CN113388349B - Preparation process of copper foil adhesive special for high CTI (comparative tracking index) and application of copper foil adhesive to paper-based copper-clad plate - Google Patents

Preparation process of copper foil adhesive special for high CTI (comparative tracking index) and application of copper foil adhesive to paper-based copper-clad plate Download PDF

Info

Publication number
CN113388349B
CN113388349B CN202110523378.XA CN202110523378A CN113388349B CN 113388349 B CN113388349 B CN 113388349B CN 202110523378 A CN202110523378 A CN 202110523378A CN 113388349 B CN113388349 B CN 113388349B
Authority
CN
China
Prior art keywords
parts
weight
copper foil
paper
phenolic resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110523378.XA
Other languages
Chinese (zh)
Other versions
CN113388349A (en
Inventor
欧阳主再
王文超
傅燕燕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FUJIAN LIHAO ELECTRONIC TECHNOLOGY CO LTD
Original Assignee
FUJIAN LIHAO ELECTRONIC TECHNOLOGY CO LTD
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by FUJIAN LIHAO ELECTRONIC TECHNOLOGY CO LTD filed Critical FUJIAN LIHAO ELECTRONIC TECHNOLOGY CO LTD
Priority to CN202110523378.XA priority Critical patent/CN113388349B/en
Publication of CN113388349A publication Critical patent/CN113388349A/en
Application granted granted Critical
Publication of CN113388349B publication Critical patent/CN113388349B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/12—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B29/005—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to another layer of paper or cardboard 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
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C08G14/10—Melamines
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a preparation process of a copper foil adhesive special for high CTI (comparative tracking index) and application of the copper foil adhesive to a paper-based copper-clad plate, belongs to the field of the paper-based copper-clad plate, reduces the carbon content in a formula system through resin modification, prepares the copper foil adhesive with high CTI resistance, and is applied to the paper-based copper-clad plate. The beneficial effects of the invention are: the melamine modified phenolic resin is adopted as the main resin of the glue solution, and after the melamine modification, the carbon-containing proportion of the resin is reduced, so that the formation of carbonized traces of the material is not facilitated, and the copper foil glue which has a high relative tracking index (CTI is more than or equal to 600V) and meets the peeling resistance requirement of a copper foil is prepared.

Description

Preparation process of special copper foil adhesive with high CTI (comparative tracking index) and application of special copper foil adhesive to paper-based copper-clad plate
Technical Field
The invention relates to the field of paper-based copper-clad plates, in particular to a preparation process of a copper foil adhesive special for high CTI and application of the copper foil adhesive to the paper-based copper-clad plate.
Background
At present, the use safety of electronic products is more and more emphasized, the CTI (tracking resistance index) of a copper clad laminate is a characteristic of the insulating capability of an insulating material in a humid and dirty environment, and the requirement that the CTI is more than or equal to 600V is met through the improvement of a copper foil adhesive formula and a process. In the traditional technology, the paper-based copper-clad plate meeting the CTI value of more than or equal to 600V is obtained by improving the performance of glue for the paper-based PP sheet, but the method has the characteristics of high cost and complex process.
For example, the invention patent application with publication number CN107603543A discloses a two-side high CTI glue solution, which comprises the following raw materials in parts by weight: 30-40 parts of epoxy resin, 15-32 parts of bromine-free epoxy resin, 18-25 parts of modified isocyanate, 20-30 parts of modified phenolic resin, 8-20 parts of polymeric phosphate and 5-10 parts of aluminum hydroxide. Epoxy resin and bromine-free epoxy resin are adopted as main raw materials, the CTI value of the glue solution is prepared by controlling the ratio of the epoxy resin and the bromine-free epoxy resin, high-pressure-resistant modified isocyanate is added in the formula, the flame retardance, the thermal stability and the compatibility of the glue solution are improved by utilizing the synergistic effect of the polymeric phosphate and the aluminum hydroxide, the impact toughness, the adhesion property, the heat resistance, the flame retardance, the curing speed and the like of the glue solution are further improved by adding the modified phenolic resin, and the improvement of the glue performance of the paper-based PP sheet is realized.
And for another example, the invention patent with the publication number CN102492259B discloses a tung oil modified alkylphenol-phenolic resin composition and a method for producing a high CTI flame-retardant paper-based copper-clad plate. The method for producing the high CTI flame-retardant paper-based copper-clad plate by using the tung oil modified alkylphenol-phenolic resin composition comprises the following steps: the resin composition was prepared as follows: preparing primary paint; preparing paint for two times; (II) preparing a sizing material sheet: painting and gluing the bleached wood pulp paper for one time, drying and then dip-coating the paper for two times to obtain a sizing sheet; (III) preparing the high CTI flame-retardant paper-based copper-clad plate: n pieces of the upper sizing sheets are overlapped, one piece of the sizing copper foil is attached, hot pressing is carried out for 80-110 minutes under the pressure of 26-30MPa and the temperature of 178-182 ℃, and then the board is cooled and unloaded, so that the high CTI flame retardant paper-based copper-clad board is prepared. It is also an improvement in the properties of a glue for sizing a web.
Accordingly, the present inventors have made extensive studies on the above problems and have made the present invention.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation process of a copper foil adhesive special for high CTI, which comprises the following steps:
step one, adding phenol and a first solvent into a reaction kettle, and stirring;
step two, adding polyformaldehyde, melamine and a catalyst into the mixture obtained in the step one, and continuously stirring;
step three, the temperature is raised to the specified temperature, timing is started, then the temperature is controlled in a reaction temperature range, and the reaction temperature range is kept for a certain time and then cooled;
and step four, adding a first solvent into the obtained product for dilution to obtain the melamine modified phenolic resin.
Preferably, the phenol is one or a combination of phenol and o-cresol.
Preferably, the first solvent is methanol or ethanol.
Preferably, in the first step, 180 to 230 parts by weight of phenol and 140 to 160 parts by weight of the first solvent are added to the reaction vessel.
Preferably, the polyoxymethylene in step two is paraformaldehyde.
Preferably, the catalyst in the second step is aliphatic ammonia catalyst, preferably ethylenediamine or triethylamine.
Preferably, 200 to 220 parts by weight of polyoxymethylene, 140 to 160 parts by weight of melamine and 0.5 to 3 parts by weight of catalyst are added to the mixture in step two in step one.
Preferably, in the third step, the temperature is raised to 60 +/-2 ℃ and the timing is started, then the temperature is controlled to be 60-100 ℃ and kept for 20-120 minutes, and then the temperature is reduced to below 50 ℃.
Preferably, 250 to 350 parts by weight of the first solvent is added in step four for dilution.
Preferably, in the second step, the polyformaldehyde and the melamine are added into the mixture in the first step, and the catalyst is added after the stirring is continued for 5 to 15 minutes.
Preferably, 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of phenolic epoxy resin and 2-10 parts of rubber vulcanizing agent are added into a stirring kettle, and the copper foil adhesive is obtained after stirring.
Preferably, the second solvent includes 140 to 180 parts by weight of toluene, 50 to 80 parts by weight of butanone, and 140 to 180 parts by weight of the first solvent.
Preferably, the solid phenolic resin is an electronic grade toughened solid phenolic resin, and the preferred type is PF-8020 linear phenolic resin.
Preferably, the novolac epoxy resin is F-51 novolac epoxy resin.
Preferably, the rubber vulcanizing agent is methylene dichloroaniline.
The melamine modified phenolic resin is adopted as the main resin of the glue solution, and after the melamine modification, the carbon-containing proportion of the resin is reduced, so that the formation of carbonized traces of the material is not facilitated, and the copper foil glue which has a high relative tracking index (CTI is more than or equal to 600V) and meets the peeling resistance requirement of a copper foil is prepared.
Adjusting the viscosity at 25 ℃, coating the mixture on the rough surface of a copper foil, drying the mixture to form a gummed copper foil, combining a paper-based prepreg, and pressing the combined paper-based prepreg on a hot press to form a paper-based copper-clad plate by controlling the temperature and the pressure; after the high CTI copper foil adhesive is crosslinked and cured, a macromolecular reticular structure is formed, and meanwhile, the high CTI copper foil adhesive has the insulating capability in humid and dirty environments, namely, the high CTI copper foil adhesive has the characteristic of higher relative tracking index.
The invention also provides an application of the high CTI special copper foil adhesive on the paper-based copper-clad plate, which is characterized in that the copper foil adhesive is coated on the rough surface of a copper foil with the thickness of 15-35 mu m, dried to be made into a glued copper foil and cut into the required size, and the glued copper foil and the paper-based prepreg are hot-pressed together to obtain the paper-based copper-clad plate.
In the traditional technology, the paper-based copper-clad plate meeting the CTI value of more than or equal to 600V is obtained by improving the performance of glue for a paper-based PP sheet, but the method has the characteristics of high cost and complex process; the invention improves the copper foil adhesive, has simple process and low cost, and can meet the requirement of mass production.
According to the invention, the carbon content in a formula system is reduced through the modification of resin, and the copper foil adhesive with high CTI resistance is prepared and applied to the paper-based copper-clad plate; meanwhile, the invention is independently improved from the copper foil adhesive, the leakage resistance of the product is greatly improved under the condition of keeping the other performances of the product, the production cost of the product is reduced, and the cost performance is higher, namely the product meeting the CTI value of more than or equal to 600V can be produced at lower cost.
Has the beneficial effects that:
the technical scheme of the invention has the following beneficial effects:
(1) The melamine modified phenolic resin is adopted as the main resin of the glue solution, and after the melamine modification, the carbon-containing proportion of the resin is reduced, so that the formation of a carbonization trace of the material is not facilitated, and the copper foil glue which has a high relative tracking index (CTI is more than or equal to 600V) and meets the peeling resistance requirement of a copper foil is prepared;
(2) Adjusting the viscosity at 25 ℃, coating the mixture on the rough surface of a copper foil, drying the mixture to form a coated copper foil, combining a paper-based prepreg, and pressing the combined paper-based prepreg and the coated copper foil on a hot press to form a paper-based copper-clad plate by controlling the temperature and the pressure; after the high CTI copper foil adhesive is crosslinked and cured, a macromolecular reticular structure is formed, and meanwhile, the high CTI copper foil adhesive has the insulating capability in a humid and dirty environment, namely, the characterization of a higher relative electric leakage tracking index is realized;
(3) In the traditional technology, the paper-based copper-clad plate meeting the CTI value of more than or equal to 600V is obtained by improving the performance of glue for a paper-based PP sheet, but the method has the characteristics of high cost and complex process; the invention improves the copper foil adhesive aspect, has simple process and low cost, and can meet the requirement of mass production;
(4) The carbon content in a formula system is reduced through resin modification, and the copper foil adhesive with high CTI resistance is prepared and applied to the paper-based copper-clad plate; meanwhile, the invention is independently improved from the copper foil adhesive, the leakage resistance of the product is greatly improved under the condition of keeping the other performances of the product, the production cost of the product is reduced, and the cost performance is higher, namely the product meeting the CTI value of more than or equal to 600V can be produced at lower cost.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the embodiments of the present invention will be described in detail and completely with reference to the examples of the present invention, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without inventive efforts based on the embodiments of the present invention, are within the scope of protection of the present invention. Thus, the following detailed description of the embodiments of the present invention, provided in the examples, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The embodiment reduces the carbon content in a formula system through the modification of resin, prepares the copper foil adhesive with high CTI resistance, is applied to the paper-based copper-clad plate, and has the following specific scheme:
a preparation process of a high CTI special copper foil adhesive comprises the following steps:
step one, adding 180-230 parts by weight of phenol and 140-160 parts by weight of first solvent into a reaction kettle, and stirring;
step two, adding 200-220 parts by weight of polyformaldehyde, 140-160 parts by weight of melamine and 0.5-3 parts by weight of catalyst into the mixture obtained in the step one, and continuing stirring;
step three, raising the temperature to 60 +/-2 ℃, starting timing, controlling the temperature to 60-100 ℃, keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
As a preferred embodiment, the phenol is one or a combination of phenol and o-cresol.
As a preferred embodiment, the first solvent is methanol or ethanol.
In a preferred embodiment, the polyoxymethylene in step two is paraformaldehyde.
In a preferred embodiment, the catalyst in step two is an aliphatic ammonia catalyst, preferably ethylenediamine or triethylamine.
As a preferred embodiment, in the second step, the polyformaldehyde and the melamine are added into the mixture in the first step, and the catalyst is added after the stirring is continued for 5 to 15 minutes.
As a preferable embodiment, 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of phenolic epoxy resin and 2-10 parts of rubber vulcanizing agent are added into a stirring kettle, and the copper foil adhesive is obtained after stirring.
As a preferred embodiment, the second solvent comprises 140 to 180 parts by weight of toluene, 50 to 80 parts by weight of methyl ethyl ketone and 140 to 180 parts by weight of methanol or ethanol.
As a preferable embodiment, the solid phenolic resin is an electronic grade toughened solid phenolic resin, and the preferable model is PF-8020 linear phenolic resin.
As a preferred embodiment, the novolac epoxy resin is F-51 novolac epoxy resin.
As a preferred embodiment, the rubber vulcanizing agent is methylene dichloroaniline.
The melamine modified phenolic resin is adopted as the main resin of the glue solution, the carbon-containing proportion of the resin is reduced after the melamine modification, the carbonization trace of the material is not favorably formed, and the copper foil glue which has high relative tracking index (CTI is more than or equal to 600V) and meets the peeling resistance requirement of the copper foil is prepared.
Adjusting the viscosity at 25 ℃, coating the mixture on the rough surface of a copper foil, drying the mixture to form a coated copper foil, combining a paper-based prepreg, and pressing the combined paper-based prepreg and the coated copper foil on a hot press to form a paper-based copper-clad plate by controlling the temperature and the pressure; after the high CTI copper foil adhesive is crosslinked and cured, a macromolecular reticular structure is formed, and meanwhile, the high CTI copper foil adhesive has the insulating capability in humid and dirty environments, namely, the high CTI copper foil adhesive has the characteristic of higher relative tracking index.
The embodiment also provides an application of the high CTI special copper foil adhesive to the paper-based copper-clad plate, wherein the copper foil adhesive is coated on the rough surface of a copper foil with the thickness of 15-35 mu m, dried to prepare a coated copper foil, cut into required size, and hot-pressed together with a paper-based prepreg to obtain the paper-based copper-clad plate.
In the traditional technology, the paper-based copper-clad plate meeting the CTI value of more than or equal to 600V is obtained by improving the performance of glue for a paper-based PP sheet, but the method has the characteristics of high cost and complex process; the embodiment is improved from the aspect of copper foil glue, so that the process is simple, the cost is low, and the requirement of mass production can be met.
The embodiment reduces the carbon content in the formula system through the modification of the resin, prepares the copper foil adhesive with high CTI resistance, and applies the copper foil adhesive to the paper-based copper-clad plate; meanwhile, the embodiment is independently improved from the copper foil adhesive, the electric leakage resistance of the product is greatly improved under the condition of keeping the other performances of the product, the production cost of the product is reduced, and the cost performance is higher, namely the product meeting the CTI value of more than or equal to 600V can be produced at lower cost.
The following examples and comparative examples further illustrate the beneficial effects of the product prepared by the technical solution of the present embodiment.
Example one
The embodiment relates to a preparation process of copper foil adhesive and application thereof on a paper-based copper-clad plate, which comprises the following specific steps:
step one, adding 180-200 parts by weight of phenol and 140-160 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 200-220 parts by weight of paraformaldehyde and 140-160 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of ethylenediamine;
step three, raising the temperature to 60 +/-2 ℃ and starting timing, then controlling the temperature to 60-100 ℃ and keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And step five, adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of methanol; the solid phenolic resin is electronic grade toughened solid phenolic resin, and the model is PF-8020 linear phenolic resin.
The copper foil adhesive prepared by the embodiment is coated on the hair side of a copper foil used for roughening 215 g/square meter, and after drying, the solubility is controlled within the range of 22-26, and the glue content is controlled within the range of 18-24 g/square meter; and superposing the prepared 1 piece of glued copper foil with 6 pieces of paper-based PP (propene Polymer) sheets, and pressing the laminated sheets for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, thus obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
Example two
The embodiment is a preparation process of copper foil adhesive and application thereof on a paper-based copper-clad plate, and the preparation process comprises the following specific steps:
step one, adding 210-230 parts by weight of o-cresol and 140-160 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 200-220 parts by weight of paraformaldehyde and 140-160 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of triethylamine;
step three, raising the temperature to 60 +/-2 ℃ and starting timing, then controlling the temperature to 60-100 ℃ and keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And fifthly, adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of methanol; the solid phenolic resin is an electronic grade toughened solid phenolic resin with the model of PF-8020 linear phenolic resin.
Coating the copper foil adhesive prepared by the embodiment on the rough surface of a copper foil for roughening a square meter of 215 g/square meter, and controlling the solubility to be within the range of 22-26 and the gum content to be within the range of 18-24 g/square meter after drying; and superposing the prepared 1 piece of glued copper foil with 6 pieces of paper-based PP (propene Polymer) sheets, and pressing the laminated sheets for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, thus obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
EXAMPLE III
The embodiment is a preparation process of copper foil adhesive and application thereof on a paper-based copper-clad plate, and the preparation process comprises the following specific steps:
step one, adding 180-200 parts by weight of phenol and 150-160 parts by weight of ethanol into a reaction kettle, and stirring;
step two, adding 210-220 parts by weight of paraformaldehyde and 150-160 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of ethylenediamine;
step three, raising the temperature to 60 +/-2 ℃ and starting timing, then controlling the temperature to 60-100 ℃ and keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of ethanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And fifthly, adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of ethanol; the solid phenolic resin is an electronic grade toughened solid phenolic resin with the model of PF-8020 linear phenolic resin.
Coating the copper foil adhesive prepared by the embodiment on the rough surface of a copper foil for roughening a square meter of 215 g/square meter, and controlling the solubility to be within the range of 22-26 and the gum content to be within the range of 18-24 g/square meter after drying; and superposing the prepared 1 piece of glued copper foil with 6 pieces of paper-based PP (propene Polymer) sheets, and pressing the laminated sheets for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, thus obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
Example four
The embodiment is a preparation process of copper foil adhesive and application thereof on a paper-based copper-clad plate, and the preparation process comprises the following specific steps:
step one, adding 180-200 parts by weight of phenol and 140-160 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 200-220 parts by weight of paraformaldehyde and 140-160 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of triethylamine;
step three, raising the temperature to 60 +/-2 ℃ and starting timing, then controlling the temperature to 60-100 ℃ and keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And fifthly, adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of methanol; the solid phenolic resin is an electronic grade toughened solid phenolic resin with the model of PF-8020 linear phenolic resin.
Coating the copper foil adhesive prepared by the embodiment on the rough surface of a copper foil for roughening a square meter of 215 g/square meter, and controlling the solubility to be within the range of 22-26 and the gum content to be within the range of 18-24 g/square meter after drying; and (3) overlapping the prepared 1 piece of the gluing copper foil with 6 pieces of paper-based PP sheets, pressing for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, and obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
Comparative example 1
The comparative example is a preparation process of copper foil adhesive and application thereof on a paper-based copper-clad plate, and comprises the following specific steps:
step one, adding 180-200 parts by weight of phenol and 140-160 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 540-590 parts by weight of formaldehyde solution and 140-160 parts by weight of melamine into the mixture obtained in the step one, continuing to stir for 5-15 minutes, and then adding 0.5-3 parts by weight of ethylenediamine;
step three, raising the temperature to 60 +/-2 ℃ and starting timing, then controlling the temperature to 60-100 ℃ and keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And step five, adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of methanol; the solid phenolic resin is electronic grade toughened solid phenolic resin, and the model is PF-8020 linear phenolic resin.
Coating the copper foil adhesive prepared by the embodiment on the rough surface of a copper foil for roughening a square meter of 215 g/square meter, and controlling the solubility to be within the range of 22-26 and the gum content to be within the range of 18-24 g/square meter after drying; and superposing the prepared 1 piece of glued copper foil with 6 pieces of paper-based PP (propene Polymer) sheets, and pressing the laminated sheets for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, thus obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
Comparative example No. two
The comparative example is a preparation process of copper foil adhesive and application thereof on a paper-based copper-clad plate, and comprises the following specific steps:
step one, adding 600-630 parts by weight of cardanol and 140-160 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 200-220 parts by weight of paraformaldehyde and 140-160 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of ethylenediamine;
step three, raising the temperature to 60 +/-2 ℃ and starting timing, then controlling the temperature to 60-100 ℃ and keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And fifthly, adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of methanol; the solid phenolic resin is an electronic grade toughened solid phenolic resin with the model of PF-8020 linear phenolic resin.
Coating the copper foil adhesive prepared by the embodiment on the rough surface of a copper foil for roughening a square meter of 215 g/square meter, and controlling the solubility to be within the range of 22-26 and the gum content to be within the range of 18-24 g/square meter after drying; and (3) overlapping the prepared 1 piece of the gluing copper foil with 6 pieces of paper-based PP sheets, pressing for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, and obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
Comparative example No. three
The comparative example is a preparation process of copper foil adhesive and application thereof on a paper-based copper-clad plate, and comprises the following specific steps:
step one, adding 220-240 parts by weight of phenol and 180-200 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 200-220 parts by weight of paraformaldehyde and 140-160 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of ethylenediamine;
step three, raising the temperature to 60 +/-2 ℃ and starting timing, then controlling the temperature to 60-100 ℃ and keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And fifthly, adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of methanol; the solid phenolic resin is an electronic grade toughened solid phenolic resin with the model of PF-8020 linear phenolic resin.
Coating the copper foil adhesive prepared by the embodiment on the rough surface of a copper foil for roughening a square meter of 215 g/square meter, and controlling the solubility to be within the range of 22-26 and the gum content to be within the range of 18-24 g/square meter after drying; and superposing the prepared 1 piece of glued copper foil with 6 pieces of paper-based PP (propene Polymer) sheets, and pressing the laminated sheets for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, thus obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
Comparative example No. four
The comparative example is a preparation process of copper foil adhesive and application thereof on a paper-based copper-clad plate, and comprises the following specific steps:
step one, adding 140-160 parts by weight of phenol and 100-120 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 200-220 parts by weight of paraformaldehyde and 140-160 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of ethylenediamine;
step three, raising the temperature to 60 +/-2 ℃, starting timing, controlling the temperature to 60-100 ℃, keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And fifthly, adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of methanol; the solid phenolic resin is electronic grade toughened solid phenolic resin, and the model is PF-8020 linear phenolic resin.
The copper foil adhesive prepared by the embodiment is coated on the hair side of a copper foil used for roughening 215 g/square meter, and after drying, the solubility is controlled within the range of 22-26, and the glue content is controlled within the range of 18-24 g/square meter; and superposing the prepared 1 piece of glued copper foil with 6 pieces of paper-based PP (propene Polymer) sheets, and pressing the laminated sheets for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, thus obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
Comparative example five
The comparative example is a preparation process of copper foil adhesive and application thereof in a paper-based copper-clad plate, and comprises the following specific steps:
step one, adding 180-200 parts by weight of phenol and 140-160 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 200-220 parts by weight of paraformaldehyde and 140-160 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of formic acid;
step three, raising the temperature to 60 +/-2 ℃ and starting timing, then controlling the temperature to 60-100 ℃ and keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And fifthly, adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of methanol; the solid phenolic resin is electronic grade toughened solid phenolic resin, and the model is PF-8020 linear phenolic resin.
Coating the copper foil adhesive prepared by the embodiment on the rough surface of a copper foil for roughening a square meter of 215 g/square meter, and controlling the solubility to be within the range of 22-26 and the gum content to be within the range of 18-24 g/square meter after drying; and superposing the prepared 1 piece of glued copper foil with 6 pieces of paper-based PP (propene Polymer) sheets, and pressing the laminated sheets for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, thus obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
Comparative example six
The comparative example is a preparation process of copper foil adhesive and application thereof on a paper-based copper-clad plate, and comprises the following specific steps:
step one, adding 180-200 parts by weight of phenol and 140-160 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 220-240 parts by weight of paraformaldehyde and 180-200 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of ethylenediamine;
step three, raising the temperature to 60 +/-2 ℃ and starting timing, then controlling the temperature to 60-100 ℃ and keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And fifthly, adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of methanol; the solid phenolic resin is an electronic grade toughened solid phenolic resin with the model of PF-8020 linear phenolic resin.
The copper foil adhesive prepared by the embodiment is coated on the hair side of a copper foil used for roughening 215 g/square meter, and after drying, the solubility is controlled within the range of 22-26, and the glue content is controlled within the range of 18-24 g/square meter; and superposing the prepared 1 piece of glued copper foil with 6 pieces of paper-based PP (propene Polymer) sheets, and pressing the laminated sheets for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, thus obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
Comparative example seven
The comparative example is a preparation process of copper foil adhesive and application thereof in a paper-based copper-clad plate, and comprises the following specific steps:
step one, adding 180-200 parts by weight of phenol and 140-160 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 220-240 parts by weight of paraformaldehyde and 100-120 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of ethylenediamine;
step three, raising the temperature to 60 +/-2 ℃ and starting timing, then controlling the temperature to 60-100 ℃ and keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And fifthly, adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of methanol; the solid phenolic resin is electronic grade toughened solid phenolic resin, and the model is PF-8020 linear phenolic resin.
Coating the copper foil adhesive prepared by the embodiment on the rough surface of a copper foil for roughening a square meter of 215 g/square meter, and controlling the solubility to be within the range of 22-26 and the gum content to be within the range of 18-24 g/square meter after drying; and superposing the prepared 1 piece of glued copper foil with 6 pieces of paper-based PP (propene Polymer) sheets, and pressing the laminated sheets for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, thus obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
Comparative example eight
The comparative example is a preparation process of copper foil adhesive and application thereof on a paper-based copper-clad plate, and comprises the following specific steps:
step one, adding 180-200 parts by weight of phenol and 140-160 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 200-220 parts by weight of paraformaldehyde and 140-160 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of ethylenediamine;
step three, raising the temperature to 70 +/-2 ℃ and starting timing, then controlling the temperature to 70-100 ℃ and keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And fifthly, adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of methanol; the solid phenolic resin is an electronic grade toughened solid phenolic resin with the model of PF-8020 linear phenolic resin.
Coating the copper foil adhesive prepared by the embodiment on the rough surface of a copper foil for roughening a square meter of 215 g/square meter, and controlling the solubility to be within the range of 22-26 and the gum content to be within the range of 18-24 g/square meter after drying; and (3) overlapping the prepared 1 piece of the gluing copper foil with 6 pieces of paper-based PP sheets, pressing for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, and obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
Comparative example No. nine
The comparative example is a preparation process of copper foil adhesive and application thereof in a paper-based copper-clad plate, and comprises the following specific steps:
step one, adding 180-200 parts by weight of phenol and 140-160 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 200-220 parts by weight of paraformaldehyde and 140-160 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of ethylenediamine;
step three, raising the temperature to 50 +/-2 ℃ and starting timing, then controlling the temperature to be 50-60 ℃ and keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And step five, adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of methanol; the solid phenolic resin is electronic grade toughened solid phenolic resin, and the model is PF-8020 linear phenolic resin.
The copper foil adhesive prepared by the embodiment is coated on the hair side of a copper foil used for roughening 215 g/square meter, and after drying, the solubility is controlled within the range of 22-26, and the glue content is controlled within the range of 18-24 g/square meter; and (3) overlapping the prepared 1 piece of the gluing copper foil with 6 pieces of paper-based PP sheets, pressing for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, and obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
Comparative example ten
The comparative example is a preparation process of copper foil adhesive and application thereof in a paper-based copper-clad plate, and comprises the following specific steps:
step one, adding 180-200 parts by weight of phenol and 140-160 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 200-220 parts by weight of paraformaldehyde and 140-160 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of ethylenediamine;
step three, raising the temperature to 60 +/-2 ℃ and starting timing, then controlling the temperature to 60-100 ℃ and keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And step five, adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein, the second solvent in the fifth step comprises 140 to 180 weight parts of acetone, 50 to 80 weight parts of butanone and 140 to 180 weight parts of methanol; the solid phenolic resin is an electronic grade toughened solid phenolic resin with the model of PF-8020 linear phenolic resin.
The copper foil adhesive prepared by the embodiment is coated on the hair side of a copper foil used for roughening 215 g/square meter, and after drying, the solubility is controlled within the range of 22-26, and the glue content is controlled within the range of 18-24 g/square meter; and superposing the prepared 1 piece of glued copper foil with 6 pieces of paper-based PP (propene Polymer) sheets, and pressing the laminated sheets for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, thus obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
Comparative example eleven
The comparative example is a preparation process of copper foil adhesive and application thereof in a paper-based copper-clad plate, and comprises the following specific steps:
step one, adding 180-200 parts by weight of phenol and 140-160 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 200-220 parts by weight of paraformaldehyde and 140-160 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of ethylenediamine;
step three, raising the temperature to 60 +/-2 ℃ and starting timing, then controlling the temperature to 60-100 ℃ and keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And fifthly, adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of E-51 epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of methanol.
Coating the copper foil adhesive prepared by the embodiment on the rough surface of a copper foil for roughening a square meter of 215 g/square meter, and controlling the solubility to be within the range of 22-26 and the gum content to be within the range of 18-24 g/square meter after drying; and superposing the prepared 1 piece of glued copper foil with 6 pieces of paper-based PP (propene Polymer) sheets, and pressing the laminated sheets for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, thus obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
Comparative example twelve
The comparative example is a preparation process of copper foil adhesive and application thereof on a paper-based copper-clad plate, and comprises the following specific steps:
step one, adding 180-200 parts by weight of phenol and 140-160 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 200-220 parts by weight of paraformaldehyde and 140-160 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of ethylenediamine;
step three, raising the temperature to 60 +/-2 ℃ and starting timing, then controlling the temperature to 60-100 ℃ and keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And step five, adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of organic silicon epoxy resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of methanol.
The copper foil adhesive prepared by the embodiment is coated on the hair side of a copper foil used for roughening 215 g/square meter, and after drying, the solubility is controlled within the range of 22-26, and the glue content is controlled within the range of 18-24 g/square meter; and superposing the prepared 1 piece of glued copper foil with 6 pieces of paper-based PP (propene Polymer) sheets, and pressing the laminated sheets for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, thus obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
Comparative example thirteen
The comparative example is a preparation process of copper foil adhesive and application thereof in a paper-based copper-clad plate, and comprises the following specific steps:
step one, adding 180-200 parts by weight of phenol and 140-160 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 200-220 parts by weight of paraformaldehyde and 140-160 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of ethylenediamine;
step three, raising the temperature to 60 +/-2 ℃, starting timing, controlling the temperature to 60-100 ℃, keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And step five, adding 70-90 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of methanol; the solid phenolic resin is an electronic grade toughened solid phenolic resin with the model of PF-8020 linear phenolic resin.
The copper foil adhesive prepared by the embodiment is coated on the hair side of a copper foil used for roughening 215 g/square meter, and after drying, the solubility is controlled within the range of 22-26, and the glue content is controlled within the range of 18-24 g/square meter; and superposing the prepared 1 piece of glued copper foil with 6 pieces of paper-based PP (propene Polymer) sheets, and pressing the laminated sheets for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, thus obtaining the paper-based copper-clad plate with the thickness of 1.2 mm.
Comparative example fourteen
The comparative example is a preparation process of copper foil adhesive and application thereof in a paper-based copper-clad plate, and comprises the following specific steps:
step one, adding 180-200 parts by weight of phenol and 140-160 parts by weight of methanol into a reaction kettle, and stirring;
step two, adding 200-220 parts by weight of paraformaldehyde and 140-160 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of ethylenediamine;
step three, raising the temperature to 60 +/-2 ℃, starting timing, controlling the temperature to 60-100 ℃, keeping the temperature for 20-120 minutes, and then cooling to below 50 ℃;
and step four, adding 250-350 parts by weight of methanol into the obtained product for dilution to obtain the melamine modified phenolic resin.
And fifthly, adding 110-130 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of F-51 phenolic epoxy resin and 2-10 parts of methylene dichloroaniline into a stirring kettle, and stirring for 2 hours at 36rpm to obtain the copper foil adhesive.
Wherein the second solvent in the fifth step comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of methanol; the solid phenolic resin is an electronic grade toughened solid phenolic resin with the model of PF-8020 linear phenolic resin.
Coating the copper foil adhesive prepared by the embodiment on the rough surface of a copper foil for roughening a square meter of 215 g/square meter, and controlling the solubility to be within the range of 22-26 and the gum content to be within the range of 18-24 g/square meter after drying; and (3) overlapping the prepared 1 piece of the gluing copper foil with 6 pieces of paper-based PP sheets, pressing for 80-150 minutes by a hot press under the pressing conditions of 0-8.5Mpa and 160-185 ℃, and obtaining the paper-based copper-clad plate with the thickness of 1.2 mm. The paper-based copper-clad plate with the thickness of 1.2mm prepared by the four groups of embodiments and the fourteen groups of embodiments in proportion and the paper-based copper-clad plate with the thickness of 1.2mm sold in the market are subjected to CTI, thermal stress, peeling strength tests and appearance requirement detection, wherein the CTI tests are tested according to the regulations of GB/T4207-2012, and the specific results are shown in Table 1:
table 1 test results of paper-based copper-clad plate prepared by each group of examples and comparative examples
Figure BDA0003064852060000251
Figure BDA0003064852060000261
As can be seen from Table 1, the product produced by the third example is slightly better than that produced by the first example, but the production cost of the third example is 0.1 yuan/piece of product more than that of the first example, and 9 yuan more than that of the first comparative example calculated by 90 million products per month, the product produced by the first comparative example is close to that of the first example in performance, but the first comparative example generates waste water and increases the environmental protection cost, namely, the first example has lower manufacturing cost and cost performance, and the products produced by other comparative examples and the commercial products are obviously inferior to the product produced by the examples in performance; therefore, the product produced by the embodiment has high relative tracking index (CTI is more than or equal to 600V), high thermal stress, high peel strength, good processing performance (such as no copper foil bubble point after etching), low manufacturing cost and high cost performance, and has the insulating capability in humid and dirty environments.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (2)

1. A preparation process of a high CTI special copper foil adhesive is characterized by comprising the following steps:
step one, adding 180-230 parts by weight of phenol and 140-160 parts by weight of first solvent into a reaction kettle, and stirring;
step two, adding 200-220 parts by weight of polyformaldehyde and 140-160 parts by weight of melamine into the mixture obtained in the step one, continuously stirring for 5-15 minutes, and then adding 0.5-3 parts by weight of a catalyst; the catalyst is ethylenediamine or triethylamine;
step three, the temperature is raised to 60 +/-2 ℃ and timing is started, then the temperature is controlled to be 60-100 ℃ and kept for 20-120 minutes, and then the temperature is reduced to be below 50 ℃;
step four, adding a first solvent into the obtained product for dilution to obtain melamine modified phenolic resin; adding 90-110 parts by weight of melamine modified phenolic resin, 370-410 parts of second solvent, 5-15 parts of solid phenolic resin, 40-60 parts of polyvinyl butyral, 2-10 parts of phenolic epoxy resin and 2-10 parts of rubber vulcanizing agent into a stirring kettle, and stirring to obtain copper foil adhesive;
the phenol is one or a composition of two of phenol and o-cresol; the first solvent is methanol or ethanol; the second solvent comprises 140-180 parts by weight of toluene, 50-80 parts by weight of butanone and 140-180 parts by weight of the first solvent.
2. The application of the copper foil adhesive special for high CTI (comparative tracking index) on the paper-based copper-clad plate is characterized in that the copper foil adhesive as claimed in claim 1 is coated on the rough surface of a copper foil with the thickness of 15-35 microns, dried to prepare a coated copper foil, cut into required size, and hot-pressed together with a paper-based prepreg to obtain the paper-based copper-clad plate.
CN202110523378.XA 2021-05-13 2021-05-13 Preparation process of copper foil adhesive special for high CTI (comparative tracking index) and application of copper foil adhesive to paper-based copper-clad plate Active CN113388349B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110523378.XA CN113388349B (en) 2021-05-13 2021-05-13 Preparation process of copper foil adhesive special for high CTI (comparative tracking index) and application of copper foil adhesive to paper-based copper-clad plate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110523378.XA CN113388349B (en) 2021-05-13 2021-05-13 Preparation process of copper foil adhesive special for high CTI (comparative tracking index) and application of copper foil adhesive to paper-based copper-clad plate

Publications (2)

Publication Number Publication Date
CN113388349A CN113388349A (en) 2021-09-14
CN113388349B true CN113388349B (en) 2023-03-31

Family

ID=77617257

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110523378.XA Active CN113388349B (en) 2021-05-13 2021-05-13 Preparation process of copper foil adhesive special for high CTI (comparative tracking index) and application of copper foil adhesive to paper-based copper-clad plate

Country Status (1)

Country Link
CN (1) CN113388349B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114015001A (en) * 2021-11-10 2022-02-08 可隆化工（苏州）有限公司 Preparation method of phenolic resin
CN114000372B (en) * 2021-12-08 2023-01-03 福建利豪电子科技股份有限公司 Preparation process of wastewater-free cardanol modified phenolic resin and application of cardanol modified phenolic resin in copper-clad plate

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3209767B2 (en) * 1991-12-17 2001-09-17 住友ベークライト株式会社 Adhesive for copper clad laminate
CN102199264A (en) * 2011-03-18 2011-09-28 江阴市明康绝缘玻纤有限公司 Preparation method of water-soluble phenolic resin applied to preparation of copper-clad foil laminated board adhesive
CN103200772B (en) * 2013-03-01 2016-12-28 广东生益科技股份有限公司 A kind of pcb board of high CTI and preparation method thereof
CN104531030B (en) * 2014-12-22 2017-05-31 湖北宏洋电子股份有限公司 Flexible copper-clad plate and preparation method prepared by epobond epoxyn and the adhesive
CN105542692B (en) * 2015-12-17 2018-08-03 福建利豪电子科技股份有限公司 A kind of manufacturing method of paper-based copper-coated board copper foil glue

Also Published As

Publication number Publication date
CN113388349A (en) 2021-09-14

Similar Documents

Publication Publication Date Title
CN113388349B (en) Preparation process of copper foil adhesive special for high CTI (comparative tracking index) and application of copper foil adhesive to paper-based copper-clad plate
CN108297519B (en) Manufacturing method of paper-based copper-clad plate
CN110951216B (en) Thermosetting resin composition, and prepreg and laminated board using same
CN103213356B (en) Preparation method of bisphenol A modified paper-base glass cloth copper-clad foil single-sided copper-clad plate
CN110734735A (en) high-branched polymer wood adhesive and preparation method and application thereof
CN113292852A (en) Resin composition containing phosphorus-containing phenyl bisphenol polymer and preparation method and application thereof
CN109504319B (en) Aqueous adhesive for electrochemical aluminum and preparation method thereof
CN114851648B (en) High-toughness high-temperature-resistant CEM-1 plate and preparation method thereof
CN114000372B (en) Preparation process of wastewater-free cardanol modified phenolic resin and application of cardanol modified phenolic resin in copper-clad plate
CN109082252B (en) Copper foil adhesive for high-peel-strength paper-based copper-clad plate
CN114030039B (en) High-strength ecological board without added aldehyde and production process
CN114456759B (en) High-strength environment-friendly multilayer composite board and preparation method thereof
KR0162709B1 (en) Manufacture of laminated sheet
CN117384574B (en) Manufacturing method and application of glue solution meeting CHCC (common cold rolled copper) paper-based copper-clad plate
CN114248319A (en) Preparation method of formaldehyde-free thick-core plywood
JPH10168146A (en) Production of phenol resin
CN111073213A (en) Resin composition and high-frequency high-speed metal-based copper-clad plate
CN114919017A (en) Anti-bubbling layering glue-stripping production process for plywood, impregnated bond paper veneer plywood and laminated wood board
JPH04224857A (en) Phenol resin composition
JPH03140355A (en) Thermosetting resin composition for laminate
JPS5920327A (en) Production of phenolic resin laminated sheet
CN114736345A (en) Modified phenolic resin for copper-clad plate and preparation method thereof
JPS606716A (en) Phenolic resin for laminated sheet
JPS6049216B2 (en) Manufacturing method of laminates
JPH02308827A (en) Production of flame retardant phenol resin laminate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant