CN110564111A - Halogen-free high-Tg flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board and preparation method thereof - Google Patents
Halogen-free high-Tg flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board and preparation method thereof Download PDFInfo
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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
- 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
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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
- 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
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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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/08—Impregnating
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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
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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
- B32B5/22—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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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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
- 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
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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
- 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
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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
- 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
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/04—Epoxynovolacs
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- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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Abstract
The invention provides a halogen-free high-Tg flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board and a preparation method thereof, wherein the preparation method mainly comprises the following steps of 101, filler dispersion: taking 18-22 parts by weight of phosphorus-containing epoxy resin and 48-52 parts by weight of novolac epoxy resin, adding 18-22 parts by weight of PMA, mixing and stirring, adding 18-22 parts by weight of filler while stirring, and then accelerating stirring to form dispersed filler; the filler is aluminum hydroxide and/or silicon dioxide, wherein the mixing ratio of the aluminum hydroxide to the silicon dioxide is 1: 1; step 102, resin entering: mixing 48-52 parts of novolac epoxy resin, 18-22 parts of high-heat-resistance epoxy resin and the dispersed filler obtained in the step 101 to obtain a mixture; 103, adding a curing agent; step 104, stopping the machine and measuring the S/G; step 2, impregnation; step 3, stacking; step 4, combining; and 5, pressing, and 6, cutting. The invention has Tg greater than 170 ℃ (DSC), excellent heat resistance (T-288>60min), low Z-axis expansion coefficient, low water absorption and CAF resistance.
Description
Technical Field
The invention relates to the technical field of electronic materials, in particular to a halogen-free high-Tg flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board and a preparation method thereof.
background
copper Clad Laminate (CCL) is a product which is prepared by using wood pulp paper or glass fiber cloth as a reinforcing material, soaking the reinforcing material with resin, coating Copper foil on one side or two sides, and carrying out hot pressing. The copper-clad plate is a basic material in the electronic industry, is mainly used for processing and manufacturing Printed Circuit Boards (PCBs), and is widely applied to electronic products such as televisions, radios, computers, mobile communication and the like.
the copper-clad plates available in the market can be mainly classified into the following types from the viewpoint of base materials: paper substrates, glass fiber cloth substrates, synthetic fiber cloth substrates, nonwoven fabric substrates, composite substrates, and others.
the preparation process flow of the glass fiber cloth substrate is as follows approximately: cutting → pre-stacking → combining → pressing → disassembling → cutting → packaging → warehousing → delivering.
the traditional high-heat-resistance high-Tg copper-clad plate suitable for the lead-free process adopts halogen (Br and other elements) as a flame retardant, but the substance can generate a carcinogenic substance-dioxin under the condition of incomplete combustion, so that the environment is influenced to a certain extent, and the environment is not protected.
On the other hand, the traditional common Tg sheet material adopts amine compounds as curing agents which react with epoxy resin, and the copper-clad plate has the defects of low Tg and unsuitability for a lead-free tin spraying process with environmental protection requirements.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a halogen-free high-Tg flame-retardant heat-resistant copper foil-clad epoxy glass fiber cloth-based laminated board and a preparation method thereof.
in order to solve the technical problems, the invention adopts the following technical scheme:
A preparation method of a halogen-free high-Tg flame-retardant heat-resistant copper-clad foil epoxy fiberglass cloth-based laminated board comprises the following steps:
Step 1, preparing ingredients;
Wherein, the preparation of the ingredients comprises the following steps:
Step 101, filler dispersion: taking 18-22 parts by weight of phosphorus-containing epoxy resin and 48-52 parts by weight of novolac epoxy resin, adding 18-22 parts by weight of PMA (propylene glycol monomethyl ether acetate), mixing and stirring, adding 18-22 parts by weight of filler while stirring, and then accelerating stirring to form dispersed filler;
the filler is aluminum hydroxide and/or silicon dioxide, wherein the mixing ratio of the aluminum hydroxide to the silicon dioxide is 1: 1;
step 102, resin entering: mixing 48-52 parts of novolac epoxy resin, 18-22 parts of high-heat-resistance epoxy resin and the dispersed filler obtained in the step 101 to obtain a mixture;
step 103, adding a curing agent: adding 18-22 parts of phenolic resin, 48-52 parts of benzoxazine resin, 58-62 parts of phosphorus-containing flame retardant curing agent and 0.45-0.55 part of catalyst dimethylimidazole into the mixture obtained in the step 102, and continuously stirring to enable the mixture and the mixture to fully generate a curing reaction to form glue;
step 104, stopping and measuring S/G: extracting a sample from the ingredients formed in the step 103, measuring the S/G (gel time) value of the sample, and if the measured S/G range is in a range of 280-320S, entering the next step if the ingredients are qualified;
Step 2, impregnation: soaking glass fiber cloth into the ingredients prepared in the step 1, and drying to obtain a semi-solid sheet;
and 3, stacking: stacking at least one prepreg to a certain preset thickness so as to meet the requirements of different thicknesses;
And 4, combining: covering a single-sided or double-sided copper foil on the prepreg stacked in the step 3, combining the prepreg with a die, and then sending the combined prepreg into a hot press;
Step 5, pressing: melting the resin in the prepreg at high temperature, and expelling bubbles under high pressure to gradually harden the resin and bond the resin with the copper foil to form a substrate;
Step 6, checking: and cutting off the edge materials of the laminated substrate, and then checking the appearance, the thickness and the like to obtain a finished product.
preferably, in the step 101, after the addition of the silica and the aluminum hydroxide is completed, the rotation speed is not lower than 1000 r/Min.
preferably, in the step 101, after the addition of the silica and the aluminum hydroxide is completed, the stirring time is not less than 4.5H.
Preferably, in the step 103, the stirring is continuously carried out for not less than 5H.
preferably, in the step 2, the specific steps of immersing the glass fiber cloth into the furnish prepared in the step 1 are as follows: driving the electronic-grade glass fiber cloth on a cloth rack of an impregnation machine, controlling the glass fiber cloth to advance by tension, enabling the glass cloth to pass through an impregnation groove full of glue, enabling the glass cloth soaked with the glue to enter an oven, volatilizing redundant solvent and carrying out further reaction on resin and a curing agent; and drying to obtain the semi-fixing sheet.
Preferably, the mold in the step 4 is a steel plate.
Preferably, in the pressing process in the step 5, the temperature is increased to 1.2-1.8 ℃/min, the pressure is 3.0Mpa, and the vacuum is 730 mmhg.
preferably, in the step 104, the step of,
If the S/G is longer, adding 0.01-0.1 part of catalyst for accelerating the reaction;
if the S/G is shorter, additionally preparing a new ingredient with long S/G length according to the steps 101-103, uniformly mixing the new ingredient with the original ingredient, and then detecting the S/G, wherein in the preparation process of the new ingredient, the addition amount of the bisphenol A type bromine epoxy resin is increased by 10-20%.
Preferably, the temperature is controlled between 25 ℃ and 50 ℃ during the step 103 of curing.
the flame-retardant heat-resistant copper-clad foil epoxy fiberglass cloth-based laminated board prepared by the preparation method.
has the advantages that:
The invention has the beneficial effects of environmental protection and harmlessness. Specifically, the invention adopts another phosphorus-containing epoxy resin as a flame retardant, can meet the flame-retardant requirement and also meets the environmental protection requirement; in addition, the invention adopts a unique phenolic aldehyde curing technology and a benzoxazine resin curing technology, enhances the crosslinking density with the epoxy resin, thereby improving the Tg of the board and being suitable for the lead-free tin spraying process of the PCB.
In addition, the substrate developed by the invention has Tg higher than 170 ℃ (DSC), excellent heat resistance (T-288>60min), low Z-axis expansion coefficient, low water absorption and CAF (by-product after copper foil metal electric reaction corrosion) resistance, and the required curing temperature and time can be obviously reduced and shortened compared with other halogen-free boards, thereby improving the PCB processing efficiency.
Drawings
FIG. 1 shows a flow chart of the preparation in the example of the present invention.
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
it should be noted that all the directional indicators (such as upper, lower, left, right, front and rear … …) in the embodiment of the present invention are only used to explain the relative position relationship between the components, the movement situation, etc. in a specific posture (as shown in the drawing), and if the specific posture is changed, the directional indicator is changed accordingly.
In addition, the descriptions related to "first", "second", etc. in the present invention are only for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
The embodiment of the invention relates to a preparation method of a halogen-free high-Tg flame-retardant heat-resistant copper foil-clad epoxy fiberglass cloth-based laminated board.
Example 1:
1. preparing materials:
(1) And (3) filler dispersion: firstly, adding 20 parts by weight of phosphorus-containing epoxy resin and 50 parts by weight of novolac epoxy resin into a high-speed stirrer barrel, then adding 20 parts by weight of PMA (the PMA mainly adjusts viscosity to better disperse the filler), pushing the batching barrel to a high-speed stirrer, starting the high-speed stirrer, adding 20 parts by weight of filler (the filler is aluminum hydroxide and has the purity of more than 99%), adding the filler while stirring, starting to time each tank after the addition is finished, stirring for more than 4.5H, and starting to start high-speed stirring for more than 1000r/Min when the filler is dispersed;
(2) Resin tank feeding: then 50 parts of novolac epoxy resin and 20 parts of high-heat-resistance epoxy resin are injected into a batching big tank, after the addition of the resin amount is finished, the resin with the filler is added into the batching tank, a stirrer is started during the addition, the resin with the filler is injected while stirring, the filler is confirmed to be completely dispersed (the filler is considered to be completely dispersed when no agglomeration is observed) before the addition, and the high-speed stirring and dispersion are continuously needed when the dispersion is not complete;
(3) Adding a curing agent: after all the raw materials are added into a batching vat, 20 parts of curing agent phenolic resin, 50 parts of benzoxazine resin, 60 parts of phosphorus-containing flame retardant curing agent and 0.5 part of catalyst 2-MI (dimethylimidazole) are added into the batching vat, so that the curing reaction is fully generated between the raw materials and the epoxy resin. Note: this process required continuous stirring for 5H, with the temperature controlled at 30 ℃.
(4) stopping and measuring S/G: after the reaction is carried out for 5 hours, a proper amount of glue solution is extracted by using a sampling product to test the S/G (curing time) of the glue solution in a laboratory, and the S/G range of the glue solution with the formula is as follows: 280-320S. And after the product is qualified, carrying out the next step of impregnation and gluing production. If the S/G is too long, a proper amount of catalyst can be added to accelerate the reaction. If the S/G is shorter, glue with long S/G needs to be additionally arranged for uniform mixing. The other preparation method can be configured by referring to the method described above, but the addition amount of the resin needs to be increased to 10% -20% of the original formula.
1. The ingredients mainly comprise the following materials:
1. Epoxy resin (including bisphenol A epoxy resin, novolac epoxy resin, phosphorus-containing epoxy resin, etc.)
2. Curing agent: phenolic resin, benzoxazine, phosphorus-containing flame-retardant curing agent
3. dimethyl imidazole (catalyst)
4. Propylene glycol methyl ether acetate (PMA) solvent
The resin is generally stored by dissolving in acetone and storing in an iron bucket at a weight ratio of about 80%
The phenolic resin is used as a curing agent, and the resin is subjected to crosslinking curing reaction at a proper temperature.
2-MI is used as a catalyst to initiate and accelerate the cure rate, which is evident in the S/G adjustment.
PMA is used as a solvent for adjusting the viscosity of the glue and maintaining a relatively uniform and stable system of the glue, which is important for the sizing and semi-curing reactions in the Treating process.
2. Impregnation:
The procedure is to immerse the glass fiber cloth into the prepared glue, and then to dry the glass fiber cloth to obtain a semi-solid piece with proper parameters for subsequent production.
The method comprises the following specific steps: the electronic-grade glass fiber cloth is driven on a cloth frame of an impregnation machine, the advance of the electronic-grade glass fiber cloth is controlled by tension, the glass cloth can pass through an impregnation tank (glue is pumped into the impregnation tank through a pipeline) which is impregnated with the glue, the glass cloth impregnated with the glue can enter an oven, redundant solvent is volatilized, and further reaction of resin and curing agent is carried out. After drying, the product is a semi-finished product: prepreg (PP for short).
3. stacking:
And matching PP with different PP numbers according to different thicknesses and plan requirements. And sending the stacked materials into a combination chamber.
4. Combining:
Covering the PP stacked in front with a copper foil on one side or two sides, adding the die-steel plate, combining, and feeding into a hot press.
5. and (3) laminating:
Melting the resin in the prepreg at high temperature, and expelling bubbles under high pressure to gradually harden the resin and adhere the resin to the copper foil.
description of Hot pressing procedure
The hot pressing is to melt the (B-stage) resin at high temperature and high pressure, completely expel the gas and completely solidify the resin, and complete the firm bonding between the pp layers and the copper foil. According to the diffusion principle, the bonding is realized by mutual diffusion and permeation between macromolecules on the interface, and then interweaving is generated. The press used in the embodiment of the invention is a cold and hot split type vacuum press, and the main process parameters are temperature rising conditions and pressure and vacuum degree control. In this example, the temperature is controlled to 1.2-1.8 deg.C/min, the pressure is 3.0MPa, and the vacuum is 730 mmhg.
6. And (3) cutting and checking:
And cutting off the edge materials of the laminated substrate, and then, inspecting the appearance, the thickness and the like and then discharging.
example 2:
1. Preparing materials:
(1) And (3) filler dispersion: firstly, 18 parts by weight of phosphorus-containing epoxy resin and 48 parts by weight of novolac epoxy resin are added into a high-speed mixer barrel, 18 parts by weight of PMA (the PMA is mainly used for adjusting viscosity and enabling the filler to be better dispersed) is added, the batching barrel is pushed to a position below the high-speed mixer, the high-speed mixer is started, 18 parts of filler (the filler is obtained by mixing aluminum hydroxide and silicon dioxide according to a ratio of 1 to 1) is added, the filler must be added while stirring, each tank is started to stir for more than 4.5H after the addition is finished, and the high-speed stirring needs to be started to reach more than 1000r/Min when the filler is dispersed;
(2) resin tank feeding: then, putting 48 parts of novolac epoxy resin and 18 parts of high-heat-resistance epoxy resin into a batching big tank, adding the filled resin into the batching tank after the resin amount is added, starting a stirrer during adding, stirring while adding the filled resin, and confirming that the filler is completely dispersed (visual non-agglomeration can be regarded as complete dispersion) before adding, wherein incomplete dispersion needs to be continuously stirred and dispersed at a high speed;
(3) adding a curing agent: after all the raw materials are added into a batching vat, 18 parts of curing agent phenolic resin, 48 parts of benzoxazine resin, 58 parts of phosphorus-containing flame retardant curing agent and 0.45 part of catalyst 2-MI (dimethylimidazole) are added into the batching vat, so that the curing reaction is fully generated between the raw materials and the epoxy resin. Note: this process required continuous stirring for 5H, with the temperature controlled at 30 ℃.
(4) Stopping and measuring S/G: after the reaction is carried out for 5 hours, a proper amount of glue solution is extracted by using a sampling product to test the S/G (curing time) of the glue solution in a laboratory, and the S/G range of the glue solution with the formula is as follows: 280-320S. And after the product is qualified, carrying out the next step of impregnation and gluing production. If the S/G is too long, a proper amount of catalyst can be added to accelerate the reaction. If the S/G is shorter, glue with long S/G needs to be additionally arranged for uniform mixing. The other preparation method can be configured by referring to the method described above, but the addition amount of the resin needs to be increased to 10% -20% of the original formula.
1. The ingredients mainly comprise the following materials:
2. epoxy resin (including bisphenol A epoxy resin, novolac epoxy resin, phosphorus-containing epoxy resin, etc.)
2. Curing agent: phenolic resin, benzoxazine, phosphorus-containing flame-retardant curing agent
3. Dimethyl imidazole (catalyst)
4. Propylene glycol methyl ether acetate (PMA) solvent
The resin is generally stored by dissolving in acetone and holding in an iron tub, and about 80% by weight of phenolic resin is used as a curing agent, and the resin is subjected to a crosslinking curing reaction at a suitable temperature.
2-MI is used as a catalyst to initiate and accelerate the cure rate, which is evident in the S/G adjustment.
PMA is used as a solvent for adjusting the viscosity of the glue and maintaining a relatively uniform and stable system of the glue, which is important for the sizing and semi-curing reactions in the Treating process.
2. Impregnation:
the procedure is to immerse the glass fiber cloth into the prepared glue, and then to dry the glass fiber cloth to obtain a semi-solid piece with proper parameters for subsequent production.
The method comprises the following specific steps: the electronic-grade glass fiber cloth is driven on a cloth frame of an impregnation machine, the advance of the electronic-grade glass fiber cloth is controlled by tension, the glass cloth can pass through an impregnation tank (glue is pumped into the impregnation tank through a pipeline) which is impregnated with the glue, the glass cloth impregnated with the glue can enter an oven, redundant solvent is volatilized, and further reaction of resin and curing agent is carried out. After drying, the product is a semi-finished product: prepreg (PP for short).
3. stacking:
And matching PP with different PP numbers according to different thicknesses and plan requirements. And sending the stacked materials into a combination chamber.
4. Combining:
covering the PP stacked in front with a copper foil on one side or two sides, adding the die-steel plate, combining, and feeding into a hot press.
5. And (3) laminating:
Melting the resin in the prepreg at high temperature, and expelling bubbles under high pressure to gradually harden the resin and adhere the resin to the copper foil.
description of Hot pressing procedure
The hot pressing is to melt the (B-stage) resin at high temperature and high pressure, completely expel the gas and completely solidify the resin, and complete the firm bonding between the pp layers and the copper foil. According to the diffusion principle, the bonding is realized by mutual diffusion and permeation between macromolecules on the interface, and then interweaving is generated. The press used in the embodiment of the invention is a cold and hot split type vacuum press, and the main process parameters are temperature rising conditions and pressure and vacuum degree control. In this example, the temperature is controlled to 1.2-1.8 deg.C/min, the pressure is 3.0MPa, and the vacuum is 730 mmhg.
6. And (3) cutting and checking:
and cutting off the edge materials of the laminated substrate, and then, inspecting the appearance, the thickness and the like and then discharging.
Example 3:
1. Preparing materials:
(1) and (3) filler dispersion: firstly, 22 parts by weight of phosphorus-containing epoxy resin and 52 parts by weight of novolac epoxy resin are put into a high-speed mixer barrel, 22 parts by weight of PMA (the PMA mainly adjusts viscosity to enable the filler to be better dispersed) is added, the batching barrel is pushed to a high-speed mixer, the high-speed mixer is started, 22 parts of filler (the filler is silicon dioxide, the purity is more than 99 percent) is added, the filler must be added while stirring, each tank is started to stir for more than 4.5H after the addition is finished, and the high-speed stirring needs to be started to reach more than 1000r/Min when the filler is dispersed;
(2) Resin tank feeding: then 52 parts of novolac epoxy resin and 22 parts of high-heat-resistance epoxy resin are injected into a batching big tank, after the addition of the resin amount is finished, the resin with the filler is added into the batching tank, a stirrer is started during the addition, the resin with the filler is injected while stirring, the filler is confirmed to be completely dispersed (the filler is considered to be completely dispersed when no agglomeration is observed) before the addition, and the high-speed stirring and dispersion are continuously needed when the dispersion is not complete;
(3) Adding a curing agent: after all the raw materials are added into a batching vat, 22 parts of curing agent phenolic resin, 52 parts of benzoxazine resin, 62 parts of phosphorus-containing flame-retardant curing agent and 0.55 part of catalyst 2-MI (dimethylimidazole) are added into the batching vat, so that the curing reaction is fully generated between the raw materials and the epoxy resin. Note: this process required continuous stirring for 5H, with the temperature controlled at 30 ℃.
(4) Stopping and measuring S/G: after the reaction is carried out for 5 hours, a proper amount of glue solution is extracted by using a sampling product to test the S/G (curing time) of the glue solution in a laboratory, and the S/G range of the glue solution with the formula is as follows: 280-320S. And after the product is qualified, carrying out the next step of impregnation and gluing production. If the S/G is too long, a proper amount of catalyst can be added to accelerate the reaction. If the S/G is shorter, glue with long S/G needs to be additionally arranged for uniform mixing. The other preparation method can be configured by referring to the method described above, but the addition amount of the resin needs to be increased to 10% -20% of the original formula.
1. The ingredients mainly comprise the following materials:
3. epoxy resin (including bisphenol A epoxy resin, novolac epoxy resin, phosphorus-containing epoxy resin, etc.)
2. curing agent: phenolic resin, benzoxazine, phosphorus-containing flame-retardant curing agent
3. dimethyl imidazole (catalyst)
4. propylene glycol methyl ether acetate (PMA) solvent
The resin is generally stored by dissolving in acetone and holding in an iron tub, and about 80% by weight of phenolic resin is used as a curing agent, and the resin is subjected to a crosslinking curing reaction at a suitable temperature.
2-MI is used as a catalyst to initiate and accelerate the cure rate, which is evident in the S/G adjustment.
PMA is used as a solvent for adjusting the viscosity of the glue and maintaining a relatively uniform and stable system of the glue, which is important for the sizing and semi-curing reactions in the Treating process.
2. Impregnation:
the procedure is to immerse the glass fiber cloth into the prepared glue, and then to dry the glass fiber cloth to obtain a semi-solid piece with proper parameters for subsequent production.
the method comprises the following specific steps: the electronic-grade glass fiber cloth is driven on a cloth frame of an impregnation machine, the advance of the electronic-grade glass fiber cloth is controlled by tension, the glass cloth can pass through an impregnation tank (glue is pumped into the impregnation tank through a pipeline) which is impregnated with the glue, the glass cloth impregnated with the glue can enter an oven, redundant solvent is volatilized, and further reaction of resin and curing agent is carried out. After drying, the product is a semi-finished product: prepreg (PP for short).
3. Stacking:
and matching PP with different PP numbers according to different thicknesses and plan requirements. And sending the stacked materials into a combination chamber.
4. Combining:
Covering the PP stacked in front with a copper foil on one side or two sides, adding the die-steel plate, combining, and feeding into a hot press.
5. And (3) laminating:
Melting the resin in the prepreg at high temperature, and expelling bubbles under high pressure to gradually harden the resin and adhere the resin to the copper foil.
description of Hot pressing procedure
the hot pressing is to melt the (B-stage) resin at high temperature and high pressure, completely expel the gas and completely solidify the resin, and complete the firm bonding between the pp layers and the copper foil. According to the diffusion principle, the bonding is realized by mutual diffusion and permeation between macromolecules on the interface, and then interweaving is generated. The press used in the embodiment of the invention is a cold and hot split type vacuum press, and the main process parameters are temperature rising conditions and pressure and vacuum degree control. In this example, the temperature is controlled to 1.2-1.8 deg.C/min, the pressure is 3.0MPa, and the vacuum is 730 mmhg.
6. and (3) cutting and checking:
And cutting off the edge materials of the laminated substrate, and then, inspecting the appearance, the thickness and the like and then discharging.
Comparative example 1 (high heat resistant high Tg copper clad laminate suitable for lead-free process):
The high-Tg lead-free copper-clad plate (NY2140) which is produced by Shanghai Asia copper-clad plate Co., Ltd, has high heat resistance, excellent CAF resistance and easy PCB processing is selected in the comparative example, and the copper-clad plate mainly adopts halogen (Br and other elements) as a flame retardant.
Comparative example 2 (conventional common high Tg panel):
the comparative example selected was an FR-4 epoxy board.
examples and comparative Performance parameter tables:
t288 refers to the maximum time that the substrate can withstand the high temperatures of soldering at 288 c without causing decomposition phenomena such as blistering, delamination, etc. As can be seen from the above table, in examples 1 to 3 of the present invention, compared to the conventional high Tg sheet material, Tg is significantly higher, and compared to comparative example 1, the heat endurance time is significantly longer, and the effect is better. Therefore, the substrate developed by the invention has Tg higher than 170 ℃ (DSC), excellent heat resistance (T-288>60min), low Z-axis expansion coefficient, low water absorption and CAF resistance, and the required curing temperature and time can be obviously reduced and shortened compared with other halogen-free boards, thereby improving the processing efficiency of PCB.
The invention will now be further described with reference to the accompanying drawings. The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.
Claims (10)
1. the preparation method of the halogen-free high-Tg flame-retardant heat-resistant copper-clad foil epoxy fiberglass cloth-based laminated board is characterized by comprising the following steps of:
Step 1, preparing ingredients;
Wherein, the preparation of the ingredients comprises the following steps:
Step 101, filler dispersion: taking 18-22 parts by weight of phosphorus-containing epoxy resin and 48-52 parts by weight of novolac epoxy resin, adding 18-22 parts by weight of PMA, mixing and stirring, adding 18-22 parts by weight of filler while stirring, and then accelerating stirring to form dispersed filler;
The filler is aluminum hydroxide and/or silicon dioxide, wherein the mixing ratio of the aluminum hydroxide to the silicon dioxide is 1: 1;
Step 102, resin entering: mixing 48-52 parts of novolac epoxy resin, 18-22 parts of high-heat-resistance epoxy resin and the dispersed filler obtained in the step 101 to obtain a mixture;
Step 103, adding a curing agent: adding 18-22 parts of phenolic resin, 48-52 parts of benzoxazine resin, 58-62 parts of phosphorus-containing flame retardant curing agent and 0.45-0.55 part of catalyst dimethylimidazole into the mixture obtained in the step 102, and continuously stirring to enable the mixture and the mixture to fully generate a curing reaction to form glue;
Step 104, stopping and measuring S/G: extracting a sample from the ingredients formed in the step 103, measuring the S/G value of the sample, and if the measured S/G range is in a 280-320S interval, enabling the ingredients to be qualified and entering the next step;
Step 2, impregnation: soaking glass fiber cloth into the ingredients prepared in the step 1, and drying to obtain a semi-solid sheet;
And 3, stacking: stacking at least one prepreg to a certain preset thickness so as to meet the requirements of different thicknesses;
and 4, combining: covering a single-sided or double-sided copper foil on the prepreg stacked in the step 3, combining the prepreg with a die, and then sending the combined prepreg into a hot press;
Step 5, pressing: melting the resin in the prepreg at high temperature, and expelling bubbles under high pressure to gradually harden the resin and bond the resin with the copper foil to form a substrate;
step 6, checking: and cutting off the edge materials of the laminated substrate, and then checking the appearance, the thickness and the like to obtain a finished product.
2. The method for preparing a flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth base laminated board according to claim 1, wherein in the step 101, after the addition of the silicon dioxide is completed, the rotating speed is not lower than 1000 r/Min.
3. the preparation method of the halogen-free high-Tg flame-retardant heat-resistant copper clad foil epoxy fiberglass cloth-based laminate according to claim 1 or 2, characterized in that in the step 101, after the addition of the silicon dioxide is completed, the stirring time is not less than 4.5H.
4. The method for preparing the halogen-free high-Tg flame-retardant heat-resistant copper clad foil epoxy fiberglass cloth-based laminate according to claim 1, wherein in the step 103, the stirring is continuously carried out for not less than 5H.
5. the preparation method of the halogen-free high-Tg flame-retardant heat-resistant copper clad foil epoxy fiberglass cloth-based laminate according to claim 1, wherein in the step 2, the specific steps of immersing the fiberglass cloth into the ingredients prepared in the step 1 are as follows: driving the electronic-grade glass fiber cloth on a cloth rack of an impregnation machine, controlling the glass fiber cloth to advance by tension, enabling the glass cloth to pass through an impregnation groove full of glue, enabling the glass cloth soaked with the glue to enter an oven, volatilizing redundant solvent and carrying out further reaction on resin and a curing agent; and drying to obtain the semi-fixing sheet.
6. the method for preparing the halogen-free high-Tg flame-retardant heat-resistant copper clad laminate based on epoxy fiberglass cloth as claimed in claim 1, wherein the mold in the step 4 is a mold-steel plate.
7. The method for preparing the flame-retardant heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board as claimed in claim 1, wherein in the step 5, during the pressing process, the temperature is controlled to be 1.2-1.8 ℃/min, the pressure is 3.0Mpa, and the vacuum is 730 mmhg.
8. The method for preparing the flame-retardant and heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board as claimed in claim 1, wherein in the step 104,
if the S/G is longer, adding 0.01-0.1 part of catalyst for accelerating the reaction;
if the S/G is shorter, additionally preparing a new ingredient with long S/G length according to the steps 101-103, uniformly mixing the new ingredient with the original ingredient, and then detecting the S/G, wherein in the preparation process of the new ingredient, the addition amount of the bisphenol A type bromine epoxy resin is increased by 10-20%.
9. the method for preparing the flame-retardant and heat-resistant copper foil-coated epoxy fiberglass cloth-based laminated board as claimed in claim 1, wherein the temperature is controlled to be between 25 and 50 ℃ during the curing process of step 103.
10. the flame-retardant heat-resistant copper-clad epoxy fiberglass cloth-based laminated board prepared by the preparation method of claims 1-9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113912981A (en) * | 2021-11-04 | 2022-01-11 | 江苏耀鸿电子有限公司 | High-heat-resistance medium-Tg copper-clad plate and preparation method thereof |
| CN117165028A (en) * | 2023-09-06 | 2023-12-05 | 江苏耀鸿电子有限公司 | Halogen-free heat-resistant phenolic resin copper-clad plate and forming process thereof |
| CN117656540A (en) * | 2023-11-28 | 2024-03-08 | 明光瑞智电子科技有限公司 | Preparation method and preparation equipment of halogen-free high Tg low-loss resin composition |
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| CN103214794A (en) * | 2013-05-17 | 2013-07-24 | 宏昌电子材料股份有限公司 | Halogen-free epoxy resin composition for copper-clad plate and application thereof |
| CN106166874A (en) * | 2016-06-29 | 2016-11-30 | 上海南亚覆铜箔板有限公司 | Halogen-free copper-clad plate and preparation method thereof |
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| JPH0471287A (en) * | 1990-07-12 | 1992-03-05 | Toshiba Chem Corp | Copper-clad laminated board |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113912981A (en) * | 2021-11-04 | 2022-01-11 | 江苏耀鸿电子有限公司 | High-heat-resistance medium-Tg copper-clad plate and preparation method thereof |
| CN117165028A (en) * | 2023-09-06 | 2023-12-05 | 江苏耀鸿电子有限公司 | Halogen-free heat-resistant phenolic resin copper-clad plate and forming process thereof |
| CN117165028B (en) * | 2023-09-06 | 2024-03-22 | 江苏耀鸿电子有限公司 | Halogen-free heat-resistant phenolic resin copper-clad plate and forming process thereof |
| CN117656540A (en) * | 2023-11-28 | 2024-03-08 | 明光瑞智电子科技有限公司 | Preparation method and preparation equipment of halogen-free high Tg low-loss resin composition |
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