CN115339195B - Copper-clad plate with low thermal expansion coefficient suitable for PCB lead-free process and preparation method thereof - Google Patents

Copper-clad plate with low thermal expansion coefficient suitable for PCB lead-free process and preparation method thereof Download PDF

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CN115339195B
CN115339195B CN202210883560.0A CN202210883560A CN115339195B CN 115339195 B CN115339195 B CN 115339195B CN 202210883560 A CN202210883560 A CN 202210883560A CN 115339195 B CN115339195 B CN 115339195B
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copper
epoxy resin
prepreg
inches
clad plate
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CN115339195A (en
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况小军
叶志
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Jiangxi Hongruixing Technology Co ltd
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Jiangxi Hongruixing Technology 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
    • 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
    • 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
    • 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
    • B32B38/0036—Heat treatment
    • 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
    • B32B38/08—Impregnating
    • 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
    • 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
    • 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
    • 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
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/02—Coating on the layer surface on 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
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—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
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • 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

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Fluid Mechanics (AREA)
  • Thermal Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention discloses a copper-clad plate with a low thermal expansion coefficient suitable for a lead-free PCB (printed circuit board) process and a preparation method thereof. The copper-clad plate prepared by the method has the advantages of common glass transition temperature (Tg is greater than or equal to 135 ℃), excellent heat resistance and low thermal expansion coefficient, and can be suitable for manufacturing the lead-free printed circuit board in the PCB industry.

Description

Copper-clad plate with low thermal expansion coefficient suitable for PCB lead-free process and preparation method thereof
Technical Field
The invention relates to the technical field of copper-clad plate preparation, in particular to a copper-clad plate with low thermal expansion coefficient suitable for a lead-free PCB (printed circuit board) process and a preparation method thereof.
Background
With the high density and high performance of PCBs, HDI/BUM boards, embedded component multilayer boards, high multilayer boards, and the like have been rapidly developed, and the number of layers, thickness, and area of PCBs have been increased, and in high temperature soldering, particularly lead-free soldering, it is necessary to withstand higher soldering temperatures or longer soldering times in order to ensure soldering reliability, and thus, higher requirements are placed on substrate materials thereof, and such boards should have higher glass transition temperatures and heat resistance as compared with conventional materials.
The formal implementation of two instructions in the european union (instructions for restricting the use of harmful substances in electronic and electric products and instructions for scrapping electronic and electric products) began on 1, 7 in 2006, marks the global electronic industry as coming into the lead-free welding era. Because the welding temperature is high, the thermal reliability of the copper-clad plate is correspondingly improved, the traditional lead-tin solder can not be used any more, and the welding temperature required by replacing solders such as tin, silver, copper and the like is greatly improved. The conventional FR-4 copper clad laminate has a glass transition temperature of 130-140 ℃ and a thermal decomposition temperature of 300-310 ℃ because of low heat resistance, and is widely used in general electronic products, but cannot be used in the fields of high density interconnection and integrated circuits, and the electronic products are rapidly developed, and along with the development of the light weight, multi-layered and semiconductor mounting technology of printed circuits, the substrate is required to have good heat resistance and PCB processability so as to improve the reliability of interconnection and mounting.
At present, market competition is more and more severe, tg of lead-free products developed in the industry is mostly 150 ℃ or above, the variety of copper-clad plate materials is more and more mature, and based on cost consideration, the development of common Tg copper-clad plates and materials with low thermal expansion coefficient and good heat resistance also become a trend.
Disclosure of Invention
In view of the above problems, the present invention is directed to providing a copper-clad plate with low thermal expansion coefficient suitable for a lead-free process of a PCB and a method for preparing the same. The copper-clad plate material prepared by the method has the advantages of low thermal expansion coefficient, good heat resistance and lower material cost.
In order to achieve the purpose of the invention, the technical scheme of the invention is as follows:
the copper-clad plate with low thermal expansion coefficient suitable for PCB lead-free process is prepared from adhesive, glass fiber cloth and copper foil, wherein the adhesive consists of solid matters and organic solvent, the weight percentage of the solid matters is 50-75%, the organic solvent is the rest,
the solid comprises the following components in percentage by weight:
in a preferred embodiment of the present invention, the base epoxy resin physical properties require an epoxy equivalent EEW (g/eq) in the range of 160-210;
the range of hydrolyzable chlorine was 300MAX.
In a preferred embodiment of the present invention, the base epoxy resin is preferably BE188 resin of Taiwan vinca chemical company of China, but is not limited thereto.
In a preferred embodiment of the present invention, the physical properties of the low bromine epoxy resin require an epoxy equivalent weight EEW (g/eq) in the range of 380-450;
the range of hydrolyzable chlorine is 300MAX;
bromine content (wt%) is 17-24.
In a preferred embodiment of the present invention, the low bromine epoxy resin is preferably GEBR454A80 epoxy resin manufactured by Hongchang electronics, guangzhou, but is not limited thereto.
In a preferred embodiment of the invention, the toughening agent is a core shell rubber type toughening agent.
In a preferred embodiment of the invention, the phenolic resin is a phenol-formaldehyde crosslinked phenolic resin, the phenol being phenol, xylenol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, isobutylphenol, t-butylphenol or bisphenol A phenolic resin crosslinked with formaldehyde, or a mixture of phenol phenolic resins and bisphenol A phenolic resins.
In a preferred embodiment of the present invention, the phenolic resin is preferably KPH-2003 resin of Korean Kelong chemical industry.
In a preferred embodiment of the present invention, the curing accelerator is any one or more of 2-ethyl-4-methylimidazole, 2-methylimidazole or 1-benzyl-2-methylimidazole. 2-methylimidazole is preferred.
In a preferred embodiment of the present invention, the inorganic filler is any one or more of talc, quartz powder, ceramic powder, aluminum hydroxide or metal oxide particles,
the metal oxide particles are any one or more of silicon dioxide, clay and boron nitride.
Any one or more of silica, aluminum hydroxide or talc is preferred.
The resin composition of the invention is added with proper filler to reduce the expansion coefficient of the resin composition for manufacturing the copper-clad plate material, and the inorganic filler can improve the chemical property and the electrical property of the cured resin, such as reducing the thermal expansion Coefficient (CTE), increasing the modulus, accelerating the heat transmission, assisting the flame retardance and the like.
In a preferred embodiment of the present invention, the organic solvent is one or a mixture of two or more of acetone, methyl ethyl ketone, methyl isobutyl ketone, or propylene glycol methyl ether.
A method for preparing a copper-clad plate with a low thermal expansion coefficient suitable for a lead-free PCB (printed circuit board) process, comprising the following steps:
the preparation method of the adhesive comprises the following steps:
1) Adding part of organic solvent, phenolic resin curing agent and toughening agent into the stirring tank according to the formula amount, starting the stirrer, and continuously stirring for 2-2.5 hours at the rotation speed of 800-1000 rpm to ensure complete dissolution of the solid in the tank, and controlling the temperature of the tank at 20-45 ℃;
then adding inorganic filler, and continuously stirring for 90-120 minutes after the addition is finished;
2) Sequentially adding basic epoxy resin and low-bromine epoxy resin into a stirring tank according to the formula amount, stirring at a rotation speed of 1000-1400 rpm in the feeding process, starting high-efficiency shearing and emulsifying for 1-3 hours after the adding is finished, and simultaneously circulating cooling water to keep the temperature of the tank at 20-45 ℃;
3) Weighing epoxy resin curing accelerator according to the formula amount, adding the epoxy resin curing accelerator into the residual organic solvent, adding the solution into a stirring tank after complete dissolution, and continuously keeping 1000-1500 rpm for stirring for 4-12 hours to obtain the adhesive;
preparing a prepreg:
1) The adhesive is circulated to a sizing machine, and is uniformly coated on the glass fiber cloth after presoaking and primary dipping,
2) Baking the glass fiber cloth coated with the adhesive by a baking box at 110-250 ℃ to volatilize the solvent, and primarily reacting and solidifying the adhesive to prepare a prepreg; wherein, the line speed of sizing is controlled to be 8-25m/min,
controlling physical parameters of the prepreg: the gelation time is 80-175 seconds, the mass percentage of the resin component in the prepreg is 35-78%, the resin fluidity is 15-45%, and the volatile is less than 0.75%;
typesetting and pressing:
1) Cutting the prepreg into a group of 1-18 sheets with the same size, overlapping the prepreg with copper foil, and pressing;
2) The pressing parameters were controlled as follows:
a. pressure: 100-550psi;
b. hot plate temperature: 80-200 ℃;
c. vacuum degree: 0.030-0.080Mpa;
d. pressing time: 150-180 minutes;
e. curing time: and maintaining at 190 deg.c for 40-100 min.
In a preferred embodiment of the present invention, the glass fiber cloth in the prepreg preparation step is grade E, with specifications of 101, 104, 106, 1078, 1080, 1086, 2113, 2313, 2116, 1506 or 7628.
In a preferred embodiment of the present invention, the copper foil is 1/3oz, hoz, 1oz, 2oz, 3oz, 4oz or 5oz.
The copper clad laminate prepared by the invention has the specification of 36X 48 inches, 36.5X 48.5 inches, 37X 49 inches, 40X 48 inches, 40.5X 48.5 inches, 41X 49 inches, 42X 48 inches, 42.5X 48.5 inches or 43X 49 inches, and the thickness of 0.05-3.2mm.
The invention has the beneficial effects that:
the copper-clad plate prepared by the invention has the advantages of common glass transition temperature (Tg is greater than or equal to 135 ℃), excellent heat resistance and low thermal expansion coefficient (CTE (50-260 ℃) is less than or equal to 3.2%), and can be suitable for manufacturing lead-free printed circuit boards in the PCB industry.
Detailed Description
The invention is further illustrated by the following examples and comparative examples.
The characteristics of the copper clad laminate of examples 1 to 4 and comparative example were measured by the following method (refer to IPC-TM-650).
(1) Glass transition temperature (Tg)
Glass transition temperature
The detection method comprises the following steps: differential Scanning Calorimetry (DSC) is used to refer to the temperature (DEG C) at which the sheet material changes from a glassy state to a highly elastic (rubbery) state under heating.
(2) Time of thermal stratification (T-288)
T-288 thermal delamination time refers to the time that the sheet material has been delaminated by heat at a set temperature of 288℃, and is continued.
The detection method comprises the following steps: thermo-mechanical analysis (TMA) was used.
(3) Peel strength
Tested according to the IPC-TM-650-2.4.8C method.
(4) Solder heat resistance
Solder heat resistance refers to the duration of time during which the board is immersed in molten solder at 288 ℃ without delamination and foaming.
The detection method comprises the following steps: cutting the etched substrate into 5.0cm by 5.0cm, polishing the edges with 120 mesh and 800 mesh sand paper, steaming with an autoclave for a certain time, placing into a 288 ℃ tin melting furnace, and observing the existence of layering.
(5) Water absorption rate
Tested according to the IPC-TM-650-2.6.2.1 method.
The present invention will BE described in detail with reference to the following examples, which refer to BE188 resin from Changchun chemical industry, taiwan, unless otherwise specified;
the low-bromine epoxy resin is GEBR454A80 epoxy resin produced by Guangzhou Hongchang electronic materials company;
the phenolic resin curing agent is KPH-2003 resin of Korea Kelong chemical industry, and the toughening agent is STR-8330 of Siro chemical industry.
The glass fiber cloth can be grade E, and the specification can be 101, 104, 106, 1078, 1080, 1086, 2113, 2313, 2116, 1506 or 7628. The copper foil used may be 1/3oz, hoz, 1oz, 2oz, 3oz, 4oz or 5oz.
Example 1
1. The mass percentage of solids in the resin composition of this example was 66.8% and the balance was an organic solvent (methyl ethyl ketone) wherein the solids were formulated as shown in table 1 below (by weight).
TABLE 1
Raw materials Weight of solids (g)
Base epoxy resin 4.2
Low bromine epoxy resin 41
Phenolic resin curing agent 13.5
Toughening agent 3
Epoxy resin curing accelerator 0.008
Inorganic filler 42
2. The preparation method of the epoxy resin composition comprises the following steps:
(1) Adding 50 g of organic solvent methyl ethyl ketone and a toughening agent into a stirring tank according to the weight, starting a stirrer, stirring for 120 minutes continuously until the toughening agent is completely dissolved, adding an inorganic filler, and stirring for 100 minutes continuously after the adding is finished;
(2) Sequentially adding a phenolic resin curing agent, a basic epoxy resin and a low-bromine epoxy resin into a stirring tank according to the formula amount, and stirring at a rotating speed of 1000 rpm in the feeding process;
(3) Weighing 2-methylimidazole according to the formula weight, and mixing the components in a weight ratio of 1:10 and the organic solvent methyl ethyl ketone were completely dissolved, and the solution was fed into a stirring tank and stirred for 2 hours at 1200 rpm continuously to prepare a resin composition.
3. Preparation of copper-clad plate
The resin adhesive prepared by the method is continuously coated or impregnated with glass fiber cloth, the prepreg is obtained by drying under the baking condition of 170 ℃, 8 prepregs are overlapped, 1 copper foil with the height of Wen Yanzhan um is respectively placed on the upper part and the lower part of the prepreg, and the prepreg is heated and pressurized for 60 minutes under the pressure of 190 ℃ and 350PSI, so that the copper-clad plate with the thickness of 1.5mm is obtained.
4. The performance parameters of the copper clad laminate prepared in this example are shown in table 2 below:
TABLE 2
Project Test results
Glass transition temperature (DSC, °C) 138
Copper foil peel strength (1 oz, lb/in) 8.5
T288(TMA,min) 25
Soldering tin heat resistance (288 ℃ dip tin, min) >10
CTE(％) 3.1
Td(℃,5％wt loss) 332
Water absorption (%) 0.13
Example 2
1. The mass percentage of solids in the resin composition of this example was 63% and the balance was an organic solvent (methyl ethyl ketone) wherein the solids were formulated as shown in table 3 below (by weight).
TABLE 3 Table 3
Raw materials Weight of solids (g)
Base epoxy resin 5
Low bromine epoxy resin 31
Phenolic resin curing agent 11
Toughening agent 5
Epoxy resin curing accelerator 0.01
Inorganic filler 48
2. The preparation method of the epoxy resin composition comprises the following steps:
(1) Adding 58 g of organic solvent methyl ethyl ketone and a toughening agent into a stirring tank according to the weight, starting a stirrer, rotating at 1000 revolutions per minute, continuously stirring for 120 minutes until the toughening agent is completely dissolved, then adding an inorganic filler, and continuously stirring for 100 minutes after the addition is finished;
(2) Sequentially adding a phenolic resin curing agent, a basic epoxy resin and a low-bromine epoxy resin into a stirring tank according to the formula amount, and stirring at a rotating speed of 1000 rpm in the feeding process;
(3) Weighing 2-methylimidazole according to the formula weight, and mixing the components in a weight ratio of 1:10 and the organic solvent methyl ethyl ketone were completely dissolved, and the solution was fed into a stirring tank and stirred for 2 hours at 1200 rpm continuously to prepare a resin composition.
3. Preparation of copper-clad plate
The resin adhesive prepared by the method is continuously coated or impregnated with glass fiber cloth, the prepreg is obtained by drying under the baking condition of 170 ℃, 8 prepregs are overlapped, 1 copper foil with the height of Wen Yanzhan um is respectively placed on the upper part and the lower part of the prepreg, and the prepreg is heated and pressurized for 60 minutes under the pressure of 190 ℃ and 350PSI, so that the copper-clad plate with the thickness of 1.5mm is obtained.
4. The performance parameters of the copper clad laminate prepared in this example are shown in table 4 below:
TABLE 4 Table 4
Example 3
1. The mass percentage of solids in the resin composition of this example was 60%, and the balance was an organic solvent (methyl ethyl ketone), wherein the solid formulation is shown in Table 5 (by weight).
TABLE 5
Raw materials Weight of solids (g)
Base epoxy resin 6
Low bromine epoxy resin 44
Phenolic resin curing agent 15
Toughening agent 4
Epoxy resin curing accelerator 0.01
Inorganic filler 32
2. The preparation method of the epoxy resin composition comprises the following steps:
(1) Adding 67 g of organic solvent methyl ethyl ketone and a toughening agent into a stirring tank according to the weight, starting a stirrer, rotating at 1000 r/min, continuously stirring for 120 min until the toughening agent is completely dissolved, then adding an inorganic filler, and continuously stirring for 100 min after the addition is completed;
(2) Sequentially adding a phenolic resin curing agent, a basic epoxy resin and a low-bromine epoxy resin into a stirring tank according to the formula amount, and stirring at a rotating speed of 1000 rpm in the feeding process;
(3) Weighing 2-methylimidazole according to the formula weight, and mixing the components in a weight ratio of 1:10 and the organic solvent methyl ethyl ketone were completely dissolved, and the solution was fed into a stirring tank and stirred for 2 hours at 1200 rpm continuously to prepare a resin composition.
3. Preparation of copper-clad plate
The resin adhesive prepared by the method is continuously coated or impregnated with glass fiber cloth, the prepreg is obtained by drying under the baking condition of 170 ℃, 8 prepregs are overlapped, 1 copper foil with the height of Wen Yanzhan um is respectively placed on the upper part and the lower part of the prepreg, and the prepreg is heated and pressurized for 60 minutes under the pressure of 190 ℃ and 350PSI, so that the copper-clad plate with the thickness of 1.5mm is obtained.
4. The performance parameters of the copper-clad plate prepared in this example are shown in table 6 below:
TABLE 6
Project Test results
Glass transition temperature (DSC, °C) 138
Copper foil peel strength (1 oz, lb/in) 8.0
T288(TMA,min) 29
Soldering tin heat resistance (288 ℃ dip tin, min) >10
CTE(％) 3.2
Td(℃,5％wt loss) 338
Water absorption (%) 0.11
Comparative example 1
1. The mass percent of solids in the resin composition was 66.4% with the remainder being an organic solvent (e.g., dimethylformamide), wherein the solids were formulated as shown in table 7 below (by weight).
TABLE 7
Raw materials Weight of solids (g)
Low bromine epoxy resin 100
Dicyandiamide 2.5
2-methylimidazole (2-MI) 0.09
2. The preparation method of the epoxy resin composition comprises the following steps:
(1) 52 g of dicyandiamide and organic solvent dimethylformamide are added into the stirring tank according to the weight, a stirrer is started, the rotating speed is 600 revolutions per minute, and stirring is continued for 30 minutes until dicyandiamide solid is completely dissolved;
(2) Adding low-bromine epoxy resin into a stirring tank according to the formula amount, and stirring at a rotating speed of 1000 rpm in the feeding process;
(3) Weighing 2-methylimidazole according to the formula weight, and mixing the components in a weight ratio of 1:10 and the organic solvent propylene glycol methyl ether were completely dissolved, and the solution was added to a stirring tank and stirred for 2 hours at 1200 rpm continuously to prepare a resin composition.
3. Preparation of copper-clad plate
The resin adhesive prepared by the method is continuously coated or impregnated with glass fiber cloth, the prepreg is obtained by drying under the baking condition of 170 ℃, 8 prepregs are overlapped, 1 copper foil with the height of Wen Yanzhan um is respectively placed on the upper part and the lower part of the prepreg, and the prepreg is heated and pressurized for 40 minutes under the pressure of 190 ℃ and 350PSI, so that the copper-clad plate with the thickness of 1.5mm is obtained.
4. The performance parameters of the copper-clad plate prepared in this example are shown in table 8 below:
TABLE 8
Project Test results
Glass transition temperature (DSC, °C) 135
Copper foil peel strength (1 oz, lb/in) 10.5
T288(TMA,min) 1
Soldering tin heat resistance (288 ℃ dip tin, min) 0.5
CTE(％) 3.85
Td(℃,5％wt loss) 308
Water absorption (%) 0.14
Comparative example 2
1. The mass percentage of the solid content in the resin composition was 63%, the balance being an organic solvent (e.g., propylene glycol methyl ether),
wherein the solids formulation is shown in table 9 below (by weight).
TABLE 9
Raw materials Weight of solids (g)
Low bromine epoxy resin 48
Phenolic resin curing agent 13
Epoxy resin curing accelerator 0.015
Inorganic filler 40
2. The preparation method of the epoxy resin composition comprises the following steps:
(1) Adding 60 g of propylene glycol methyl ether serving as an organic solvent into a stirring tank according to the weight, starting a stirrer, stirring for 30 minutes at a rotating speed of 800 rpm, adding inorganic filler, and stirring for 100 minutes after the addition;
(2) Sequentially adding low-bromine epoxy resin and phenolic resin curing agent in a stirring tank according to the formula amount, and stirring at a rotating speed of 1000 rpm in the feeding process;
(3) The propylene glycol methyl ether is weighed according to the formula weight, and the weight ratio of the propylene glycol methyl ether is 1:10 and the organic solvent propylene glycol methyl ether were completely dissolved, and the solution was added to a stirring tank and stirred for 2 hours at 1200 rpm continuously to prepare a resin composition.
3. Preparation of copper-clad plate
The resin adhesive prepared by the method is continuously coated or impregnated with glass fiber cloth, the prepreg is obtained by drying under the baking condition of 170 ℃, 8 prepregs are overlapped, 1 copper foil with the height of Wen Yanzhan um is respectively placed on the upper part and the lower part of the prepreg, and the prepreg is heated and pressurized for 90 minutes under the pressure of 190 ℃ and 350PSI, so that the copper-clad plate with the thickness of 1.5mm is obtained.
4. The performance parameters of the copper-clad plate prepared in this example are shown in the following table 10:
table 10
Project Test results
Glass transition temperature (DSC, °C) 131
Copper foil peel strength (1 oz, lb/in) 7.5
T288(TMA,min) 29
Soldering tin heat resistance (288 ℃ dip tin, min) >10
CTE(％) 3.50
Td(℃,5％wt loss) 338
Water absorption (%) 0.11
Comparative example 3
1. The mass percentage of solids in the resin composition of this example was 65%, and the balance was an organic solvent (methyl ethyl ketone) wherein the solid formulation is shown in Table 5 below (by weight).
TABLE 5
Raw materials Weight of solids (g)
Base epoxy resin 25
Low bromine epoxy resin 20
Phenolic resin curing agent 25
Toughening agent 0.5
Epoxy resin curing accelerator 0.001
Inorganic filler 25
2. The preparation method of the epoxy resin composition comprises the following steps:
(1) Adding 49 g of organic solvent methyl ethyl ketone and a toughening agent into a stirring tank according to the weight, starting a stirrer, rotating at 1000 revolutions per minute, continuously stirring for 120 minutes until the toughening agent is completely dissolved, then adding an inorganic filler, and continuously stirring for 90 minutes after the addition is finished;
(2) Sequentially adding a phenolic resin curing agent, a basic epoxy resin and a low-bromine epoxy resin into a stirring tank according to the formula amount, and stirring at a rotating speed of 1000 rpm in the feeding process;
(3) Weighing 2-methylimidazole according to the formula weight, and mixing the components in a weight ratio of 1:10 and the organic solvent methyl ethyl ketone were completely dissolved, and the solution was fed into a stirring tank and stirred for 2 hours at 1200 rpm continuously to prepare a resin composition.
3. Preparation of copper-clad plate
The resin adhesive prepared by the method is continuously coated or impregnated with glass fiber cloth, the prepreg is obtained by drying under the baking condition of 170 ℃, 8 prepregs are overlapped, 1 copper foil with the height of Wen Yanzhan um is respectively placed on the upper part and the lower part of the prepreg, and the prepreg is heated and pressurized for 60 minutes under the pressure of 190 ℃ and 350PSI, so that the copper-clad plate with the thickness of 1.5mm is obtained.
4. The performance parameters of the copper-clad plate prepared in this example are shown in table 6 below:
TABLE 6
Project Test results
Glass transition temperature (DSC, °C) 143
Copper foil peel strength (1 oz, lb/in) 7.2
T288(TMA,min) 35
Soldering tin heat resistance (288 ℃ dip tin, min) >10
CTE(％) 3.9
Td(℃,5％wt loss) 339
Water absorption (%) 0.11
The epoxy glass cloth-based copper-clad laminate prepared in the above way has the advantages of common glass transition temperature (Tg is larger than or equal to 135 ℃), excellent heat resistance and low coefficient of thermal expansion (CTE (50-260 ℃) is smaller than or equal to 3.2%), and can be suitable for manufacturing printed circuit boards in lead-free processes in the PCB industry.
The material has low thermal expansion coefficient, can ensure that the material has good heat resistance and dimensional stability, and is not easy to cause the heat resistance problems of explosion board and the like in the use process of the PCB.

Claims (5)

1. The copper-clad plate with low thermal expansion coefficient suitable for the lead-free manufacturing process of the PCB is characterized in that the copper-clad plate is prepared from an adhesive, glass fiber cloth and copper foil, wherein the adhesive consists of solid matters and an organic solvent, the weight percentage of the solid matters is 50-75%, the organic solvent is the rest,
the solid comprises the following components in percentage by weight:
4.2% -6% of basic epoxy resin;
31% -44% of low-bromine epoxy resin;
11% -15% of phenolic resin curing agent;
3% -5% of a toughening agent;
epoxy resin curing accelerator 0.008-0.01%;
32% -42% of inorganic filler;
the physical property requirement of the basic epoxy resin is that the epoxy equivalent EEW (g/eq) is 160-210;
the hydrolyzable chlorine is 300MAX;
the physical property requirement of the low-bromine epoxy resin is that the epoxy equivalent EEW (g/eq) is 380-450;
the hydrolyzable chlorine is 300MAX;
bromine content (wt%) is 17-24;
the toughening agent is a core-shell rubber toughening agent;
the phenolic resin is phenolic resin formed by crosslinking phenol and formaldehyde;
the epoxy resin curing accelerator is any one or more of 2-ethyl-4-methylimidazole, 2-methylimidazole or 1-benzyl-2-methylimidazole;
the inorganic filler is any one or more of talcum powder, quartz powder, ceramic powder, aluminum hydroxide or metal oxide particles.
2. The copper-clad plate with low thermal expansion coefficient suitable for the lead-free PCB manufacturing process according to claim 1, wherein the organic solvent is one or a mixture of more than two of acetone, methyl ethyl ketone, methyl isobutyl ketone or propylene glycol methyl ether.
3. The method for preparing the copper-clad plate with low thermal expansion coefficient, which is suitable for the lead-free manufacturing process of the PCB, according to any one of claims 1 to 2, is characterized in that the method comprises the following steps:
the preparation method of the adhesive comprises the following steps:
1) Adding part of organic solvent, phenolic resin curing agent and toughening agent into the stirring tank according to the formula amount, starting the stirrer, and continuously stirring for 2-2.5 hours at the rotation speed of 800-1000 rpm to ensure complete dissolution of the solid in the tank, and controlling the temperature of the tank at 20-45 ℃;
then adding inorganic filler, and continuously stirring for 90-120 minutes after the addition is finished;
2) Sequentially adding basic epoxy resin and low-bromine epoxy resin into a stirring tank according to the formula amount, stirring at a rotation speed of 1000-1400 rpm in the feeding process, starting high-efficiency shearing and emulsifying for 1-3 hours after the adding is finished, and simultaneously circulating cooling water to keep the temperature of the tank at 20-45 ℃;
3) Weighing epoxy resin curing accelerator according to the formula amount, adding the epoxy resin curing accelerator into the residual organic solvent, adding the solution into a stirring tank after complete dissolution, and continuously keeping 1000-1500 rpm for stirring for 4-12 hours to obtain the adhesive;
preparing a prepreg:
1) The adhesive is circulated to a sizing machine, and is uniformly coated on the glass fiber cloth after presoaking and primary dipping,
2) Baking the glass fiber cloth coated with the adhesive by a baking box at 110-250 ℃ to volatilize the solvent, and primarily reacting and solidifying the adhesive to prepare a prepreg; wherein, the line speed of sizing is controlled to be 8-25m/min,
controlling physical parameters of the prepreg: the gelation time is 80-175 seconds, the mass percentage of the resin component in the prepreg is 35-78%, the resin fluidity is 15-45%, and the volatile is less than 0.75%;
typesetting and pressing:
1) Cutting the prepreg into a group of 1-18 sheets with the same size, overlapping the prepreg with copper foil, and pressing;
2) The pressing parameters were controlled as follows:
a. pressure: 100-550psi;
b. hot plate temperature: 80-200 ℃;
c. vacuum degree: 0.030-0.080Mpa;
d. pressing time: 150-180 minutes;
e. curing time: and maintaining at 190 deg.c for 40-100 min.
4. The method for manufacturing a copper-clad plate with low thermal expansion coefficient for lead-free PCB manufacturing process according to claim 3, wherein the glass fiber cloth in the prepreg manufacturing step is grade E, and the specifications are 101, 104, 106, 1078, 1080, 1086, 2113, 2313, 2116, 1506 or 7628;
the copper foil is 1/3oz, hoz, 1oz, 2oz, 3oz, 4oz or 5oz.
5. The method of manufacturing a copper clad laminate having a low thermal expansion coefficient suitable for a lead-free process of a PCB according to claim 3, wherein the copper clad laminate has a gauge of 36 x 48 inches, 36.5 x 48.5 inches, 37 x 49 inches, 40 x 48 inches, 40.5 x 48.5 inches, 41 x 49 inches, 42 x 48 inches, 42.5 x 48.5 inches or 43 x 49 inches and a thickness of 0.05-3.2mm.
CN202210883560.0A 2022-07-26 2022-07-26 Copper-clad plate with low thermal expansion coefficient suitable for PCB lead-free process and preparation method thereof Active CN115339195B (en)

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