 40 parts by weight.
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Comparative example 10
A halogen-free resin composition whose composition differs from that of example 2 in that the carboxyl group-containing saturated polyester resin H204 was contained in an amount of 8 parts by weight.
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Comparative example 11
A halogen-free resin composition whose composition is different from that of example 2 in that the content of the carboxyl group-containing saturated polyester resin H204 was 25 parts by weight.
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Comparative example 12
A halogen-free resin composition whose composition is different from that of example 2 in that the content of polyester polyol XCP-3000M is 3 parts by weight.
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Comparative example 13
A halogen-free resin composition whose composition is different from that of example 2 in that the content of polyester polyol XCP-3000M is 15 parts by weight.
The halogen-free resin composition is used for preparing a flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
Comparative example 14
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 flexible copper clad laminate, and the specific method is the same as that of the embodiment 2 to obtain the flexible copper clad laminate.
And (3) performance testing:
(1) peel strength: the test was carried out according to the method specified in the IPC-TM-6502.4.9 standard.
(2) Heat resistance: testing the limit dip soldering temperature, sequentially placing the flexible copper clad laminate in a tin furnace at different temperatures for dipping for 20s, taking out and observing, and detecting whether layered blistering exists; the test temperature starts from 280 ℃, the test is carried out by taking 10 ℃ as a step and gradually raising the temperature, and the temperature before the layered foaming is generated is the ultimate dip-soldering temperature.
(3) The secondary appearance: etching the copper foil of the flexible copper clad laminate sample, and observing whether the poor appearance such as bubbles exists under a magnifying lens of 100 times.
(4) Chemical resistance: the test was carried out according to the method specified in the IPC-TM-6502.3.2 standard.
The performance of the flexible copper clad laminates obtained in examples 1-10 and comparative examples 1-14 were tested according to the performance test method, and the test results are shown in table 1.
TABLE 1
Figure BDA0002342948430000191
Figure BDA0002342948430000201
As can be seen from the data in Table 1, when the halogen-free resin composition provided in the embodiments 1 to 3 of the present invention is used for preparing a flexible copper clad laminate, the curing temperature is not higher than 100 ℃, the rapid curing at the intermediate temperature can be realized, and the halogen-free resin composition can be matched with a roll-to-roll preparation process of the flexible copper clad laminate. The obtained flexible copper clad laminate has excellent peel strength, heat resistance and chemical resistance, the peel strength of the flexible copper clad laminate reaches 1.3-1.5N/mm, the ultimate dip soldering temperature reaches 350 ℃, the chemical resistance reaches 93-95%, the secondary appearance of an adhesive layer is good, and no air bubbles exist.
In the halogen-free resin composition, when the epoxy equivalent of the epoxidized polybutadiene is 120-170 g/eq, the composition can be endowed with high flexibility, crosslinking density and cohesive strength. When the epoxy equivalent value is too high (example 4), the crosslinking density of the resin composition is reduced, and the heat resistance, peel strength and chemical resistance of the flexible copper clad laminate are reduced.
In the halogen-free resin composition provided by the invention, the carboxyl-containing saturated polyester resin with the acid value of 10-25 mg KOH/g can toughen the composition, and the polyester polyol with the hydroxyl value of 30-60 mg KOH/g can provide good touch viscosity, and can react with residual carboxyl in a system to play a role in reducing hygroscopicity. If the acid value of the carboxyl-containing saturated polyester resin is out of the above range (examples 5 and 6) or the hydroxyl value of the polyester polyol is out of the above range (examples 7 and 8), the properties of the halogen-free resin composition, such as heat resistance and chemical resistance, are reduced, and the application of the halogen-free resin composition in a flexible copper clad laminate is not satisfied.
In the halogen-free resin composition, when the epoxy equivalent of the multifunctional epoxy resin is 150-220 g/eq, the resin composition can be endowed with proper crosslinking density. When the epoxy equivalent is less than 150g/eq (example 9), the resin composition has an excessively high crosslinking density, resulting in a brittle adhesive layer and a relatively low peel strength; when the epoxy equivalent is more than 220g/eq (example 10), the crosslinking density of the resin composition is insufficient, and the heat resistance and chemical resistance are lowered.
The halogen-free resin composition provided by the invention takes epoxidized polybutadiene and multifunctional epoxy resin as main body resin, takes saturated polyester resin containing carboxyl as a toughening agent, and uses polyester polyol, a curing agent and a flame retardant in a matching way, and 6 components are compounded in a synergistic way according to a specific mass ratio to meet the application requirement of the halogen-free resin composition in a flexible copper clad laminate. If any one of the multifunctional epoxy resin, the carboxyl-containing saturated polyester resin or the polyester polyol is absent in the composition (comparative examples 1 to 3) or the amount of each component exceeds the blending ratio range of the invention (comparative examples 6 to 13), the peel strength, the heat resistance, the chemical resistance and the sub-appearance of the flexible copper clad laminate containing the composition are adversely affected to different degrees. Thirdly, if bisphenol A epoxy resin is used for replacing multifunctional epoxy resin (comparative example 4) or polyether polyol is used for replacing polyester polyol (comparative example 5), the heat resistance and chemical resistance of the obtained halogen-free resin composition are obviously reduced, and the use requirement of the flexible copper-clad plate cannot be met. In addition, if other epoxy resins without butadiene structural units are used to replace the epoxidized polybutadiene (comparative example 14), the heat resistance, peel strength and chemical resistance of the flexible copper clad laminate prepared from the obtained halogen-free resin composition are obviously reduced.
The applicant states that the present invention is illustrated by the above examples to a halogen-free resin composition and a flexible copper clad laminate comprising the same, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must rely on the above examples to be implemented. 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 (17)

1. The halogen-free resin composition is characterized by comprising the following components in parts by weight: 20-30 parts of epoxidized polybutadiene, 18-25 parts of multifunctional epoxy resin, 10-20 parts of carboxyl-containing saturated polyester resin, 5-10 parts of polyester polyol, 20-30 parts of curing agent and 15-25 parts of flame retardant;
the epoxy equivalent of the epoxidized polybutadiene is 120-170 g/equivalent; the multifunctional epoxy resin is selected from any one or a combination of at least two of phenol type novolac epoxy resin, bisphenol A type novolac epoxy resin, o-cresol novolac epoxy resin or tetraphenol ethane tetraglycidyl ether epoxy resin, and the epoxy equivalent of the multifunctional epoxy resin is 150-220 g/equivalent; the acid value of the carboxyl-containing saturated polyester resin is 10-25 mg KOH/g; the number average molecular weight of the polyester polyol is 2000-3000 g/mol; the curing agent is polyether amine curing agent and/or polyamide curing agent.
2. 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.
3. Halogen-free resin composition according to claim 1, characterised in that the multifunctional epoxy resin has a functionality > 2.
4. The halogen-free resin composition according to claim 1, wherein the carboxyl group-containing saturated polyester resin has a number average molecular weight of 5000 to 20000 g/mol.
5. The halogen-free resin composition according to claim 1, wherein the glass transition temperature of the carboxyl group-containing saturated polyester resin is-10 to 50 ℃.
6. The halogen-free resin composition according to claim 1, wherein the polyester polyol has a hydroxyl value of 30 to 60mg KOH/g.
7. The halogen-free resin composition according to claim 1, wherein the curing temperature of the curing agent is 50 to 100 ℃.
8. The halogen-free resin composition according to claim 1, wherein the flame retardant is a phosphorus-containing flame retardant.
9. A resin glue solution, which is characterized in that the resin glue solution is obtained by dissolving or dispersing the halogen-free resin composition as defined in any one of claims 1 to 8 in a solvent.
10. The resin cement as claimed in claim 9, 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.
11. The resin cement as claimed in claim 9, wherein the solid content of the resin cement is 20-30%.
12. A flexible copper clad laminate is characterized in that the flexible copper clad laminate comprises a base film and a resin layer positioned on one side or two sides of the base film, wherein the surface of the resin layer is provided with a copper foil;
the resin layer is a coating layer of the halogen-free resin composition according to any one of claims 1 to 8.
13. The flexible copper clad laminate according to claim 12 wherein the base film is a polyimide insulating film.
14. The flexible copper clad laminate according to claim 12, wherein the thickness of the base film is 10 to 75 μm.
15. The flexible copper clad laminate according to claim 12, wherein the thickness of the resin layer is 10 to 35 μm.
16. The flexible copper clad laminate according to claim 12, wherein the copper foil is a rolled copper foil or an electrolytic copper foil.
17. The flexible copper clad laminate according to claim 12, wherein the copper foil has a thickness of 12 to 50 μm.
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