CN111154231A - Epoxy resin composition and flexible copper clad laminate prepared from same - Google Patents

Epoxy resin composition and flexible copper clad laminate prepared from same Download PDF

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Publication number
CN111154231A
CN111154231A CN201911426058.1A CN201911426058A CN111154231A CN 111154231 A CN111154231 A CN 111154231A CN 201911426058 A CN201911426058 A CN 201911426058A CN 111154231 A CN111154231 A CN 111154231A
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parts
epoxy resin
resin composition
clad laminate
flexible copper
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Inventor
龚霈云
陈敬通
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Hongyang Electronics Ltd
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Hongyang Electronics 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
    • 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
    • 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
    • B32B2307/302—Conductive
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/02—Polyglycidyl ethers of bis-phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides an epoxy resin composition and a flexible copper clad laminate prepared from the same, which comprise the following components in parts by weight: bisphenol a epoxy resin: 5-50 parts of dicyclopentadiene epoxy resin: 5-30 parts of synthetic rubber: 5-35 parts of nitrogen flame retardant: 1-30 parts of curing agent: 1-10 parts of a curing catalyst: 0.01-2.0 parts of antioxidant: 0.01 to 2.0 parts; an ion scavenger: 0.01-2.0 parts of heat conduction material: 1 to 80 portions. Compared with the prior art, the invention has the beneficial effects that: the excellent flexibility of the resin composition is ensured on the premise of effectively reducing the rubber dosage, and the halogen-free phosphorus-free resin composition can be obtained by simply mixing the nitrogen-containing flame retardant; the flexible copper clad laminate prepared by the composition has excellent flexibility, heat resistance and processability, and the flame retardance reaches UL94VTM-0 level; the flexible copper clad laminate prepared by the composite material is added with heat conduction materials, so that the heat dissipation performance of the flexible copper clad laminate is improved.

Description

Epoxy resin composition and flexible copper clad laminate prepared from same
Technical Field
The invention belongs to the field of preparation of flexible copper clad laminates, and particularly relates to an epoxy resin composition and a flexible copper clad laminate prepared from the same.
Background
With the increasing integration density of microelectronic devices, the heat dissipation requirement of microelectronic devices is also increasing, and in addition, due to the requirement for environmental protection, the halogen-containing and phosphorus-containing products may generate phosphorus-containing waste or halogen-containing harmful gas, which is harmful to the environment. In the process of preparing the flexible copper clad laminate, in order to realize the flame retardant function, an epoxy resin functional layer needs to be added, most functional layers are easy to generate halogen-containing phosphorus-containing harmful gas at present, and the heat conduction performance is poor, so that the development of the environment-friendly flexible copper clad laminate material with high heat conduction performance and no halogen and phosphorus has important significance.
Disclosure of Invention
In order to solve the technical defects that in the prior art, an epoxy resin material for a copper-clad plate easily generates halogen-containing phosphorus-containing harmful gas and has poor heat conductivity, the invention provides an epoxy resin composition for a flexible copper-clad plate and the flexible copper-clad plate prepared from the epoxy resin composition.
The specific technical scheme is as follows:
the epoxy resin composition is characterized in that the epoxy resin comprises the following components in parts by weight:
bisphenol a epoxy resin: 5-50 parts of dicyclopentadiene epoxy resin: 5-30 parts of synthetic rubber: 5-35 parts of nitrogen flame retardant: 1-30 parts of curing agent: 1-10 parts of a curing catalyst: 0.01-2.0 parts of antioxidant: 0.01 to 2.0 parts; an ion scavenger: 0.01-2.0 parts of heat conduction material: 1-80 parts;
the epoxy resin also comprises a solvent, and the mass percentage of the solid substance dissolved in the solvent is 20-80%.
Further, the epoxy resin comprises the following components in parts by weight:
bisphenol a epoxy resin: 6-30 parts of dicyclopentadiene epoxy resin: 5-15 parts of synthetic rubber: 8-30 parts of nitrogen flame retardant: 8-28 parts of curing agent: 2-6 parts of a curing catalyst: 0.01-0.08 parts of antioxidant: 0.08-1.5 parts of ion scavenger: 0.1-1.0 part of heat conduction material: 10 to 80 portions.
Further, the epoxy resin comprises the following components in parts by weight:
bisphenol a epoxy resin: 8-20 parts of dicyclopentadiene epoxy resin: 5-12 parts of synthetic rubber: 9-25 parts of nitrogen flame retardant: 8-25 parts of curing agent: 3-5 parts of a curing catalyst: 0.02-0.06 parts of antioxidant: 0.1-0.2 parts of ion capturing agent: 0.1-0.5 parts of heat conducting material: 10 to 70 portions.
Further, the heat conducting material comprises one or two of boron nitride or spherical alumina.
Further, the weight portion of the boron nitride is 1 to 40 portions, and the weight portion of the spherical alumina is 10 to 35 portions.
Further, the curing agent is 4, 4-diaminobenzene sulfone, the nitrogen flame retardant is melamine cyanurate, and the antioxidant is pentaerythritol tetrakis [ methyl- β - (3, 5-di-tert-butyl-4 hydroxyphenyl) propionate.
Further, the solvent is methyl ethyl ketone.
The flexible copper clad laminate is characterized by comprising a polyimide film, the epoxy resin composition layer coated on the polyimide film and a copper foil pressed on the epoxy resin composition layer.
Further, the thickness of the polyimide film is 10-100 μm, the copper foil is a rolled copper foil or an electrolytic copper foil, the thickness is 9-70 μm, the gluing thickness is 10-35 μm, and the dry thickness of the epoxy resin composition coating is 5-45 μm.
Compared with the prior art, the invention has the beneficial effects that: (1) the excellent flexibility of the resin composition is ensured on the premise of effectively reducing the rubber dosage, and the halogen-free phosphorus-free resin composition can be obtained by simply mixing the nitrogen-containing flame retardant; (2) the flexible copper clad laminate prepared by the composition has excellent flexibility, heat resistance and processability, and the flame retardance reaches UL94VTM-0 level; (3) the flexible copper clad laminate prepared by the composite material is added with heat conduction materials, so that the heat dissipation performance of the flexible copper clad laminate is improved.
Detailed Description
The principles and features of this invention are described below in conjunction with embodiments, which are included to explain the invention and not to limit the scope of the invention.
In the embodiment of the invention, two types of bisphenol A epoxy resin are adopted, and the names of the bisphenol A epoxy resin are bisphenol A epoxy resin 901 and bisphenol A epoxy resin 188;
two types of dicyclopentadiene epoxy resin are adopted, and are commercially available DCEP-EL and XD 1000;
the synthetic rubber is a commercially available product with the name of 1072G, a curing agent is 4, 4-diaminobenzene sulfone (4,4-DDS), a curing catalyst is imidazole, a heat conduction material is boron nitride and spherical alumina, a nitrogen flame retardant is commercially available Melamine Cyanurate (MCA), an antioxidant is commercially available tetrakis [ methyl- β - (3,5 di-tert-butyl-4 hydroxyphenyl) propionate pentaerythritol ester) (EVERNOX-10), a solvent is Methyl Ethyl Ketone (MEK), and an ion scavenger is commercially available IXE-100.
Example one
The raw materials are mixed according to the following weight portions
90111 parts of bisphenol A epoxy resin, 1885 parts of bisphenol A epoxy resin, 6.5 parts of DCEP-EL, 10004 parts of XD, 1072G 23 parts, 4.5 parts of 4,4-DDS, 0.05 part of imidazole, 10.65 parts of boron nitride, 14 parts of spherical alumina, 21 parts of MCA, 0.1 part of EVERNOX-10, and IXE-10: 0.2 part of the raw materials are uniformly mixed and added with a proper amount of MEK solvent to obtain the composition with the solid mass percent of 45 percent.
Example two
The raw materials are mixed according to the following weight portions
9019 parts of bisphenol A epoxy resin, 1884 parts of bisphenol A epoxy resin, 4 parts of DCEP-EL, 10005.5 parts of XD, 1072G 23 parts, 4,4-DDS 4 parts, 0.045 part of imidazole, 30.59 parts of spherical alumina, 19.5 parts of MCA, 0.115 part of EVERNOX-10, and IXE-10: 0.25 part of the raw materials are uniformly mixed and added with a proper amount of MEK solvent to obtain the composition with the solid mass percent of 45 percent.
EXAMPLE III
The raw materials are mixed according to the following weight portions
9018 parts of bisphenol A epoxy resin, 1884 parts of bisphenol A epoxy resin, 5 parts of DCEP-EL, 10003 parts of XD, 19 parts of 1072G, 3.5 parts of 4,4-DDS, 0.04 part of imidazole, 8.4 parts of boron nitride, 19.75 parts of spherical alumina, 19 parts of MCA, 0.11 part of EVERNOX-10, and IXE-10: 0.2 part of the raw materials are uniformly mixed and added with a proper amount of MEK solvent to obtain the composition with the solid mass percent of 45 percent.
Example four
The raw materials are mixed according to the following weight portions
9017.5 parts of bisphenol A epoxy resin, 1883 parts of bisphenol A epoxy resin, 4.5 parts of DCEP-EL, 10003 parts of XD, 1072G 14 parts, 4,4-DDS 3.2 parts, 0.04 part of imidazole, 32 parts of boron nitride, 17.49 parts of spherical alumina, 15 parts of MCA, 0.1 part of EVERNOX-10, and IXE-10: 0.2 part of the raw materials are uniformly mixed and added with a proper amount of MEK solvent to obtain the composition with the solid mass percent of 45 percent.
EXAMPLE five
The raw materials are mixed according to the following weight portions
9015.5 parts of bisphenol A epoxy resin, 1883 parts of bisphenol A epoxy resin, 3 parts of DCEP-EL, 10002 parts of XD, 9.5 parts of 1072G, 2.5 parts of 4,4-DDS, 0.03 part of imidazole, 39.5 parts of boron nitride, 25.72 parts of spherical alumina, 9 parts of MCA, 0.1 part of EVERNOX-10, and IXE-10: 0.15 portion of the raw materials are evenly mixed and added with a proper amount of MEK solvent to obtain the composition with the solid content of 45 percent.
EXAMPLE six
The raw materials are mixed according to the following weight portions
9012.5 parts of bisphenol A epoxy resin, 1882.5 parts of bisphenol A epoxy resin, 2.5 parts of DCEP-EL, 0.5 part of spherical alumina, 1 part of MCA, 0.01 part of EVERNOX-10, 0.01 part of IXE-10: 0.01 part of the raw materials are uniformly mixed and added with a proper amount of MEK solvent to obtain a composition with the solid mass percent of 45%.
EXAMPLE seven
The raw materials are mixed according to the following weight portions
90125 parts of bisphenol A epoxy resin, 18825 parts of bisphenol A epoxy resin, 15 parts of DCEP-EL, 100015 parts of XD, 35 parts of 1072G, 10 parts of 4,4-DDS, 40 parts of imidazole 2, 40 parts of boron nitride, 40 parts of spherical alumina, 30 parts of MCA, 2 parts of EVERNOX-10, 2 parts of IXE-10: 2 parts of the raw materials are uniformly mixed and added with a proper amount of MEK solvent to obtain the composition with the solid mass percent of 45%.
Example eight
The raw materials are mixed according to the following weight portions
90111 parts of bisphenol A epoxy resin, 1885 parts of bisphenol A epoxy resin, 6.5 parts of DCEP-EL, 10004 parts of XD, 1072G 23 parts, 4.5 parts of 4,4-DDS, 0.05 part of imidazole, 24.65 parts of spherical alumina, 21 parts of MCA, 0.1 part of EVERNOX-10, IXE-10: 0.2 part of the raw materials are uniformly mixed and added with a proper amount of MEK solvent to obtain the composition with the solid mass percent of 45 percent.
Example nine
The raw materials are mixed according to the following weight portions
90111 parts of bisphenol A epoxy resin, 1885 parts of bisphenol A epoxy resin, 6.5 parts of DCEP-EL, 10004 parts of XD, 1072G 23 parts, 4.5 parts of 4,4-DDS, 0.05 part of imidazole, 24.65 parts of boron nitride, 21 parts of MCA, 0.1 part of EVERNOX-10, IXE-10: 0.2 part of the raw materials are uniformly mixed and added with a proper amount of MEK solvent to obtain the composition with the solid mass percent of 45 percent.
Example ten
The raw materials are mixed according to the following weight portions
90111 parts of bisphenol A epoxy resin, 1885 parts of bisphenol A epoxy resin, 6.5 parts of DCEP-EL, 10004 parts of XD, 1072G 23 parts, 4.5 parts of 4,4-DDS, 0.05 part of imidazole, 0.5 part of boron nitride, 9 parts of spherical alumina, 21 parts of MCA, 0.1 part of EVERNOX-10, and IXE-10: 0.2 portion of the raw materials are evenly mixed and added with a proper amount of MEK solvent to obtain the composition with the solid content of 45 percent.
The weight portion of the boron nitride is 1 to 40 portions, and the weight portion of the spherical alumina is 10 to 35 portions.
EXAMPLE eleven
The raw materials are mixed according to the following weight portions
90111 parts of bisphenol A epoxy resin, 1885 parts of bisphenol A epoxy resin, 6.5 parts of DCEP-EL, 10004 parts of XD, 1072G 23 parts, 4.5 parts of 4,4-DDS, 0.05 part of imidazole, 42 parts of boron nitride, 36 parts of spherical alumina, 21 parts of MCA, 0.1 part of EVERNOX-10, and IXE-10: 0.2 part of the raw materials are uniformly mixed and added with a proper amount of MEK solvent to obtain the composition with the solid mass percent of 45 percent.
Example twelve
Coating the composition of the embodiment on a polyimide insulating film with the thickness of 12.5 mu m by a glue coater, wherein the glue thickness is 13 mu m, heating the polyimide insulating film in an oven at 160 ℃ for 3 minutes to form a partially cured composition layer on the polyimide thin insulating film, then pressing the partially cured composition layer with a 18 mu m pressed copper foil through a roller, and finally putting the polyimide thin insulating film in the oven for curing at 120-170 ℃ to obtain the flexible copper-clad plate.
EXAMPLE thirteen
The two compositions of the examples are prepared into the flexible copper clad laminate according to the preparation method of the example twelve.
Example fourteen
The three compositions of the embodiment are prepared into the flexible copper clad laminate according to the preparation method of the embodiment twelve.
Example fifteen
The four compositions of the examples are prepared into the flexible copper clad laminate according to the preparation method of the example twelve.
Example sixteen
The five compositions of the example are prepared into the flexible copper clad laminate according to the twelve preparation methods of the example.
Example seventeen
The composition of the sixth embodiment is prepared into the flexible copper clad laminate according to the preparation method of the twelfth embodiment.
EXAMPLE eighteen
The seven composition of the example was prepared into a flexible copper clad laminate according to the twelve preparation methods of the example.
Example nineteen
The composition of the eighth embodiment is prepared into the flexible copper clad laminate according to the preparation method of the twelfth embodiment.
Example twenty
The composition of the ninth embodiment is prepared into the flexible copper clad laminate according to the twelfth embodiment.
Example twenty one
The flexible copper clad laminate is prepared by the composition in the embodiment by the preparation method in the embodiment twelve.
Example twenty two
The flexible copper clad laminate is prepared by the composition of the eleventh embodiment according to the preparation method of the twelfth embodiment.
Comparative example 1
The raw materials are mixed according to the following weight portions
90111 parts of bisphenol A epoxy resin, 1885 parts of bisphenol A epoxy resin, 6.5 parts of DCEP-EL, 10004 parts of XD, 1072G 23 parts, 4.5 parts of 4,4-DDS, 0.05 part of imidazole, 21 parts of MCA, 0.1 part of EVERNOX-10, and IXE-10: 0.2 part of the raw materials are uniformly mixed and added with a proper amount of MEK solvent to obtain the composition with the solid mass percent of 45 percent.
Comparative example No. two
The raw materials are mixed according to the following weight portions
90111 parts of bisphenol A epoxy resin, 1885 parts of bisphenol A epoxy resin, 6.5 parts of DCEP-EL, 10004 parts of XD, 1072G 23 parts, 4.5 parts of 4,4-DDS, 0.05 part of imidazole, 0.2 part of boron nitride, 0.5 part of spherical alumina, 21 parts of MCA, 0.1 part of EVERNOX-10, and IXE-10: 0.2 part of the raw materials are uniformly mixed and added with a proper amount of MEK solvent to obtain the composition with the solid mass percent of 45 percent.
Comparative example No. three
And preparing the composition of the comparative example into the flexible copper clad laminate according to the preparation method of the example twelve.
Comparative example No. four
And preparing the comparative example composition into a flexible copper-clad plate according to the preparation method of the twelfth embodiment.
Example twenty two
The copper-clad plates prepared in the twelfth embodiment to the twenty-first embodiment and the third comparative example to the fourth comparative example are subjected to performance detection, and the detection method and the standard are as follows:
(1) peeling force: the peel strength was measured according to IPC-YM-6502.4.9;
(2) the resilience can quantitatively reflect the flexibility of the flexible copper clad laminate, and the smaller the resilience, the softer the flexible copper clad laminate;
(3) flame retardancy: measured according to the UL94 vertical burning method;
(4) resistance to soldering
(5) Thermal conductivity test
The test results are shown in table 1.
TABLE 1 detection result of flexible copper clad laminate performance
Figure BDA0002351982370000071
Figure BDA0002351982370000081
As can be seen from Table 1, the flexible copper clad laminate prepared by using the composition of the invention as a raw material shows excellent flexibility, heat resistance, processability and flame retardance, and is greatly improved in thermal conductivity.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. The epoxy resin composition is characterized in that the epoxy resin for the flexible copper clad laminate comprises the following components in parts by weight:
bisphenol a epoxy resin: 5-50 parts of dicyclopentadiene epoxy resin: 5-30 parts of synthetic rubber: 5-35 parts of nitrogen flame retardant: 1-30 parts of curing agent: 1-10 parts of a curing catalyst: 0.01-2.0 parts of antioxidant: 0.01 to 2.0 parts; an ion scavenger: 0.01-2.0 parts of heat conduction material: 1-80 parts;
the epoxy resin also comprises a solvent, and the mass percentage of the solid substance dissolved in the solvent is 20-80%.
2. The epoxy resin composition as claimed in claim 1, wherein the epoxy resin comprises the following components in parts by weight:
bisphenol a epoxy resin: 6-30 parts of dicyclopentadiene epoxy resin: 5-15 parts of synthetic rubber: 8-30 parts of nitrogen flame retardant: 8-28 parts of curing agent: 2-6 parts of a curing catalyst: 0.01-0.08 parts of antioxidant: 0.08-1.5 parts of ion scavenger: 0.1-1.0 part of heat conduction material: 10 to 80 portions.
3. The epoxy resin composition as claimed in claim 1, wherein the epoxy resin comprises the following components in parts by weight:
bisphenol a epoxy resin: 8-20 parts of dicyclopentadiene epoxy resin: 5-12 parts of synthetic rubber: 9-25 parts of nitrogen flame retardant: 8-25 parts of curing agent: 3-5 parts of a curing catalyst: 0.02-0.06 parts of antioxidant: 0.1-0.2 parts of ion capturing agent: 0.1-0.5 parts of heat conducting material: 10 to 70 portions.
4. The epoxy resin composition as claimed in any one of claims 1 to 3, wherein the thermally conductive material comprises one or more of boron nitride or spherical alumina.
5. The epoxy resin composition as claimed in claim 4, wherein the amount of boron nitride is 1-40 parts by weight, and the amount of spherical alumina is 10-35 parts by weight.
6. The epoxy resin composition as claimed in claim 1, wherein the curing agent is 4, 4-diaminophenylsulfone, the nitrogen-based flame retardant is melamine cyanurate, and the antioxidant is pentaerythritol tetrakis [ methyl- β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
7. The epoxy resin composition as claimed in claim 1, wherein the solvent is methyl ethyl ketone.
8. A flexible copper clad laminate comprising a polyimide film, the epoxy resin composition layer of claim 1 coated on the polyimide film, and a copper foil laminated on the epoxy resin composition layer.
9. The flexible copper clad laminate according to claim 8, wherein the thickness of the polyimide film is 10 μm to 100 μm, the copper foil is a rolled copper foil or an electrolytic copper foil, the thickness is 9 μm to 70 μm, the thickness of the glue is 10 μm to 35 μm, and the dry thickness of the epoxy resin composition layer coating is 5 μm to 45 μm.
CN201911426058.1A 2019-12-31 2019-12-31 Epoxy resin composition and flexible copper clad laminate prepared from same Pending CN111154231A (en)

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TW200906959A (en) * 2007-05-10 2009-02-16 Hitachi Chemical Co Ltd Sealing epoxy resin compostion and eletronic component apparatus using the same
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Application publication date: 20200515