CN115073711B - MDI modified epoxy resin solution for copper-clad plate glue solution fluidity improver and preparation method and application thereof - Google Patents

MDI modified epoxy resin solution for copper-clad plate glue solution fluidity improver and preparation method and application thereof Download PDF

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CN115073711B
CN115073711B CN202210732067.9A CN202210732067A CN115073711B CN 115073711 B CN115073711 B CN 115073711B CN 202210732067 A CN202210732067 A CN 202210732067A CN 115073711 B CN115073711 B CN 115073711B
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copper
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CN115073711A (en
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叶伦学
黄杰
唐文东
王立
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Jiangsu Dongcai New Materials Co ltd
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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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

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  • Polymers & Plastics (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention relates to an MDI modified epoxy resin solution for a copper-clad plate glue solution fluidity improver, which is prepared by reacting phenyl ether amine epoxy resin, MDI, bisphenol A and ethyl triphenylphosphine acetate and then diluting with cyclohexanone; the preparation method of the MDI modified epoxy resin solution and the composition formed by the MDI modified epoxy resin solution are also disclosed. The epoxy resin with high heat resistance and the MDI are adopted, the high-temperature and high-catalyst ethyl triphenylphosphine acetate is adopted to generate the high-heat-resistant oxazolidone structure, meanwhile, the double-functional MDI reacts with the epoxy groups, the length of an epoxy main chain is prolonged, the crosslinking density is reduced, the toughness of the resin is improved, the condition that the copper-clad plate is not cracked and powder is removed when drilling is applied is met, finally, the bisphenol A is used for further chain extension of the resin, the number average molecular weight of the resin is controlled to 8000-12000, and the fluidity of the composition glue solution for the copper-clad plate can be well controlled.

Description

MDI modified epoxy resin solution for copper-clad plate glue solution fluidity improver and preparation method and application thereof
Technical Field
The invention relates to an MDI modified epoxy resin solution for a copper-clad plate glue solution fluidity improver, a preparation method of the MDI modified epoxy resin solution and an MDI modified phenyl ether amine epoxy resin solution composition.
Background
The copper-clad plate is a basic material of the electronic industry, is mainly used for processing and manufacturing a printed circuit board (PCB for short), and is widely used for various electronic products such as televisions, computers, mobile communication and the like. The existing resin for the copper-clad plate is basically produced by adopting various common epoxy resins, brominated epoxy resins, halogen-free flame-retardant epoxy resins, heat-resistant epoxy resins, phenolic resins, benzoxazine resins and the like which are matched with curing agents and a large amount of solvents. However, the current benzoxazine resin and some low-activity epoxy resins have low curing activity in the process of pressing the copper-clad plate, gel is slow, glue solution easily flows away in the process of pressing the plate, so that the performance of the plate is poor, and meanwhile, the heat resistance (Tg) is low, the brittleness is high, and the application of the benzoxazine resin and the epoxy resins in the aspect of high-end copper-clad plates is limited.
Disclosure of Invention
The invention aims to solve the technical problem of providing an MDI modified epoxy resin solution for a copper-clad plate glue solution fluidity improver, and also relates to a preparation method of the MDI modified epoxy resin solution and an MDI modified phenyl ether amine epoxy resin solution composition.
In order to solve the technical problems, the technical scheme of the invention is as follows: the MDI modified epoxy resin solution for the copper-clad plate glue solution fluidity improver has the innovation points that: the MDI modified phenylamine epoxy resin solution is prepared by reacting phenylamine epoxy resin, MDI, bisphenol A and ethyl triphenylphosphine acetate and diluting with cyclohexanone, and the MDI modified phenylamine epoxy resin in the MDI modified phenylamine epoxy resin solution has a chemical structure shown in the following formula:
further, the mass percentage content of the solid content of the MDI modified phenyl ether amine epoxy resin solution is 57+/-2%, the viscosity is 10000-15000 mpas, and the number average molecular weight is 8000-12000.
Further, the chemical structural formula of the phenyl ether amine epoxy resin is as follows:
the preparation method of the MDI modified epoxy resin solution for the copper-clad plate glue solution fluidity improver has the innovation points that: comprising the following steps:
s1: 90-100 parts by mass of phenyl ether amine epoxy resin and 70-80 parts by mass of cyclohexanone are added into a reactor, the temperature of the reactor is raised to 97-103 ℃ and stirred for 0.5 hour;
s2: adding 0.02-0.1 part by mass of ethyl triphenylphosphine acetate into a reactor, dropwise adding 15-20 parts by mass of MDI liquid into the reactor, stirring after 1-2 hours, heating the reactor to 140-150 ℃ again, and reacting for 2-4 hours;
s3: adding 30-40 parts by mass of bisphenol A into a reactor, heating the reactor to 160-180 ℃, stirring, and reacting for 5-7 hours;
s4: adding 30-40 parts by mass of cyclohexanone into a reactor, and uniformly stirring to obtain the MDI modified phenylate amine epoxy resin solution with the mass percent of the solid content of 57+/-2%.
An MDI modified epoxy resin solution composition for a copper-clad plate glue solution fluidity improver is characterized in that: the composition comprises the following components: 20 to 30 parts by mass of MDI modified phenyl ether amine epoxy resin solution with the solid content of 57+/-2 percent, 50 to 60 parts by mass of naphthoquinone phosphorus-containing epoxy resin, 30 to 40 parts by mass of XY-8800 anthracene epoxy resin, 40 to 50 parts by mass of ODA benzoxazine, 5 to 8 parts by mass of 2-ethyl-4-methylimidazole and 40 to 50 parts by mass of butanone.
Further, the structural formula of the naphthoquinone type phosphorus-containing epoxy resin is as follows:
further, the structural formula of the XY-8800 anthracene type epoxy resin is as follows:
the invention has the advantages that: the epoxy resin with good heat resistance and MDI are adopted to generate the high heat resistance oxazolidone structure under the action of high temperature and catalyst ethyl triphenylphosphine acetate phosphine, meanwhile, the double functional MDI reacts with epoxy groups, the length of an epoxy main chain is prolonged, the crosslinking density is reduced, the toughness of the resin is improved, the condition that the copper-clad plate is not cracked and powder is removed when drilling is applied is met, and finally bisphenol A is used for further chain extension of the resin, so that the number average molecular weight of the resin is controlled to 8000-12000, and the fluidity of the composition glue solution for the copper-clad plate can be well controlled;
the composition is prepared from MDI modified phenylate amine epoxy resin, anthracene epoxy resin with high heat resistance, low dielectric property and low dielectric loss structure, naphthoquinone type phosphorus epoxy resin with heat resistance and phosphorus flame retardant structure, ODA type benzoxazine resin with high heat resistance, low dielectric property and low dielectric loss structure, a small amount of curing accelerator and solvent butanone to prepare the resin composition for the copper-clad plate, and the resin composition with high heat resistance, halogen-free flame retardance, low dielectric property, low dielectric loss, high toughness and anti-gummosis is provided;
the Tg of the copper-clad plate prepared by the product is more than or equal to 230 ℃, the dielectric constant is less than or equal to 3.4, the dielectric loss is less than or equal to 0.02, the drilling surface is smooth, the copper-clad plate has good toughness, no cracking and powder falling and flame retardance UL94-V0 when drilling is applied, the adhesive flow of a pressing plate (the adhesive flow loss mass accounts for the percentage of the total adhesive mass when pressing the pressing plate) is less than 0.2%, and the resin performance requirement of the high-end copper-clad plate is met.
Detailed Description
The following examples will provide those skilled in the art with a more complete understanding of the present invention and are not intended to limit the invention to the embodiments described.
The MDI modified epoxy resin solution for the copper-clad plate glue solution fluidity improver is prepared by reacting phenyl ether amine epoxy resin, MDI, bisphenol A and ethyl triphenylphosphine acetate and diluting cyclohexanone, and the MDI is 4,4' -diisocyanate diphenylmethane.
The MDI modified epoxy resin in the MDI modified epoxy resin solution has a chemical structural formula as shown below:
the preparation method of the MDI modified epoxy resin solution for the copper-clad plate glue solution fluidity improver is realized by the following steps:
s1: 90 to 100 mass parts of phenyl ether amine epoxy resin and 70 to 80 mass parts of cyclohexanone are added into a reactor, and the chemical structural formula of the phenyl ether amine epoxy resin is that
The reactor was warmed to 97-103 ℃ and stirred for 0.5 hours.
S2: adding 0.02-0.1 part by mass of ethyl triphenylphosphine acetate into a reactor, wherein the chemical structural formula of the ethyl triphenylphosphine acetate isAnd dropwise adding 15-20 parts by mass of MDI liquid into the reactor, wherein the chemical structural formula of the MDI in the MDI liquid is +.>After 1-2 hours, stirring, heating the reactor to 140-150 ℃ again, and reacting for 2-4 hours.
S3: adding 30-40 parts by mass of bisphenol A into the reactor, heating the reactor to 160-180 ℃, stirring and reacting for 5-7 hours.
S4: adding 30-40 parts by mass of cyclohexanone into a reactor, and uniformly stirring to obtain the MDI modified phenylate amine epoxy resin solution with the mass percent of the solid content of 57+/-2%.
Examples 1-1 to 1-8 employ different amounts and process conditions, as shown in table 1,
table 1: preparing an MDI modified phenyl ether amine epoxy resin solution formula amount (unit: kg) for the copper-clad plate glue solution fluidity improver, and a process condition table:
TABLE 1
In table 1, temperature a is the temperature of the reactor in step S1, temperature B is the temperature of the reactor in step S2, time a is the reaction time of the reactor in step S2, temperature C is the temperature of the reactor in step S3, and time B is the reaction time of the reactor in step S3.
The invention relates to an MDI modified phenyl ether amine epoxy resin solution composition for a copper-clad plate glue solution fluidity improver, which comprises the following components: 20 to 30 parts by mass of MDI modified phenylamine epoxy resin solution with the solid content of 57+/-2 percent, 50 to 60 parts by mass of naphthoquinone type phosphorus-containing epoxy resin, 30 to 40 parts by mass of XY-8800 anthracene type epoxy resin, 40 to 50 parts by mass of ODA type benzoxazine, 5 to 8 parts by mass of 2-ethyl-4-methylimidazole and 40 to 50 parts by mass of butanone,
the structural formula of the naphthoquinone type phosphorus-containing epoxy resin is as follows:
the structural formula of the XY-8800 anthracene type epoxy resin is as follows:
the structural formula of the ODA type benzoxazine resin is as follows:
the structural formula of the 2-ethyl-4-methylimidazole is as follows:
the components are mixed and stirred uniformly to prepare the required composition.
Examples 2-1 to 2-8 employ different amounts and process conditions, as in particular table 2,
table 2: preparing a formula table (unit: mass parts) of an MDI modified phenyl ether amine epoxy resin solution composition for the copper-clad plate glue solution fluidity improver:
TABLE 2
1-1 to 1-8 in Table 2 are MDI modified phenylamine epoxy resin solutions prepared in the above examples.
Table 3 shows the comparison of the performance results of the copper-clad plate of the MDI-modified phenylamine epoxy resin solution composition for the copper-clad plate glue solution fluidity improver in examples 2-1 to 2-8:
TABLE 3 Table 3
As can be seen from the comparison of the data in Table 3, the MDI modified phenyl ether amine epoxy resin solution composition prepared by the invention is used for preparing the copper-clad plate, the Tg of the prepared copper-clad plate is more than or equal to 230 ℃, the dielectric constant is less than or equal to 3.4, the dielectric loss is less than or equal to 0.02, the drilling surface is smooth, the toughness of the copper-clad plate is good, the powder is not cracked and removed when drilling is applied, the flame retardance is UL94-V0, the glue flow of a pressing plate (the mass of glue solution flowing loss in the pressing plate accounts for less than 0.2 percent of the mass of the total glue solution), and the resin performance requirement of the high-end copper-clad plate is met.
Example 3:
90 parts by mass of phenyl ether amine epoxy resin and 70 parts by mass of cyclohexanone are added into a reactor, and the temperature of the reactor is raised to 100 ℃; adding 0.02 part by mass of ethyl triphenylphosphine acetate into the reactor, dropwise adding 15 parts by mass of MDI liquid, stirring, heating to 150 ℃ and reacting for 4 hours; adding 30 parts by mass of bisphenol A into the reactor, heating to 180 ℃, stirring, and reacting for 5 hours; finally, 30 parts by mass of cyclohexanone is added into the reactor and stirred uniformly, so as to prepare the MDI modified phenylamine epoxy resin solution with the mass percent of the solid content of 57+/-2%, and the viscosity of the solution is 12000mpas, and the solution is light yellow liquid.
Example 4:
adding 100 parts by mass of phenyl ether amine epoxy resin and 80 parts by mass of cyclohexanone into a reactor, and heating to 100 ℃; adding 0.1 part by mass of ethyl triphenylphosphine acetate into the reactor, dropwise adding 20 parts by mass of MDI liquid, stirring, heating to 140 ℃, and reacting for 3 hours; adding 40 parts by mass of bisphenol A into a reactor, heating to 170 ℃, stirring, and reacting for 6 hours; finally, 40 parts by mass of cyclohexanone is added into the reactor, and the mixture is stirred uniformly to prepare the MDI modified phenylamine epoxy resin solution with the mass percent of the solid content of 57+/-2 percent, wherein the viscosity of the solution is 13000mpas, and the solution is light yellow liquid.
Example 5:
95 parts by mass of phenyl ether amine epoxy resin and 75 parts by mass of cyclohexanone are added into a reactor, and the temperature is raised to 100 ℃; adding 0.06 parts by mass of ethyl triphenylphosphine acetate into the reactor, dropwise adding 18 parts by mass of MDI liquid, stirring, heating to 150 ℃ and reacting for 4 hours; then adding 35 parts by mass of bisphenol A into the reactor, heating to 180 ℃, stirring, and reacting for 6 hours; finally, adding 35 parts by mass of cyclohexanone into the reactor, and uniformly stirring to obtain an MDI modified phenylamine epoxy resin solution with the mass percent of 57+/-2% of the solid content, wherein the viscosity of the solution is 11000mpas, and the solution is light yellow liquid.
Example 6:
adding 98 parts by mass of phenyl ether amine epoxy resin and 77 parts by mass of cyclohexanone into a reactor, and heating to 100 ℃; adding 0.08 mass part of ethyl triphenylphosphine acetate into the reactor, dropwise adding 19 mass parts of MDI liquid, stirring, heating to 145 ℃, and reacting for 3 hours; then 38 parts by mass of bisphenol A is added into the reactor, the temperature is raised to 175 ℃, and the mixture is stirred and reacts for 6 hours; finally, 37 parts by mass of cyclohexanone is added into the reactor, and the mixture is stirred uniformly to prepare the MDI modified phenylamine epoxy resin solution with the mass percent of the solid content of 57+/-2 percent, wherein the viscosity of the solution is 14000mpas, and the solution is light yellow liquid.
Example 7:
93 parts by mass of phenyl ether amine epoxy resin and 74 parts by mass of cyclohexanone are added into a reactor, and the temperature is raised to 100 ℃; adding 0.04 parts by mass of ethyl triphenylphosphine acetate into a reactor, dropwise adding 16 parts by mass of MDI liquid, stirring, and heating to 142 ℃; reacting for 4 hours; adding 33 parts by mass of bisphenol A into the reactor, heating to 171 ℃, stirring, and reacting for 7 hours; finally, 32 parts by mass of cyclohexanone is added into the reactor, and the mixture is stirred uniformly to prepare the MDI modified phenylate amine epoxy resin solution with the mass percent of the solid content of 57+/-2%, and the viscosity of the solution is 13500mpas, which is light yellow liquid.
From examples 1-1 to 1-8 and examples 3-7, it is known that the MDI modified epoxy resin solution with high heat resistance oxazolidinone structure is produced by adopting phenyl ether amine epoxy resin, MDI (4, 4' -diisocyanate diphenylmethane), bisphenol A and cyclohexanone under the action of high temperature and catalyst ethyl triphenylphosphine acetate, and then the chain is extended by bisphenol A, so that the MDI modified epoxy resin with high toughness and good fluidity for the copper-clad plate with excellent comprehensive performance is provided.
Example 8:
the MDI modified phenyl ether amine epoxy resin solution composition for the copper-clad plate glue solution fluidity improver is prepared by uniformly mixing and stirring 20 parts by mass of MDI modified phenyl ether amine epoxy resin solution with the solid content of 57+/-2%, 50 parts by mass of naphthoquinone type phosphorus-containing epoxy resin, 30 parts by mass of XY-8800 anthracene type epoxy resin, 40 parts by mass of ODA type benzoxazine, 5 parts by mass of 2-ethyl-4-methylimidazole and 40 parts by mass of butanone, and curing by a 7628 glass fiber cloth pressing plate to obtain a laminated plate, wherein Tg of the obtained product is as follows: 232 ℃. Dielectric constant: 3.40; dielectric loss: 0.018; pressure plate gumming amount: 0.15 percent, the drilling surface is smooth, and the copper-clad plate has good toughness, no cracking, powder falling and flame retardance when being used for drilling: UL94-V0.
Example 9:
the MDI modified phenyl ether amine epoxy resin solution composition for the copper-clad plate glue solution fluidity improver is prepared by uniformly mixing and stirring 30 parts by mass of MDI modified phenyl ether amine epoxy resin solution with the solid content of 57+/-2%, 60 parts by mass of naphthoquinone type phosphorus-containing epoxy resin, 40 parts by mass of XY-8800 anthracene type epoxy resin, 50 parts by mass of ODA type benzoxazine, 8 parts by mass of 2-ethyl-4-methylimidazole and 50 parts by mass of butanone, and then curing the mixture by a 7628 glass fiber cloth pressing plate, wherein the Tg of the obtained product is as follows: 236 ℃; dielectric constant: 3.32; dielectric loss: 0.016; pressure plate gumming amount: 0.14 percent, the drilling surface is smooth, and the copper-clad plate has good toughness, no cracking, powder falling and flame retardance when being used for drilling: UL94-V0.
Example 10:
the MDI modified phenyl ether amine epoxy resin solution composition for the copper-clad plate glue solution fluidity improver is prepared by uniformly mixing and stirring 25 parts by mass of MDI modified phenyl ether amine epoxy resin solution with the solid content of 57+/-2%, 55 parts by mass of naphthoquinone type phosphorus-containing epoxy resin, 36 parts by mass of XY-8800 anthracene type epoxy resin, 44 parts by mass of ODA type benzoxazine, 6 parts by mass of 2-ethyl-4-methylimidazole and 45 parts by mass of butanone, and curing the mixture by a 7628 glass fiber cloth pressing plate, wherein the Tg of the obtained product is as follows: 242 deg.c; dielectric constant: 3.30; dielectric loss: 0.010; pressure plate gumming amount: 0.16 percent, the drilling surface is smooth, and the copper-clad plate has good toughness, no cracking, powder falling and flame retardance when being used for drilling: UL94-V0.
Example 11:
the MDI modified phenyl ether amine epoxy resin solution composition for the copper-clad plate glue solution fluidity improver is prepared by uniformly mixing and stirring 28 parts by mass of MDI modified phenyl ether amine epoxy resin solution with the solid content of 57+/-2%, 57 parts by mass of naphthoquinone type phosphorus-containing epoxy resin, 36 parts by mass of XY-8800 anthracene type epoxy resin, 47 parts by mass of ODA type benzoxazine, 7 parts by mass of 2-ethyl-4-methylimidazole and 48 parts by mass of butanone, and curing the mixture by a 7628 glass fiber cloth pressing plate, wherein the Tg of the obtained product is as follows: 242 deg.c; dielectric constant: 3.28; dielectric loss: 0.011; pressure plate gumming amount: 0.10 percent, the drilling surface is smooth, and the copper-clad plate has good toughness, no cracking, powder falling and flame retardance when being used for drilling: UL94-V0.
Example 12:
the MDI modified phenyl ether amine epoxy resin solution composition for the copper-clad plate glue solution fluidity improver is prepared by uniformly mixing and stirring 23 parts by mass of MDI modified phenyl ether amine epoxy resin solution with the solid content of 57+/-2%, 52 parts by mass of naphthoquinone type phosphorus-containing epoxy resin, 33 parts by mass of XY-8800 anthracene type epoxy resin, 42 parts by mass of ODA type benzoxazine, 5.5 parts by mass of 2-ethyl-4-methylimidazole and 41 parts by mass of butanone, and then curing by a 7628 glass fiber cloth pressing plate, wherein Tg of the obtained product is as follows: 233 ℃; dielectric constant: 3.31; dielectric loss: 0.014; pressure plate gumming amount: 0.17 percent, the drilling surface is smooth, and the copper-clad plate has good toughness, no cracking, powder falling and flame retardance when being used for drilling: UL94-V0.
In examples 8 to 12, the MDI-modified phenylene ether amine epoxy resin having a solid content of 57±2% was MDI-modified phenylene ether amine epoxy resin having a solid content of 57±2% in examples 1 to 8 above, and specific preparation steps were the same, and no description was omitted.
From examples 2-1 to 2-8 and examples 8-12, it is apparent that the composition of the resin for copper-clad plates is prepared from MDI modified phenyl ether amine epoxy resin for the copper-clad plate glue solution fluidity improver, XY-8800 anthracene epoxy resin with high heat resistance, low dielectric and low dielectric loss structure, naphthoquinone phosphorus epoxy resin with phosphorus flame retardant structure, ODA type benzoxazine resin with high heat resistance, low dielectric and low dielectric loss structure, a small amount of curing accelerator and solvent butanone, and the resin composition of the resin for copper-clad plates is provided.
The Tg of the copper-clad plate prepared by the product is more than 230 ℃, the dielectric constant is less than 3.4, the dielectric loss is less than 0.02, the drilling surface is smooth, the toughness of the copper-clad plate is good, the powder is not broken and removed when drilling is applied, the flame retardance is UL94-V0, the adhesive flow of the pressing plate is less than 0.2%, and the resin performance requirement of the high-end copper-clad plate is met.
The amounts of solids mentioned herein are defined as follows: 1g of sample is baked in a 160 ℃ oven for 1 hour, the mass of the non-volatile matter accounts for the percentage of the total mass, and the mass blending of the added cyclohexanone is calculated according to the mass of the non-volatile matter to finally determine the solid amount;
namely: the MDI modified phenyl ether amine epoxy resin solution for the copper-clad plate glue solution fluidity improver with the solid content of 57+/-2 percent is defined as follows: 1g of the sample was baked in an oven at 160℃for 1 hour, the mass of non-volatiles representing 57.+ -. 2% of the total mass.
In the above embodiment: the percentages used are not particularly indicated, and are all percentages by mass (weight) or percentages known to those skilled in the art; the proportions used are not particularly specified, but are mass (weight) proportions; the parts by weight may all be g or kg.
In the above embodiment: the process parameters (temperature, time, etc.) and the amount of each component in each step are within the range, and any point is applicable.
The technical contents of the invention and the technical contents not specifically described in the above embodiments are the same as the prior art, and the raw materials are all commercial products.
It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (4)

1. An MDI modified phenyl ether amine epoxy resin solution for a copper-clad plate glue solution fluidity improver is characterized in that: the MDI modified phenylamine epoxy resin solution is prepared by reacting phenylamine epoxy resin, MDI, bisphenol A and ethyl triphenylphosphine acetate and diluting with cyclohexanone;
the mass percentage content of the solid content of the MDI modified phenyl ether amine epoxy resin solution is 57+/-2%, the viscosity is 10000-15000 mpas, and the number average molecular weight is 8000-12000;
the chemical structural formula of the phenyl ether amine epoxy resin is as follows:
the method comprises the steps of carrying out a first treatment on the surface of the The preparation of the MDI modified phenyl ether amine epoxy resin solution for the copper-clad plate glue solution fluidity improver comprises the following steps:
s1: 90-100 parts by mass of phenyl ether amine epoxy resin and 70-80 parts by mass of cyclohexanone are added into a reactor, the temperature of the reactor is raised to 97-103 ℃ and stirred for 0.5 hour;
s2: adding 0.02-0.1 part by mass of ethyl triphenylphosphine acetate into a reactor, dropwise adding 15-20 parts by mass of MDI liquid into the reactor, stirring after 1-2 hours, heating the reactor to 140-150 ℃ again, and reacting for 2-4 hours;
s3: adding 30-40 parts by mass of bisphenol A into a reactor, heating the reactor to 160-180 ℃, stirring, and reacting for 5-7 hours;
s4: adding 30-40 parts by mass of cyclohexanone into a reactor, and uniformly stirring to obtain the MDI modified phenylate amine epoxy resin solution with the mass percent of the solid content of 57+/-2%.
2. An MDI modified phenyl ether amine epoxy resin solution composition for a copper-clad plate glue solution fluidity improver is characterized in that: the composition comprises the following components: 20 to 30 parts by mass of the MDI-modified phenylamine epoxy resin solution with the solid content of 57+/-2%, 50 to 60 parts by mass of naphthoquinone-type phosphorus-containing epoxy resin, 30 to 40 parts by mass of XY-8800 anthracene-type epoxy resin, 40 to 50 parts by mass of ODA-type benzoxazine, 5 to 8 parts by mass of 2-ethyl-4-methylimidazole and 40 to 50 parts by mass of butanone.
3. The MDI modified phenylene ether amine epoxy resin solution composition for a copper-clad plate glue solution fluidity improver according to claim 2, characterized in that: the structural formula of the naphthoquinone type phosphorus-containing epoxy resin is as follows:
。
4. the MDI modified phenylene ether amine epoxy resin solution composition for a copper-clad plate glue solution fluidity improver according to claim 2, characterized in that: the structural formula of the XY-8800 anthracene type epoxy resin is as follows:
。
CN202210732067.9A 2022-06-27 2022-06-27 MDI modified epoxy resin solution for copper-clad plate glue solution fluidity improver and preparation method and application thereof Active CN115073711B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105778049A (en) * 2016-03-08 2016-07-20 广东广山新材料有限公司 Isocyanate modified epoxide resin and application thereof
CN113717348A (en) * 2021-06-18 2021-11-30 江苏东材新材料有限责任公司 MDI modified epoxy resin with high heat resistance, low dielectric loss and good toughness for copper-clad plate, composition and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105778049A (en) * 2016-03-08 2016-07-20 广东广山新材料有限公司 Isocyanate modified epoxide resin and application thereof
CN113717348A (en) * 2021-06-18 2021-11-30 江苏东材新材料有限责任公司 MDI modified epoxy resin with high heat resistance, low dielectric loss and good toughness for copper-clad plate, composition and preparation method thereof

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