CN111718678A - Glue solution for copper-clad plate, copper-clad plate and preparation method thereof - Google Patents
Glue solution for copper-clad plate, copper-clad plate and preparation method thereof Download PDFInfo
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- CN111718678A CN111718678A CN202010567479.2A CN202010567479A CN111718678A CN 111718678 A CN111718678 A CN 111718678A CN 202010567479 A CN202010567479 A CN 202010567479A CN 111718678 A CN111718678 A CN 111718678A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- 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
- 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
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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- 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
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- 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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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
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Abstract
The invention provides a glue solution for a copper-clad plate, the copper-clad plate and a preparation method thereof. The glue solution for the copper-clad plate comprises the following components in parts by weight: 80-100 parts of epoxy resin, 15-35 parts of curing agent, 0.05-0.15 part of accelerator, 10-30 parts of flame retardant, 60-80 parts of inorganic filler, 0.1-0.2 part of interface bonding agent and 90-110 parts of solvent. The flame retardance of the copper-clad plate prepared by the glue solution for the copper-clad plate can meet the requirement of UL94V-0, and the copper-clad plate has good thermal reliability, low water absorption, lower dielectric constant and dielectric loss and excellent comprehensive performance.
Description
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to a glue solution for a copper-clad plate, the copper-clad plate and a preparation method thereof.
Background
In order to comply with the world environmental protection trend and green regulations, Halogen-free (Halogen-free) is the current trend of the global electronic industry, and the yield schedule of Halogen-free electronic products is established for the electronic products of countries and related electronic factories in the world. After the Restriction of Hazardous Substances (RoHS) of the european union is implemented, Substances including lead, cadmium, mercury, hexavalent chromium, polybrominated biphenyls, polybrominated diphenyl ethers, and the like, have not been used for manufacturing electronic products or parts thereof, so that printed wiring boards are required to be free of halogenation and meet the requirements of lead-free processes.
The conventional halogen-free board is usually made of DOPO modified epoxy resin or added with phosphorus-containing flame retardant such as phosphazene, so that the conventional halogen-free board meets the UL94V-0 requirement. Meanwhile, the curing agent is generally cured by Dicy, and has low heat resistance, high water absorption and large Z-CTE value, so that the dielectric loss of the substrate is more than 0.018(1 MHz); in addition, the conventional flame retardant has poor solubility, and is phase-separated from the main resin, thereby limiting the application thereof in lead-free processes and high-end products.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a glue solution for a copper-clad plate, the copper-clad plate and a preparation method thereof, wherein the flame retardance of the copper-clad plate prepared by the glue solution for the copper-clad plate can meet the UL94V-0 requirement, and the copper-clad plate has excellent thermal reliability, low water absorption, and lower dielectric constant and dielectric loss.
The invention provides a glue solution for a copper-clad plate, which comprises the following components in parts by weight: 80-100 parts of epoxy resin, 15-35 parts of curing agent, 0.05-0.15 part of accelerator, 10-30 parts of flame retardant, 60-80 parts of inorganic filler, 0.1-0.2 part of interface bonding agent and 90-110 parts of solvent.
In the present invention, the curing agent includes a phenolic curing agent and an amine curing agent. Furthermore, the mass ratio of the phenolic aldehyde curing agent to the amine curing agent in the curing agent can be (10-30): 5; wherein, the phenolic aldehyde curing agent can be at least one selected from phenolic resin and bisphenol A type phenolic resin, and is more preferably bisphenol A type phenolic resin; the amine-based curing agent may be selected from at least one of diaminodiphenyl sulfone and dicyandiamide, more preferably dicyandiamide. Namely, the curing agent preferably comprises bisphenol A type phenolic resin and dicyandiamide, and the mass ratio of the bisphenol A type phenolic resin to the dicyandiamide is (10-30): 5.
in the present invention, the flame retardant may include at least one of a phosphorus-based flame retardant and a nitrogen-based flame retardant; wherein the phosphorus flame retardant can be at least one selected from diphenyl cresyl phosphate, trichloropropyl phosphate, DOPO, hexaphenoxycyclotriphosphazene and modified diphenyl phosphate ester, preferably, the modified diphenyl phosphate ester is biphenol bis (2, 6-dimethylphenyl) phosphate ester; further, the preparation method of the diphenol bis (2, 6-dimethylphenyl) phosphate comprises the following steps: under the protective atmosphere, reacting phosphorus oxychloride with 4, 4-dihydroxybiphenyl in the presence of a catalyst, and then adding 2, 6-dimethylphenol for continuous reaction; the nitrogen-based flame retardant may be at least one selected from melamine and melamine phosphate.
More specifically, the preparation method of the biphenol bis (2, 6-dimethylphenyl) phosphate comprises the following steps: under the protection atmosphere, mixing 30-35g of phosphorus oxychloride and 15-20g of 4, 4-dihydroxybiphenyl, heating to 70-80 ℃, then adding 0.08-0.012g of catalyst, continuously heating to 110-120 ℃, reacting for 3-4h, then adding 48-52g of 2, 6-dimethylphenol, reacting for 3.5-4.5h at 120-150 ℃, and removing the 2, 6-dimethylphenol to obtain a crude product; further, carrying out alkali washing and recrystallization on the crude product to obtain biphenol bis (2, 6-dimethylphenyl) phosphate; wherein the catalyst is anhydrous aluminum trichloride.
The research finds that: the biphenyl diphenol bis (2, 6-dimethylphenyl) phosphate is introduced as a flame retardant, which is particularly favorable for overcoming the problem of phase separation, thereby achieving the purposes of improving the dielectric property of the product and the like.
In the present invention, the epoxy resin may be at least one selected from the group consisting of a novolac type epoxy resin, a bisphenol a type novolac epoxy resin, an o-cresol novolac epoxy resin, a phosphorous epoxy resin, an isocyanate modified epoxy resin, a biphenyl epoxy resin, a trifunctional epoxy resin, and a tetrafunctional epoxy resin.
Preferably, the epoxy resin includes bisphenol a type novolac epoxy resin, DOPO type phosphorous novolac epoxy resin, and diphenylmethane-4, 4' -diisocyanate (MDI) epoxy resin; further, the epoxy resin comprises bisphenol A type novolac epoxy resin, DOPO type phosphorus-containing novolac epoxy resin and diphenylmethane-4, 4' -diisocyanate epoxy resin, wherein the mass ratio of the bisphenol A type novolac epoxy resin to the DOPO type phosphorus-containing novolac epoxy resin is (20-40): (30-50): (10-40).
In the present invention, the accelerator may be at least one selected from the group consisting of imidazole, 1-benzylbenzene-2-ethylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-aminoethyl-2-methylimidazole and 1-cyanoethylimidazole, and preferably 2-ethyl-4-methylimidazole.
In the present invention, the inorganic filler may be at least one selected from the group consisting of magnesium hydroxide, aluminum hydroxide monohydrate, soft composite fine silica powder, fused fine silica powder, talc powder, and barium sulfate. Preferably, the inorganic filler comprises soft composite silicon powder, talcum powder and aluminum hydroxide; further, the mass ratio of the soft composite silicon powder, the talcum powder and the aluminum hydroxide in the inorganic filler is (35-45): (10-20): (10-20).
In the present invention, the solvent may be at least one selected from the group consisting of propylene glycol methyl ether, propylene glycol methyl ether acetate, cyclohexanone, methyl ethyl ketone, acetone, methanol, and xylene. Preferably, the solvent comprises butanone and propylene glycol methyl ether acetate; further, the mass ratio of butanone to propylene glycol monomethyl ether acetate in the solvent is (50-60): (40-50);
in the present invention, the interfacial bonding agent is selected from at least one of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent, and is preferably a silane coupling agent.
The invention also provides a preparation method of the glue solution for the copper-clad plate, which comprises the following steps:
adding a solvent and an interface bonding agent into a glue tank according to the parts by weight, then adding a curing agent and epoxy resin, uniformly stirring, adding an accelerator, a flame retardant and an inorganic filler, stirring and curing to obtain the glue solution for the copper-clad plate.
Specifically, the stirring speed during stirring and curing can be controlled to be 800-.
The invention also provides a preparation method of the copper-clad plate, which comprises the following steps:
preparing a prepreg from the glue solution for the copper-clad plate;
and laminating the prepreg and the copper foil after overlapping to obtain the copper-clad plate.
Specifically, when the prepreg is prepared, the glue content is controlled to be 40-50%, and the fluidity is controlled to be 15-50%.
The invention also provides a copper-clad plate prepared by the preparation method.
The epoxy resin is reasonably selected for matching, the novel halogen-free flame retardant is introduced, and the PN and the amine curing agent are used for co-curing, so that the flame retardant capability of the copper-clad plate can meet the requirement of UL94V-0, and the copper-clad plate has excellent thermal reliability, low water absorption, lower dielectric constant and dielectric loss and excellent comprehensive performance.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise, and further, it is understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. 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.
Example 1
Preparation of biphenol bis (2, 6-dimethylphenyl) phosphate
Adding 33.3g of phosphorus oxychloride and 18.6g of 4, 4-dihydroxybiphenyl into a four-neck flask provided with a thermometer and a nitrogen protection device, introducing nitrogen, heating to about 75 ℃, uniformly stirring, adding 0.010g of anhydrous aluminum trichloride serving as a catalyst, slowly heating to 115 ℃, reacting for 3.5 hours, adding 50.1g of 2, 6-dimethylphenol, reacting for 4 hours at 135 ℃, removing the 2, 6-dimethylphenol under reduced pressure, and performing alkali washing and recrystallization to obtain a white solid, namely the biphenol bis (2, 6-dimethylphenyl) phosphate, wherein the yield is 85.1%.
Secondly, preparing glue solution for copper-clad plate
The glue solution for the copper-clad plate comprises the following components in parts by weight:
epoxy resin: 20 parts of bisphenol A type novolac epoxy resin, 30 parts of DOPO type phosphorus-containing novolac epoxy resin and 40 parts of diphenylmethane-4, 4' -diisocyanate epoxy resin;
curing agent: 10 parts of bisphenol A type phenolic resin and 5 parts of dicyandiamide;
curing accelerator: 0.1 part of 2-ethyl-4-methylimidazole;
flame retardant: 10 parts of biphenol bis (2, 6-dimethylphenyl) phosphate;
inorganic filler: 40 parts of soft composite silicon micropowder, 15 parts of talcum powder and 15 parts of aluminum hydroxide;
interface binding agent: 0.16 part of a silane coupling agent;
solvent: 55 parts of butanone and 45 parts of propylene glycol methyl ether acetate.
And (3) after cleaning the glue tank, adding the solvent and the interfacial bonding agent into the glue tank according to the parts by weight, then adding the curing agent and the epoxy resin, stirring for 3 hours, uniformly mixing, then sequentially adding the rest components, stirring for 6 hours at the rotating speed of 1000rpm, and curing to obtain the glue solution for the copper-clad plate.
Thirdly, preparing the copper-clad plate
The glue solution for the copper-clad plate prepared by the method is prepared into a prepreg by a vertical gluing machine, the glue content is controlled to be about 45%, and the fluidity is controlled to be about 30%.
And (3) covering the upper and lower parts of 8 prepregs with 1OZ copper foils respectively to form a stacked structure, putting the stacked structure into a laminating machine, and laminating to obtain a composite laminated board, namely the copper-clad plate.
The quality of the copper-clad plate is detected according to the IPC-650 method, and the detection result is shown in Table 1.
Example 2
Preparation of biphenol bis (2, 6-dimethylphenyl) phosphate
Adding 33.3g of phosphorus oxychloride and 18.6g of 4, 4-dihydroxybiphenyl into a four-neck flask provided with a thermometer and a nitrogen protection device, introducing nitrogen, heating to about 70 ℃, uniformly stirring, adding 0.010g of catalyst anhydrous aluminum trichloride, slowly heating to 115 ℃, reacting for 3.5 hours, adding 50.1g of 2, 6-dimethylphenol, reacting for 4 hours at 120 ℃, removing the 2, 6-dimethylphenol under reduced pressure, and performing alkaline washing and recrystallization to obtain the biphenol bis (2, 6-dimethylphenyl) phosphate.
Secondly, preparing glue solution for copper-clad plate
The glue solution for the copper-clad plate comprises the following components in parts by weight:
epoxy resin: 30 parts of bisphenol A type novolac epoxy resin, 40 parts of DOPO type phosphorus-containing novolac epoxy resin and 20 parts of diphenylmethane-4, 4' -diisocyanate epoxy resin;
curing agent: 20 parts of bisphenol A type phenolic resin and 5 parts of dicyandiamide;
curing accelerator: 0.05 part of 2-ethyl-4-methylimidazole;
flame retardant: 20 parts of biphenol bis (2, 6-dimethylphenyl) phosphate;
inorganic filler: 35 parts of soft composite silicon powder, 10 parts of talcum powder and 20 parts of aluminum hydroxide;
interface binding agent: 0.1 part of silane coupling agent;
solvent: 50 parts of butanone and 50 parts of propylene glycol methyl ether acetate.
And (3) after cleaning the glue tank, adding the solvent and the interfacial bonding agent into the glue tank according to the parts by weight, then adding the curing agent and the epoxy resin, stirring for 3 hours, uniformly mixing, then sequentially adding the rest components, stirring for 7 hours at the rotating speed of 800rpm, and curing to obtain the glue solution for the copper-clad plate.
Thirdly, preparing the copper-clad plate
The glue solution for the copper-clad plate prepared by the method is prepared into a prepreg by a vertical gluing machine, the glue content is controlled to be about 40%, and the fluidity is controlled to be about 40%.
And (3) covering the upper and lower parts of 8 prepregs with 1OZ copper foils respectively to form a stacked structure, putting the stacked structure into a laminating machine, and laminating to obtain a composite laminated board, namely the copper-clad plate.
The quality of the copper-clad plate is detected according to the IPC-650 method, and the detection result is shown in Table 1.
Example 3
Preparation of biphenol bis (2, 6-dimethylphenyl) phosphate
Adding 33.3g of phosphorus oxychloride and 18.6g of 4, 4-dihydroxybiphenyl into a four-neck flask provided with a thermometer and a nitrogen protection device, introducing nitrogen, heating to about 80 ℃, uniformly stirring, adding 0.010g of catalyst anhydrous aluminum trichloride, slowly heating to 115 ℃, reacting for 3.5 hours, adding 50.1g of 2, 6-dimethylphenol, reacting for 4 hours at 150 ℃, removing the 2, 6-dimethylphenol under reduced pressure, and performing alkaline washing and recrystallization to obtain the biphenol bis (2, 6-dimethylphenyl) phosphate.
Secondly, preparing glue solution for copper-clad plate
The glue solution for the copper-clad plate comprises the following components in parts by weight:
epoxy resin: 40 parts of bisphenol A type novolac epoxy resin, 50 parts of DOPO type phosphorus-containing novolac epoxy resin and 10 parts of diphenylmethane-4, 4' -diisocyanate epoxy resin;
curing agent: 30 parts of bisphenol A type phenolic resin and 5 parts of dicyandiamide;
curing accelerator: 0.15 part of 2-ethyl-4-methylimidazole;
flame retardant: 30 parts of biphenol bis (2, 6-dimethylphenyl) phosphate;
inorganic filler: 45 parts of soft composite silicon micropowder, 20 parts of talcum powder and 10 parts of aluminum hydroxide;
interface binding agent: 0.2 part of silane coupling agent;
solvent: 50 parts of butanone and 50 parts of propylene glycol methyl ether acetate.
And (3) after cleaning the glue tank, adding the solvent and the interfacial bonding agent into the glue tank according to the parts by weight, then adding the curing agent and the epoxy resin, stirring for 3 hours, uniformly mixing, then sequentially adding the rest components, stirring for 7 hours at the rotating speed of 800rpm, and curing to obtain the glue solution for the copper-clad plate.
Thirdly, preparing the copper-clad plate
The glue solution for the copper-clad plate prepared by the method is prepared into a prepreg by a vertical gluing machine, the glue content is controlled to be about 40%, and the fluidity is controlled to be about 40%.
And (3) covering the upper and lower parts of 8 prepregs with 1OZ copper foils respectively to form a stacked structure, putting the stacked structure into a laminating machine, and laminating to obtain a composite laminated board, namely the copper-clad plate.
The quality of the copper-clad plate is detected according to the IPC-650 method, and the detection result is shown in Table 1.
Comparative example 1
The glue solution for the copper-clad plate of the comparative example is basically the same as the glue solution of the embodiment 1 except that the epoxy resin adopted is different from the epoxy resin in the embodiment 1.
The epoxy resin composition of this comparative example is as follows:
20 parts of dicyclopentadiene epoxy resin, 30 parts of phosphorus-containing novolac epoxy resin, 35 parts of isocyanate type epoxy resin and 5 parts of tetrafunctional epoxy resin.
The copper-clad plate is prepared according to the preparation method of the embodiment 1, the quality of the copper-clad plate is detected according to the IPC-650 method, and the detection result is shown in the table 1.
Comparative example 2
The glue solution for the copper-clad plate of the comparative example is basically the same as the glue solution of the embodiment 1 except that the adopted curing agent has a different composition from the glue solution of the embodiment 1.
The curing agent composition of this comparative example was as follows:
10 parts of bisphenol A type phenolic resin and 5 parts of phenol type phenolic resin.
The copper-clad plate is prepared according to the preparation method of the embodiment 1, the quality of the copper-clad plate is detected according to the IPC-650 method, and the detection result is shown in the table 1.
Comparative example 3
The glue solution for the copper-clad plate of the comparative example is basically the same as the glue solution of the embodiment 1 except that the adopted flame retardant is different from the glue solution of the embodiment 1 in composition.
The flame retardant composition of this comparative example was: 10 parts of diphenyl cresyl phosphate.
The copper-clad plate is prepared according to the preparation method of the embodiment 1, the quality of the copper-clad plate is detected according to the IPC-650 method, and the detection result is shown in the table 1.
Comparative example 4
The glue solution for the copper-clad plate of the comparative example is basically the same as the glue solution of the embodiment 1 except that the adopted flame retardant is different from the glue solution of the embodiment 1 in composition.
The flame retardant composition of this comparative example was: tetrabromobisphenol A5 parts and aluminum hydroxide 5 parts.
The copper-clad plate is prepared according to the preparation method of the embodiment 1, the quality of the copper-clad plate is detected according to the IPC-650 method, and the detection result is shown in the table 1.
Comparative example 5
The glue solution for the copper-clad plate of the comparative example is basically the same as the glue solution of the embodiment 1 except that the composition of the glue solution is different from that of the embodiment 1.
The glue solution for the copper-clad plate of the comparative example comprises the following components:
epoxy resin: 10 parts of bisphenol A type novolac epoxy resin, 30 parts of DOPO type phosphorus-containing novolac epoxy resin and 50 parts of diphenylmethane-4, 4' -diisocyanate epoxy resin;
curing agent: 13 parts of bisphenol A type phenolic resin and 2 parts of dicyandiamide;
curing accelerator: 0.1 part of 2-ethyl-4-methylimidazole;
flame retardant: 10 parts of biphenol bis (2, 6-dimethylphenyl) phosphate;
inorganic filler: 40 parts of soft composite silicon micropowder, 15 parts of talcum powder and 15 parts of aluminum hydroxide;
interface binding agent: 0.16 part of a silane coupling agent;
solvent: 55 parts of butanone and 45 parts of propylene glycol methyl ether acetate.
The copper-clad plate is prepared according to the preparation method of the embodiment 1, the quality of the copper-clad plate is detected according to the IPC-650 method, and the detection result is shown in the table 1.
Table 1 quality test results of each copper-clad plate
According to the invention, various epoxy resins of different types are reasonably selected for matching, the novel halogen-free flame retardant modified diphenyl phosphate is introduced, and the dual curing agent system of PN and amine curing agent is used for co-curing, so that the flame retardant capability of the copper-clad plate reaches the UL94V-0 requirement, and meanwhile, the copper-clad plate has excellent thermal reliability, low water absorption, lower dielectric constant and dielectric loss and excellent comprehensive performance.
Finally, it should be noted that: 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; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The glue solution for the copper-clad plate is characterized by comprising the following components in parts by weight: 80-100 parts of epoxy resin, 15-35 parts of curing agent, 0.05-0.15 part of accelerator, 10-30 parts of flame retardant, 60-80 parts of inorganic filler, 0.1-0.2 part of interface bonding agent and 90-110 parts of solvent.
2. The glue solution for copper-clad plates according to claim 1, wherein the curing agent comprises phenolic curing agent and amine curing agent;
preferably, the mass ratio of the phenolic aldehyde curing agent to the amine curing agent in the curing agent is (10-30): 5;
preferably, the phenolic aldehyde curing agent is selected from at least one of phenolic resin and bisphenol a type phenolic resin, more preferably bisphenol a type phenolic resin;
preferably, the amine curing agent is selected from at least one of diaminodiphenyl sulfone and dicyandiamide, more preferably dicyandiamide.
3. The glue solution for copper-clad plates according to claim 1, wherein the flame retardant comprises at least one of a phosphorus flame retardant and a nitrogen flame retardant;
preferably, the phosphorus-based flame retardant is selected from at least one selected from the group consisting of cresyldiphenyl phosphate, trichloropropyl phosphate, DOPO, hexaphenoxycyclotriphosphazene and modified diphenyl phosphate;
preferably, the modified diphenyl phosphate is biphenol bis (2, 6-dimethylphenyl) phosphate;
preferably, the preparation method of the biphenol bis (2, 6-dimethylphenyl) phosphate comprises the following steps:
under the protective atmosphere, reacting phosphorus oxychloride with 4, 4-dihydroxybiphenyl in the presence of a catalyst, and then adding 2, 6-dimethylphenol for continuous reaction;
preferably, the nitrogen-based flame retardant is selected from at least one of melamine and melamine phosphate.
4. The glue solution for copper-clad plates according to claim 1, wherein the epoxy resin is at least one of phenolic epoxy resin, bisphenol A phenolic epoxy resin, o-cresol novolac epoxy resin, phosphorus-containing epoxy resin, isocyanate modified epoxy resin, biphenyl epoxy resin, trifunctional epoxy resin and tetrafunctional epoxy resin;
preferably, the epoxy resin includes bisphenol a type novolac epoxy resin, DOPO type phosphorous novolac epoxy resin, and diphenylmethane-4, 4' -diisocyanate epoxy resin;
preferably, the epoxy resin comprises bisphenol A type novolac epoxy resin, DOPO type phosphorus-containing novolac epoxy resin and diphenylmethane-4, 4' -diisocyanate epoxy resin in a mass ratio of (20-40): (30-50): (10-40).
5. The glue solution for copper-clad plates according to claim 1, wherein the accelerator is at least one selected from imidazole, 1-benzylbenzene-2-ethylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-aminoethyl-2-methylimidazole and 1-cyanoethylimidazole, and is preferably 2-ethyl-4-methylimidazole.
6. The glue solution for copper-clad plates according to claim 1, wherein the inorganic filler is at least one selected from magnesium hydroxide, aluminum hydroxide monohydrate, soft composite silica micropowder, fused silica micropowder, talcum powder and barium sulfate;
preferably, the inorganic filler comprises soft composite silicon powder, talcum powder and aluminum hydroxide;
preferably, the mass ratio of the soft composite silicon powder, the talcum powder and the aluminum hydroxide in the inorganic filler is (35-45): (10-20): (10-20).
7. The glue solution for copper-clad plates according to claim 1, wherein the solvent is at least one selected from propylene glycol methyl ether, propylene glycol methyl ether acetate, cyclohexanone, butanone, acetone, methanol and xylene;
preferably, the solvent comprises butanone and propylene glycol methyl ether acetate;
preferably, the mass ratio of the butanone to the propylene glycol monomethyl ether acetate in the solvent is (50-60): (40-50);
preferably, the interface bonding agent is selected from at least one of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent, more preferably a silane coupling agent.
8. The preparation method of the glue solution for the copper-clad plate according to any one of claims 1 to 7, which is characterized by comprising the following steps:
adding a solvent and an interface bonding agent into a glue tank according to the parts by weight, then adding a curing agent and epoxy resin, uniformly stirring, adding an accelerator, a flame retardant and an inorganic filler, stirring and curing to obtain a glue solution for the copper-clad plate;
preferably, the stirring speed during stirring and curing is controlled to be 800-1200rpm, and the stirring and curing time is controlled to be 5-7 h.
9. The preparation method of the copper-clad plate is characterized by comprising the following steps:
preparing a prepreg from the glue solution for the copper-clad plate according to any one of claims 1 to 7;
laminating the prepreg and the copper foil after overlapping to obtain a copper-clad plate;
preferably, when the prepreg is prepared, the glue content is controlled to be 40-50%, and the fluidity is controlled to be 15-50%.
10. A copper-clad plate, characterized in that it is prepared according to the preparation method of claim 9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112409968A (en) * | 2020-11-04 | 2021-02-26 | 江西省宏瑞兴科技股份有限公司 | High-reliability halogen-free adhesive applicable to high-speed communication field and preparation method thereof |
| CN113290981A (en) * | 2021-01-14 | 2021-08-24 | 南亚新材料科技股份有限公司 | Halogen-free copper-clad plate for automobile electronic material and preparation method and application thereof |
| CN115230287A (en) * | 2022-07-20 | 2022-10-25 | 广德华昌新材料有限公司 | Preparation method of copper-clad plate |
| CN115651366A (en) * | 2022-11-18 | 2023-01-31 | 江苏耀鸿电子有限公司 | Resin glue solution containing alumina for copper-clad plate and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234734A (en) * | 2020-02-27 | 2020-06-05 | 招远春鹏电子科技有限公司 | Environment-friendly glue solution for flexible copper-clad plate and preparation method thereof |
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2020
- 2020-06-19 CN CN202010567479.2A patent/CN111718678B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234734A (en) * | 2020-02-27 | 2020-06-05 | 招远春鹏电子科技有限公司 | Environment-friendly glue solution for flexible copper-clad plate and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112409968A (en) * | 2020-11-04 | 2021-02-26 | 江西省宏瑞兴科技股份有限公司 | High-reliability halogen-free adhesive applicable to high-speed communication field and preparation method thereof |
| CN113290981A (en) * | 2021-01-14 | 2021-08-24 | 南亚新材料科技股份有限公司 | Halogen-free copper-clad plate for automobile electronic material and preparation method and application thereof |
| CN115230287A (en) * | 2022-07-20 | 2022-10-25 | 广德华昌新材料有限公司 | Preparation method of copper-clad plate |
| CN115230287B (en) * | 2022-07-20 | 2024-04-02 | 广德华昌新材料有限公司 | Preparation method of copper-clad plate |
| CN115651366A (en) * | 2022-11-18 | 2023-01-31 | 江苏耀鸿电子有限公司 | Resin glue solution containing alumina for copper-clad plate and preparation method thereof |
| CN115651366B (en) * | 2022-11-18 | 2023-09-12 | 江苏耀鸿电子有限公司 | Alumina-containing resin glue solution for copper-clad plate and preparation method thereof |
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