CN110481119B - Halogen-free copper foil-clad fiberglass cloth laminated board - Google Patents

Halogen-free copper foil-clad fiberglass cloth laminated board Download PDF

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Publication number
CN110481119B
CN110481119B CN201910815206.2A CN201910815206A CN110481119B CN 110481119 B CN110481119 B CN 110481119B CN 201910815206 A CN201910815206 A CN 201910815206A CN 110481119 B CN110481119 B CN 110481119B
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epoxy resin
halogen
resin
curing agent
free copper
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CN110481119A (en
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李洪彬
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Chongqing Dekai Industry Co ltd
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Chongqing Dekai Industry Co ltd
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    • 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
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary 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
    • 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
    • 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
    • B32B37/10—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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/08—Interconnection of layers by mechanical means
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/038—Textiles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • 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
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B2037/1269—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives multi-component adhesive
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention belongs to the technical field of adhesives, and particularly relates to a halogen-free copper foil-clad fiberglass cloth laminated board. The halogen-free copper-clad foil and glass fiber cloth laminated board is characterized by comprising glass fiber cloth, an adhesive and copper foil, wherein the adhesive is prepared from raw materials including resin, a curing agent, a catalyst, rubber and a solvent, and the curing agent comprises dicyandiamide, a phosphorus-containing flame-retardant curing agent and 4, 4-diaminodiphenyl sulfone serving as a curing agent. The laminated board of the invention has excellent heat resistance.

Description

Halogen-free copper foil-clad fiberglass cloth laminated board
Technical Field
The invention relates to the field of adhesives, in particular to a halogen-free copper foil-clad fiberglass cloth laminated board.
Background
Copper clad laminates (copper clad laminates for short) are basic materials in the electronic industry, are mainly used for manufacturing printed circuit boards, and are widely used for electronic products such as radios, video recorders, televisions, computers, communication equipment and the like. The copper clad laminate is prepared by using paper or glass cloth as a base material, soaking the paper or glass cloth in phenolic resin or epoxy resin, drying the paper or glass cloth to prepare a soaking glue material, then adding copper foil on one side or two sides of the soaking glue material, and heating and pressurizing the mixture.
However, the existing copper clad laminate has poor heat resistance, and is not enough to meet the use requirements of copper clad laminates in the fields of automobiles and the like.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a halogen-free copper clad laminate having excellent heat resistance and capable of satisfying the use requirements of copper clad laminates in the fields of automobiles and the like.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the halogen-free copper-clad foil-glass fiber cloth laminated board comprises glass fiber cloth, an adhesive and copper foil, wherein the adhesive is prepared from raw materials including resin, a curing agent, a catalyst, rubber and a solvent, and the curing agent comprises dicyandiamide, a phosphorus-containing flame-retardant curing agent and 4, 4-diaminodiphenyl sulfone serving as a curing agent.
Further, the mass ratio of dicyandiamide to the phosphorus-containing flame-retardant curing agent to the curing agent 4, 4-diaminodiphenyl sulfone is 0.1-0.3:13-15: 0.5-3.
Further, the resin includes benzoxazine, multifunctional phenolic resin, toughening resin and epoxy resin.
Further, the epoxy resin includes a tetrafunctional epoxy resin, an epoxy resin MRX1026, a phosphorous epoxy resin, and a toughening type epoxy resin.
Further, the mass ratio of the tetrafunctional epoxy resin, the epoxy resin MRX1026, the phosphorus-containing epoxy resin and the toughening type epoxy resin is 4-11:1-5:4-15: 2-5.
Further, the mass ratio of the benzoxazine, the multifunctional phenolic resin, the toughening resin and the epoxy resin is 20-30:2-9:10-20: 11-36.
Further, the catalyst includes 2-phenylimidazole.
Further, the solvent comprises propylene glycol methyl ether and butanone.
Further, the composite material also comprises a filler and a coupling agent.
Further, the filler includes aluminum hydroxide, silica, and microfibrillated cellulose MFC 1007.
Further, the mass ratio of the aluminum hydroxide, the silicon dioxide and the microfibrillated cellulose MFC1007 is 5-15:9-15: 4-10.
Further, the adhesive is prepared from the raw materials of 43-85 parts of resin, 13.5-15.3 parts of curing agent, 0.05-0.1 part of catalyst, 0.1-0.3 part of rubber, 13-27 parts of solvent, 0.1-0.5 part of coupling agent and 18-40 parts of filler according to parts by mass.
The invention also aims to protect the preparation method of the halogen-free copper clad laminate, which comprises the following steps:
A. preparation of Adhesives
A1. And (3) filler dispersion: adding benzoxazine resin, toughened epoxy resin, epoxy resin MRX1026, tetrafunctional epoxy resin, toughened resin, phosphorus-containing flame retardant curing agent and rubber into a high-speed stirrer barrel, adding 20-35% of propylene glycol methyl ether serving as a solvent, aluminum hydroxide serving as a filler, silicon dioxide serving as a filler and microfibrillated cellulose serving as a functional filler, and stirring for 4 hours at the rotating speed of more than 1000r/min after the addition is finished; adding the phosphorus-containing epoxy resin EP330A7 and the phosphorus-containing epoxy resin EP280A7 into a high-speed stirrer, and continuously stirring and uniformly dispersing;
A2. a solvent system: dissolving a dicyandiamide curing agent, phenolic resin and a catalyst in a mixed solvent consisting of the residual solvent propylene glycol methyl ether and butanone to form a solvent system;
A3. mixing: adding the mixture solvent system obtained in the step (2) into the filler dispersion liquid, and stirring for 4 hours at the rotating speed of more than 1000r/min to obtain the adhesive;
B. immersing glass fiber cloth into the adhesive, drying to obtain semi-solid sheets, and then stacking the semi-solid sheets;
C. and covering copper foil on the stacked semi-solid sheets, placing the semi-solid sheets in a steel plate mould, and immersing and pressing to obtain the laminated board.
The beneficial technical effects of the invention are as follows:
the laminated board of the invention has excellent heat resistance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below.
Example 1
The halogen-free copper-clad foil and glass fiber cloth laminated board consists of glass fiber cloth, an adhesive and copper foil, wherein the adhesive is prepared from the following raw materials in parts by mass: 10 parts of propylene glycol methyl ether solvent (PM), 15 parts of phosphorus-containing flame-retardant curing agent (MPH1005), 20 parts of benzoxazine resin, 3 parts of multifunctional phenolic resin (710HK65), 3 parts of curing agent 4, 4-diaminodiphenyl sulfone (trade name MHX1007), 5 parts of filler aluminum hydroxide, 10 parts of filler silica, 6 parts of functional filler microfibrillated cellulose (MFC1007), 0.3 part of silane coupling agent, 10-20 parts of toughening type resin (MRX1025), 6 parts of tetrafunctional epoxy resin (431A70), epoxy resin (MRX1026), 7 parts of phosphorus-containing epoxy resin (EP330A7), 2 parts of phosphorus-containing epoxy resin (EP280A7), 3 parts of toughening type epoxy resin (MRM1021), 0.1 part of rubber (MRM102), 0.08 part of catalyst 2-phenylimidazole and 4 parts of solvent butanone (MEK).
The laminate was prepared according to the following steps:
A. preparation of Adhesives
A1. And (3) filler dispersion: adding benzoxazine resin, toughened epoxy resin, epoxy resin MRX1026, tetrafunctional epoxy resin, toughened resin, phosphorus-containing flame retardant curing agent and rubber into a high-speed stirrer barrel, adding 20% of propylene glycol monomethyl ether, aluminum hydroxide serving as a filler, silicon dioxide serving as a filler and functional microfibrillated cellulose serving as a filler, and stirring for 4 hours at the rotating speed of more than 1000 r/min; adding the phosphorus-containing epoxy resin EP330A7 and the phosphorus-containing epoxy resin EP280A7 into a high-speed stirrer, and continuously stirring and uniformly dispersing;
A2. a solvent system: dissolving a dicyandiamide curing agent, phenolic resin and a catalyst in a mixed solvent consisting of the residual solvent propylene glycol methyl ether and butanone to form a solvent system;
A3. mixing: adding the mixture solvent system obtained in the step (2) into the filler dispersion liquid, and stirring for 4 hours at the rotating speed of more than 1000r/min to obtain the adhesive;
B. immersing glass fiber cloth into the adhesive, drying to obtain semi-solid sheets, and then stacking the semi-solid sheets;
C. and covering copper foil on the stacked semi-solid sheets, placing the semi-solid sheets in a steel plate mould, and immersing and pressing to obtain the laminated board.
Example 2
The halogen-free copper-clad foil and glass fiber cloth laminated board consists of glass fiber cloth, an adhesive and copper foil, wherein the adhesive is prepared from the following raw materials in parts by mass: 22 parts of propylene glycol methyl ether solvent (PM), 14 parts of phosphorus-containing flame-retardant curing agent (MPH1005), 25 parts of benzoxazine resin, 6 parts of multifunctional phenolic resin (710HK65), 1 part of curing agent 4, 4-diaminodiphenyl sulfone (trade name MHX1007), 5-15 parts of filler aluminum hydroxide, 10 parts of filler silica, 5 parts of functional filler microfibrillated cellulose (MFC1007), 0.3 part of silane coupling agent, 16 parts of toughening type resin (MRX1025), 8 parts of tetrafunctional epoxy resin (431A70), epoxy resin (MRX1026), 6 parts of phosphorus-containing epoxy resin (EP330A7), 2 parts of phosphorus-containing epoxy resin (EP280A7), 3 parts of toughening type epoxy resin (MRM1021), 0.2 part of rubber (MRM1020), 0.4 part of catalyst 2-phenylimidazole and 5 parts of solvent butanone (MEK).
The laminate was prepared according to the following steps:
A. preparation of Adhesives
A1. And (3) filler dispersion: adding benzoxazine resin, toughened epoxy resin, epoxy resin MRX1026, tetrafunctional epoxy resin, toughened resin, phosphorus-containing flame retardant curing agent and rubber into a high-speed stirrer barrel, adding a solvent propylene glycol methyl ether accounting for 33 percent of the total amount, filler aluminum hydroxide, filler silicon dioxide and functional filler microfibrillated cellulose, and stirring for 4 hours at the rotating speed of more than 1000r/min after the addition is finished; adding the phosphorus-containing epoxy resin EP330A7 and the phosphorus-containing epoxy resin EP280A7 into a high-speed stirrer, and continuously stirring and uniformly dispersing;
A2. a solvent system: dissolving a dicyandiamide curing agent, phenolic resin and a catalyst in a mixed solvent consisting of the residual solvent propylene glycol methyl ether and butanone to form a solvent system;
A3. mixing: adding the mixture solvent system obtained in the step (2) into the filler dispersion liquid, and stirring for 4 hours at the rotating speed of more than 1000r/min (communicated with the inventor) to obtain the adhesive;
B. immersing glass fiber cloth into the adhesive, drying to obtain semi-solid sheets, and then stacking the semi-solid sheets;
C. and covering copper foil on the stacked semi-solid sheets, placing the semi-solid sheets in a steel plate mould, and immersing and pressing to obtain the laminated board.
Example 3
The halogen-free copper-clad foil and glass fiber cloth laminated board consists of glass fiber cloth, an adhesive and copper foil, wherein the adhesive is prepared from the following raw materials in parts by mass: 20 parts of propylene glycol methyl ether solvent (PM), 15 parts of phosphorus-containing flame-retardant curing agent (MPH1005), 28 parts of benzoxazine resin, 8 parts of multifunctional phenolic resin (710HK65), 2 parts of curing agent 4, 4-diaminodiphenyl sulfone (trade name MHX1007), 5-15 parts of filler aluminum hydroxide, 12 parts of filler silica, 9 parts of functional filler microfibrillated cellulose (MFC1007), 0.4 parts of silane coupling agent, 16 parts of toughening type resin (MRX1025), 4-11 parts of tetrafunctional epoxy resin (431A70), epoxy resin (MRX1026), 8 parts of phosphorus-containing epoxy resin (EP330A7), 3 parts of phosphorus-containing epoxy resin (EP280A7), 5 parts of toughening type epoxy resin (MRM1021), rubber (MRM1020), 0.05 part of catalyst 2-phenylimidazole and 4 parts of solvent butanone (MEK).
The laminate was prepared according to the following steps:
A. preparation of Adhesives
A1. And (3) filler dispersion: firstly, adding benzoxazine resin, toughened epoxy resin, epoxy resin MRX1026, tetrafunctional epoxy resin, toughened resin, phosphorus-containing flame retardant curing agent and rubber into a high-speed stirrer barrel, then adding 25% of solvent propylene glycol methyl ether, filler aluminum hydroxide, filler silicon dioxide and functional filler microfibrillated cellulose, and stirring for 4 hours after the addition is finished, wherein the rotating speed is more than 1000 r/min; adding the phosphorus-containing epoxy resin EP330A7 and the phosphorus-containing epoxy resin EP280A7 into a high-speed stirrer, and continuously stirring and uniformly dispersing;
A2. a solvent system: dissolving a dicyandiamide curing agent, phenolic resin and a catalyst in a mixed solvent consisting of the residual solvent propylene glycol methyl ether and butanone to form a solvent system;
A3. mixing: adding the mixture solvent system obtained in the step (2) into the filler dispersion liquid, and stirring for 4 hours at the rotating speed of more than 1000r/min (communicated with the inventor) to obtain the adhesive;
B. immersing glass fiber cloth into the adhesive, drying to obtain semi-solid sheets, and then stacking the semi-solid sheets;
C. and covering copper foil on the stacked semi-solid sheets, placing the semi-solid sheets in a steel plate mould, and immersing and pressing to obtain the laminated board.
Performance detection
The glass transition temperature Tg, the thermal decomposition temperature Td, the peel strength, the thermal stress and the bending strength of the laminates obtained in examples 1 to 3 were measured, and the results are shown in Table 1.
Table 1 results of performance testing
Figure BDA0002186166040000061
Finally, the above embodiments are merely illustrative of the technical solutions of the present invention and not restrictive, and it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solutions of the present invention and are intended to be covered by the claims of the present invention.

Claims (10)

1. The halogen-free copper-clad foil-glass fiber cloth laminated board is characterized by comprising glass fiber cloth, an adhesive and a copper foil, wherein the adhesive is prepared from raw materials including resin, a curing agent, a catalyst, rubber and a solvent, the curing agent comprises dicyandiamide, a phosphorus-containing flame-retardant curing agent and a curing agent 4, 4-diaminodiphenylsulfone, the resin comprises benzoxazine, multifunctional phenolic resin, toughening type resin and epoxy resin, the epoxy resin comprises tetrafunctional epoxy resin, epoxy resin MRX1026, phosphorus-containing epoxy resin and toughening type epoxy resin, and the mass ratio of the tetrafunctional epoxy resin, the epoxy resin MRX1026, the phosphorus-containing epoxy resin and the toughening type epoxy resin is 4-11:1-5:4-15: 2-5.
2. The halogen-free copper clad laminate according to claim 1 wherein the mass ratio of dicyandiamide to phosphorus-containing flame retardant curing agent to 4, 4-diaminodiphenyl sulfone curing agent is 0.1-0.3:13-15: 0.5-3.
3. The halogen-free copper clad laminate according to claim 1 or 2, wherein the mass ratio of the benzoxazine, the multifunctional phenolic resin, the toughening resin and the epoxy resin is 20-30:2-9:10-20: 11-36.
4. The halogen-free copper clad fiberglass cloth laminate of claim 1, wherein the catalyst comprises 2-phenylimidazole.
5. The halogen-free copper clad fiberglass cloth laminate of claim 1, 2 or 4, wherein the solvent comprises propylene glycol methyl ether and methyl ethyl ketone.
6. The halogen-free copper clad fiberglass cloth laminate of claim 3, wherein the solvent comprises propylene glycol methyl ether and methyl ethyl ketone.
7. The halogen-free copper clad fiberglass cloth laminate of claim 1, 2, 4 or 6, further comprising a filler and a coupling agent.
8. The halogen-free copper clad fiberglass cloth laminate of claim 3, further comprising a filler and a coupling agent.
9. The halogen-free copper clad fiberglass cloth laminate of claim 5, further comprising a filler and a coupling agent.
10. The method for preparing the halogen-free copper clad fiberglass cloth laminate according to any one of claims 1 to 9, comprising the steps of: A. adhesive preparation A1. Filler dispersion: adding benzoxazine resin, toughened epoxy resin, epoxy resin MRX1026, tetrafunctional epoxy resin, toughened resin, phosphorus-containing flame retardant curing agent and rubber into a high-speed stirrer barrel, adding 20-35% of propylene glycol methyl ether serving as a solvent, aluminum hydroxide serving as a filler, silicon dioxide serving as a filler and microfibrillated cellulose serving as a functional filler, and stirring for 4 hours at the rotating speed of more than 1000r/min after the addition is finished; adding the phosphorus-containing epoxy resin EP330A7 and the phosphorus-containing epoxy resin EP280A7 into a high-speed stirrer, and continuously stirring and uniformly dispersing; A2. a solvent system: dissolving a dicyandiamide curing agent, phenolic resin and a catalyst in a mixed solvent consisting of the residual solvent propylene glycol methyl ether and butanone to form a solvent system; A3. mixing: adding the mixture solvent system obtained in the step (2) into the filler dispersion liquid, and stirring for 4 hours at the rotating speed of more than 1000r/min to obtain the adhesive; B. immersing glass fiber cloth into the adhesive, drying to obtain semi-solid sheets, and then stacking the semi-solid sheets; C. and covering copper foil on the stacked semi-solid sheets, placing the semi-solid sheets in a steel plate mould, and immersing and pressing to obtain the laminated board.
CN201910815206.2A 2019-08-30 2019-08-30 Halogen-free copper foil-clad fiberglass cloth laminated board Active CN110481119B (en)

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