CN115339195A - 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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Publication number
CN115339195A
CN115339195A CN202210883560.0A CN202210883560A CN115339195A CN 115339195 A CN115339195 A CN 115339195A CN 202210883560 A CN202210883560 A CN 202210883560A CN 115339195 A CN115339195 A CN 115339195A
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copper
clad plate
thermal expansion
expansion coefficient
low thermal
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CN115339195B (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
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    • 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
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    • 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
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    • 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
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    • 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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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Thermal Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Fluid Mechanics (AREA)
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Abstract

The invention discloses a copper-clad plate with low thermal expansion coefficient suitable for a PCB lead-free process and a preparation method thereof. The copper-clad plate prepared by the invention has the advantages of common glass transition temperature (Tg ≧ 135 ℃), excellent heat resistance and low thermal expansion coefficient, and can be suitable for the production of lead-free process printed circuit boards 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 PCB lead-free process and a preparation method thereof.
Background
With the high density and high performance of the PCB, the HDI/BUM board, the embedded component multilayer board, the high-density multilayer board, and the like are rapidly developed, and the number of layers, thickness, and area of the PCB are increased, and when the high-temperature soldering is performed, particularly the lead-free soldering is performed, in order to ensure the reliability of the soldering, the high-temperature soldering temperature or the longer soldering time is required to be endured, so that higher requirements are made on the substrate material, and compared with the conventional material, the board material has higher glass transition temperature and heat resistance.
Beginning at 7/1 in 2006, the official implementation of two directives (directive on the restriction of the use of hazardous substances in electrical and electronic products and directive on the scrapping of electrical and electronic products) in the european union indicates that the global electronics industry will enter the lead-free soldering 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 reused, and the welding temperature required by the existing tin-silver-copper and other alternative solders is greatly improved. While the traditional FR-4 copper-clad plate has low heat resistance, the glass transition temperature is only 130-140 ℃, the thermal decomposition temperature is generally only 300-310 ℃, although the traditional FR-4 copper-clad plate is widely applied to general electronic products, the traditional FR-4 copper-clad plate cannot be applied to the field of high-density interconnection and integrated circuits, the development of the electronic products is rapid, and along with the lightening and thinning of printed circuits, multilayering and the development of semiconductor mounting technology, a substrate is required to have good heat resistance and PCB processing performance so as to improve the interconnection and mounting reliability.
At present, market competition is more and more severe, most of lead-free products developed in the industry have Tg of 150 ℃ or above, the copper-clad plate materials are various and are more and more mature, and the development of a common Tg copper-clad plate based on cost consideration also becomes a trend of materials with low thermal expansion coefficient and good heat resistance.
Disclosure of Invention
In view of the above problems, the invention aims to provide a copper-clad plate with low thermal expansion coefficient suitable for a PCB lead-free manufacturing process and a preparation method thereof. The copper-clad plate material prepared by the invention has low thermal expansion coefficient, good heat resistance and lower material cost.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
the copper-clad plate is suitable for a PCB lead-free process and has a low thermal expansion coefficient, the copper-clad plate is prepared from an adhesive, glass fiber cloth and a copper foil, the adhesive consists of a solid matter and an organic solvent, wherein the weight percentage content of the solid matter is 50-75%, the balance is the organic solvent,
the solid comprises the following components in percentage by weight:
Figure BDA0003765125580000011
Figure BDA0003765125580000021
in a preferred embodiment of the present invention, the physical properties of the base epoxy resin are required to have an epoxy equivalent EEW (g/eq) in the range of 160 to 210;
the hydrolysable chlorine is in the range of 300MAX.
In a preferred embodiment of the present invention, the base epoxy resin is preferably, but not limited to, BE188 resin of chemical engineering corporation of taiwan vinpocetine.
In a preferred embodiment of the present invention, the physical properties of the low-bromine epoxy resin are required to have an epoxy equivalent EEW (g/eq) in the range of 380 to 450;
hydrolyzable chlorine in the range of 300MAX;
the bromine content (wt%) is 17-24.
In a preferred embodiment of the present invention, the low-bromine epoxy resin is GEBR454a80 epoxy resin manufactured by marchand electronics, guangzhou, but is not limited thereto.
In a preferred embodiment of the present invention, the toughening agent is a core shell rubber based toughening agent.
In a preferred embodiment of the present invention, the phenol-formaldehyde resin is phenol-formaldehyde crosslinked phenol-formaldehyde, and the phenol is phenol, xylenol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, isobutylphenol, tert-butylphenol, or bisphenol a phenol-formaldehyde crosslinked phenol-formaldehyde resin, or a mixture of phenol-formaldehyde resin and bisphenol a phenol-formaldehyde resin.
In a preferred embodiment of the present invention, the phenol resin is preferably KPH-2003 resin of korea-kresome chemical.
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 invention, the inorganic filler is any one or more of talc powder, 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.
Preferably any one or more of silica, aluminium hydroxide or talc.
The resin composition of the invention is added with proper filler to reduce the expansion coefficient of the resin composition for manufacturing a 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 Coefficient of Thermal Expansion (CTE), increasing the modulus, accelerating the heat transfer, 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 preparation method of a copper-clad plate with low thermal expansion coefficient suitable for a PCB lead-free process 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 a stirring tank according to the formula amount, starting a stirrer, rotating at 800-1000 rpm, continuously stirring for 2-2.5 hours to ensure that all solids in the tank are completely dissolved, and simultaneously controlling the temperature of the tank body to be 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 according to the formula amount in a stirring tank, stirring at the rotating speed of 1000-1400 rpm in the feeding process, starting high-efficiency shearing and emulsifying for 1-3 hours after the addition is finished, and simultaneously performing cooling water circulation to keep the temperature of the tank body controlled at 20-45 ℃;
3) Weighing the epoxy resin curing accelerator according to the formula amount, adding the epoxy resin curing accelerator into the rest organic solvent, adding the solution into a stirring tank after the epoxy resin curing accelerator is completely dissolved, and continuously stirring for 4-12 hours at 1000-1500 rpm to obtain the adhesive;
a prepreg preparation step:
1) The adhesive is circulated to a gluing machine, is evenly coated on the glass fiber cloth through pre-dipping and main dipping,
2) Baking the glass fiber cloth coated with the adhesive in a drying oven at 110-250 ℃ to volatilize the solvent, and primarily reacting and curing the adhesive to obtain a prepreg; wherein the linear speed of gluing is controlled to be 8-25m/min,
controlling physical parameters of the prepreg: the gelation time is 80-175 seconds, the mass percent of resin components in the prepreg is 35-78%, the resin fluidity is 15-45%, and the volatile component 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. temperature of the hot plate: 80-200 ℃;
c. vacuum degree: 0.030-0.080Mpa;
d. pressing time: 150-180 minutes;
e. curing time: and keeping the temperature of 190 ℃ for 40-100 minutes.
In a preferred embodiment of the present invention, the glass fiber cloth in the prepreg preparation step is grade E, and the specification is 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 specification of the copper-clad plate prepared by the invention is 36 × 48 inches, 36.5 × 48.5 inches, 37 × 49 inches, 40 × 48 inches, 40.5 × 48.5 inches, 41 × 49 inches, 42 × 48 inches, 42.5 × 48.5 inches or 43 × 49 inches, and the thickness of the copper-clad plate is 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 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 the lead-free process printed circuit board in the PCB industry.
Detailed Description
The invention is further illustrated by the following examples and comparative examples.
The characteristics of the copper-clad plates 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 (. Degree. C.) at which the sheet changes from a glassy state to a highly elastic (rubbery) state when heated.
(2) Thermal stratification time (T-288)
The T-288 thermal delamination time is the time during which the sheet delaminates due to heat at a set temperature of 288 ℃ before it lasts.
The detection method comprises the following steps: thermomechanical analysis (TMA) was used.
(3) Strength of peel resistance
According to IPC-TM-650-2.4.8C method.
(4) Solder heat resistance
Solder heat resistance refers to the duration of time during which the sheet is immersed in molten solder at 288 ℃ without delamination and blistering.
The detection method comprises the following steps: cutting the etched substrate into 5.0cm × 5.0cm, sequentially polishing the edges of the substrate with 120-mesh and 800-mesh abrasive paper, cooking for a certain time with a pressure cooker, putting into a tin melting furnace at 288 ℃, and observing whether layering occurs or not.
(5) Water absorption rate
The test was carried out 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 are intended to refer to the basic epoxy resin BE188 resin from the chemical production of Taiwan Changchun, china, unless otherwise specified;
the low-bromine epoxy resin is GEBR454A80 epoxy resin produced by Guangzhou Macrochang electronic material company;
the phenolic resin curing agent is KPH-2003 resin of Korea Kelon chemical engineering, and the flexibilizer is STR-8330 of Seitv chemical engineering.
The glass fiber cloth can be selected from E grade, and the specification can be selected from 101, 104, 106, 1078, 1080, 1086, 2113, 2313, 2116, 1506 or 7628. The copper foil can be selected from 1/3oz, hoz, 1oz, 2oz, 3oz, 4oz or 5oz.
Example 1
1. The resin composition of this example contains 66.8% by weight of solids, and the balance of organic solvent (methyl ethyl ketone), wherein the formulation of solids is shown in table 1 below (by weight).
TABLE 1
Raw material Solid weight (g)
Basic epoxy resin 4.2
Low bromine epoxy resins 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, rotating at 900 rpm, 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) Adding a phenolic resin curing agent, basic epoxy resin and low-bromine epoxy resin into a stirring tank in sequence according to the formula amount, and stirring at the rotating speed of 1000 revolutions per minute in the feeding process;
(3) Weighing 2-methylimidazole according to the formula ratio of 1:10 and the organic solvent methyl ethyl ketone are completely dissolved, the solution is added into a stirring tank, and stirring is continuously carried out for 2 hours at 1200 rpm, so as to prepare the 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 glass fiber cloth is dried under the baking condition of 170 ℃ to obtain prepregs, 8 prepregs are overlapped, 1 piece of high-temperature extending copper foil with the thickness of 35 mu m is respectively placed on the prepregs and placed on the prepregs, and the prepregs are heated and pressurized for 60 minutes under the pressure of 190 ℃ and 350PSI to obtain the copper-clad plate with the thickness of 1.5 mm.
4. The performance parameters of the copper-clad plate prepared in this example are shown in table 2 below:
TABLE 2
Item Test results
Glass transition temperature (DSC,. Degree.C.) 138
Copper foil peel strength (1oz, lb/in) 8.5
T288(TMA,min) 25
Solder heat resistance (288 ℃ tin immersion, min) >10
CTE(％) 3.1
Td(℃,5％wt loss) 332
Water absorption (%) 0.13
Example 2
1. The resin composition of this example contains 63% by weight of solids, and the balance of organic solvent (methyl ethyl ketone), wherein the formulation of solids is shown in table 3 below (by weight).
TABLE 3
Raw material Solid weight (g)
Basic epoxy resin 5
Low bromine epoxy resins 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 at the rotating speed of 1000 rpm, 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) Adding a phenolic resin curing agent, basic epoxy resin and low-bromine epoxy resin into a stirring tank in a formula ratio in sequence, and stirring at the rotating speed of 1000 revolutions per minute in the feeding process;
(3) Weighing 2-methylimidazole according to the formula ratio of 1:10 and the organic solvent methyl ethyl ketone are completely dissolved, the solution is added into a stirring tank, and stirring is continuously carried out for 2 hours at 1200 rpm, so as to prepare the 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 glass fiber cloth is dried under the baking condition of 170 ℃ to obtain prepregs, 8 prepregs are overlapped, 1 piece of high-temperature extending copper foil with the thickness of 35 mu m is respectively placed on the prepregs and the prepregs, and the copper-clad plate with the thickness of 1.5mm is obtained by heating and pressurizing the prepregs under the pressure of 190 ℃ and 350PSI for 60 minutes.
4. The performance parameters of the copper-clad plate prepared in this example are shown in table 4 below:
TABLE 4
Figure BDA0003765125580000071
Figure BDA0003765125580000081
Example 3
1. The resin composition of this example contains 60% by weight of solids, and the balance of organic solvent (methyl ethyl ketone), wherein the formulation of solids is shown in table 5 below (by weight).
TABLE 5
Raw material Solid weight (g)
Basic epoxy resin 6
Low bromine epoxy resins 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 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) Adding a phenolic resin curing agent, basic epoxy resin and low-bromine epoxy resin into a stirring tank in a formula ratio in sequence, and stirring at the rotating speed of 1000 revolutions per minute in the feeding process;
(3) Weighing 2-methylimidazole according to the formula ratio of 1:10 and the organic solvent methyl ethyl ketone are completely dissolved, the solution is added into a stirring tank, and stirring is continuously carried out for 2 hours at 1200 rpm, so as to prepare the 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 glass fiber cloth is dried under the baking condition of 170 ℃ to obtain prepregs, 8 prepregs are overlapped, 1 piece of high-temperature extending copper foil with the thickness of 35 mu m is respectively placed on the prepregs and the prepregs, and the copper-clad plate with the thickness of 1.5mm is obtained by heating and pressurizing the prepregs under the pressure of 190 ℃ and 350PSI for 60 minutes.
4. The performance parameters of the copper-clad plate prepared in this example are shown in table 6 below:
TABLE 6
Item Test results
Glass transition temperature (DSC,. Degree.C.) 138
Peel strength of copper foil (1oz, lb/in) 8.0
T288(TMA,min) 29
Solder heat resistance (288 ℃ tin immersion, min) >10
CTE(％) 3.2
Td(℃,5％wt loss) 338
Water absorption (%) 0.11
Comparative example 1
1. The resin composition had a solids content of 66.4% by weight and the balance organic solvent (e.g., dimethylformamide), wherein the solids formulation is shown in table 7 below (by weight).
TABLE 7
Raw material Solid weight (g)
Low bromine epoxy resins 100
Dicyandiamide 2.5
2-methylimidazole (2-MI) 0.09
2. The preparation method of the epoxy resin composition comprises the following steps:
(1) Adding 52 g of dicyandiamide and an organic solvent dimethylformamide into a stirring tank according to the weight, starting a stirrer, rotating at 600 revolutions per minute, and continuously stirring for 30 minutes until dicyandiamide solid is completely dissolved;
(2) Adding the low-bromine epoxy resin into a stirring tank according to the formula amount, and stirring at the rotating speed of 1000 revolutions per minute in the feeding process;
(3) Weighing 2-methylimidazole according to the formula ratio of 1:10 and the organic solvent propylene glycol methyl ether are completely dissolved, and then the solution is added into a stirring tank and is continuously stirred for 2 hours at 1200 rpm, thus obtaining the 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 glass fiber cloth is dried under the baking condition of 170 ℃ to obtain prepregs, 8 prepregs are overlapped, 1 piece of high-temperature extending copper foil with the thickness of 35 mu m is respectively placed on the prepregs and the prepregs, and the copper-clad plate with the thickness of 1.5mm is obtained by heating and pressurizing the prepregs under the pressure of 190 ℃ and 350PSI for 40 minutes.
4. The performance parameters of the copper-clad plate prepared in this example are shown in table 8 below:
TABLE 8
Item Test results
Glass transition temperature (DSC,. Degree.C.) 135
Copper foil peel strength (1oz, lb/in) 10.5
T288(TMA,min) 1
Solder heat resistance (288 ℃ tin immersion, 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 is 63 percent, and the balance is an organic solvent (such as propylene glycol methyl ether),
the formulation of solids, among others, is shown in table 9 below (by weight).
TABLE 9
Raw material Solid weight (g)
Low bromine epoxy resins 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 organic solvent propylene glycol methyl ether into a stirring tank according to the weight, starting a stirrer, rotating at 800 rpm, continuously stirring for 30 minutes, then adding inorganic filler, and continuously stirring for 100 minutes after the addition is finished;
(2) Sequentially adding low-bromine epoxy resin and phenolic resin curing agent into a stirring tank according to the formula amount, and stirring at the rotating speed of 1000 revolutions per minute in the feeding process;
(3) Weighing propylene glycol methyl ether according to the formula ratio of 1:10 and the organic solvent propylene glycol methyl ether are completely dissolved, and then the solution is added into a stirring tank and is continuously stirred for 2 hours at 1200 rpm, thus obtaining the 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 glass fiber cloth is dried under the baking condition of 170 ℃ to obtain prepregs, 8 prepregs are overlapped, 1 piece of high-temperature extending copper foil with the thickness of 35 mu m is respectively placed on the prepregs and placed on the prepregs, and the prepregs are heated and pressurized for 90 minutes under the pressure of 190 ℃ and 350PSI to obtain the copper-clad plate with the thickness of 1.5 mm.
4. The performance parameters of the copper-clad plate prepared in this example are shown in table 10 below:
watch 10
Item Test results
Glass transition temperature (DSC,. Degree.C.) 131
Copper foil peel strength (1oz, lb/in) 7.5
T288(TMA,min) 29
Soldering tin heat resistance (288 ℃ tin immersion, min) >10
CTE(％) 3.50
Td(℃,5％wt loss) 338
Water absorption (%) 0.11
Comparative example 3
1. The resin composition of this example contains 65% by weight of solids, and the balance of organic solvent (methyl ethyl ketone), wherein the formulation of solids is shown in table 5 below (by weight).
TABLE 5
Raw material Solid weight (g)
Basic epoxy resin 25
Low bromine epoxy resins 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 the toughening agent into a stirring tank according to the weight, starting a stirrer, rotating at 1000 r/min, continuously stirring for 120 minutes until the toughening agent is completely dissolved, then adding the inorganic filler, and continuously stirring for 90 minutes after the addition is finished;
(2) Adding a phenolic resin curing agent, basic epoxy resin and low-bromine epoxy resin into a stirring tank in a formula ratio in sequence, and stirring at the rotating speed of 1000 revolutions per minute in the feeding process;
(3) Weighing 2-methylimidazole according to the formula ratio of 1:10 and the organic solvent methyl ethyl ketone are completely dissolved, the solution is added into a stirring tank, and stirring is continuously carried out for 2 hours at 1200 rpm, so as to prepare the 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 glass fiber cloth is dried under the baking condition of 170 ℃ to obtain prepregs, 8 prepregs are overlapped, 1 piece of high-temperature extending copper foil with the thickness of 35 mu m is respectively placed on the prepregs and the prepregs, and the copper-clad plate with the thickness of 1.5mm is obtained by heating and pressurizing the prepregs under the pressure of 190 ℃ and 350PSI for 60 minutes.
4. The performance parameters of the copper-clad plate prepared in this example are shown in table 6 below:
TABLE 6
Item Test results
Glass transition temperature (DSC,. Degree.C.) 143
Copper foil peel strength (1oz, lb/in) 7.2
T288(TMA,min) 35
Solder heat resistance (288 ℃ tin immersion, min) >10
CTE(％) 3.9
Td(℃,5％wt loss) 339
Water absorption (%) 0.11
The prepared epoxy glass cloth-based copper-clad laminate has the advantages of common glass transition temperature (Tg ≧ 135 ℃), excellent heat resistance and low coefficient of thermal expansion (CTE (50-260 ℃) is less than or equal to 3.2%), and can be suitable for manufacturing lead-free process printed circuit boards in the PCB industry.
The material has low thermal expansion coefficient, so that the material has good heat resistance and dimensional stability, and the heat resistance problems such as board explosion and the like are not easy to generate in the use process of the PCB.

Claims (10)

1. The copper-clad plate with low thermal expansion coefficient suitable for the lead-free process of the PCB is characterized in that the copper-clad plate is prepared by adhesive, glass fiber cloth and copper foil, the adhesive consists of solid and organic solvent, wherein the weight percentage content of the solid is 50-75 percent, the rest is the organic solvent,
the solid comprises the following components in percentage by weight:
Figure FDA0003765125570000011
2. the copper-clad plate suitable for the lead-free process of PCB with low thermal expansion coefficient of claim 1, wherein the physical property requirement of the basic epoxy resin is that the epoxy equivalent EEW (g/eq) range is 160-210;
the range of hydrolyzable chlorine is 300MAX.
3. The copper-clad plate suitable for the lead-free process of PCB with low thermal expansion coefficient as claimed in claim 1, wherein the physical property requirement of the low bromine epoxy resin is that the epoxy equivalent EEW (g/eq) range is 380-450;
hydrolyzable chlorine in the range of 300MAX;
the bromine content (wt%) is 17-24.
4. The copper-clad plate suitable for the lead-free PCB process with low thermal expansion coefficient according to claim 1, wherein the toughening agent is a core-shell rubber toughening agent;
the phenolic resin is phenol-formaldehyde cross-linked phenolic resin, and the phenol is phenol, xylenol, ethyl phenol, n-propyl phenol, isopropyl phenol, n-butyl phenol, isobutyl phenol, tert-butyl phenol or bisphenol A phenolic resin cross-linked by bisphenol A and formaldehyde, or a mixture of phenol phenolic resin and bisphenol A phenolic resin.
5. The copper-clad plate with low thermal expansion coefficient suitable for the lead-free process of PCB according to claim 1, wherein the curing accelerator is any one or more of 2-ethyl-4-methylimidazole, 2-methylimidazole or 1-benzyl-2-methylimidazole.
6. The copper-clad plate with low thermal expansion coefficient suitable for PCB lead-free process according to claim 1, wherein the inorganic filler is any one or more of talcum powder, 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.
7. The copper-clad plate with low thermal expansion coefficient suitable for the lead-free process of PCB 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.
8. The method for preparing the copper-clad plate with low thermal expansion coefficient suitable for the lead-free PCB process according to any one of claims 1 to 7, wherein 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 a stirring tank according to the formula amount, starting a stirrer, rotating at 800-1000 rpm, continuously stirring for 2-2.5 hours to ensure that all solids in the tank are completely dissolved, and simultaneously controlling the temperature of the tank body to be 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 according to the formula amount in a stirring tank, stirring at the rotating speed of 1000-1400 rpm in the feeding process, starting high-efficiency shearing and emulsifying for 1-3 hours after the addition is finished, and simultaneously performing cooling water circulation to keep the temperature of the tank body controlled at 20-45 ℃;
3) Weighing the epoxy resin curing accelerator according to the formula amount, adding the epoxy resin curing accelerator into the rest organic solvent, adding the solution into a stirring tank after the epoxy resin curing accelerator is completely dissolved, and continuously stirring for 4-12 hours at 1000-1500 rpm to obtain the adhesive;
a step of preparing a prepreg:
1) The adhesive is circulated to a gluing machine, is evenly coated on the glass fiber cloth through pre-dipping and main dipping,
2) Baking the glass fiber cloth coated with the adhesive in a drying oven at 110-250 ℃ to volatilize the solvent, and primarily reacting and curing the adhesive to obtain a prepreg; wherein the linear speed of gluing is controlled to be 8-25m/min,
controlling physical parameters of the prepreg: the gelation time is 80-175 seconds, the mass percent of resin components in the prepreg is 35-78%, the resin fluidity is 15-45%, and the volatile component is less than 0.75%;
typesetting and pressing:
1) Cutting the prepreg into a group of 1-18 pieces 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. temperature of the hot plate: 80-200 ℃;
c. vacuum degree: 0.030-0.080Mpa;
d. pressing time: 150-180 minutes;
e. curing time: and keeping the temperature of more than 190 ℃ for 40-100 minutes.
9. The method for preparing the copper-clad plate with low thermal expansion coefficient suitable for the lead-free process of the PCB according to claim 8, wherein the glass fiber cloth in the prepreg preparation step is E-grade with specification of 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.
10. The method for preparing the copper-clad plate with low thermal expansion coefficient suitable for the lead-free process of the PCB according to claim 8, wherein the specification of the copper-clad plate is 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 the thickness of the copper-clad plate is 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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