CN115073711A - 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 PDFInfo
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- CN115073711A CN115073711A CN202210732067.9A CN202210732067A CN115073711A CN 115073711 A CN115073711 A CN 115073711A CN 202210732067 A CN202210732067 A CN 202210732067A CN 115073711 A CN115073711 A CN 115073711A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 112
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 112
- 239000003292 glue Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 50
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 44
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 19
- JNJGROHZMWDCCM-UHFFFAOYSA-N C(C)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C(C)(=O)O Chemical compound C(C)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C(C)(=O)O JNJGROHZMWDCCM-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 diphenyl ether amine Chemical class 0.000 claims abstract description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000007865 diluting Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 30
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 20
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 9
- ACQXLBLUVICDGI-UHFFFAOYSA-N [P].C1(C=CC(C2=CC=CC=C12)=O)=O Chemical compound [P].C1(C=CC(C2=CC=CC=C12)=O)=O ACQXLBLUVICDGI-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229930192627 Naphthoquinone Natural products 0.000 claims description 4
- 150000002791 naphthoquinones Chemical class 0.000 claims description 4
- 238000005553 drilling Methods 0.000 abstract description 18
- 229920005989 resin Polymers 0.000 abstract description 18
- 239000011347 resin Substances 0.000 abstract description 18
- 239000000843 powder Substances 0.000 abstract description 10
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical group O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004593 Epoxy Substances 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000003825 pressing Methods 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000005336 cracking Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to a copper-clad plate glue solution fluidity improver MDI modified epoxy resin solution, which is prepared by reacting phenylate amine epoxy resin, MDI, bisphenol A and ethyl triphenyl phosphine acetate and diluting by cyclohexanone; also relates to a preparation method of the MDI modified epoxy resin solution and a composition formed on the basis of the MDI modified epoxy resin solution. The diphenyl ether amine epoxy resin with good heat resistance and MDI are adopted to generate an oxazolidinone structure with high heat resistance under the action of high temperature and catalyst ethyl triphenyl phosphine acetate, and simultaneously, the MDI with double functional groups reacts with the epoxy group, so that the length of an epoxy main chain is prolonged, the crosslinking density is reduced, the toughness of the resin is improved, the copper-clad plate is not cracked and powder is not dropped when the copper-clad plate is applied to drilling, 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 glue solution of the composition for the copper-clad plate can be well controlled.
Description
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 phenylate amine epoxy resin solution composition.
Background
The copper-clad plate is a basic material in the electronic industry, is mainly used for processing and manufacturing printed circuit boards (PCB for short), and is widely used in 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, and matching with a curing agent and a large amount of solvents. However, the benzoxazine resin and some low-activity epoxy resin have low curing activity and slow gelation in the process of pressing a copper-clad plate, so that glue liquid can easily flow away in the process of pressing the plate, the performance of the plate is poor, and meanwhile, the benzoxazine resin and some low-activity epoxy resin have low heat resistance (Tg) and high brittleness, so that the application of the benzoxazine resin and some low-activity epoxy resin 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 phenylate 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 phenylate amine epoxy resin solution is prepared by reacting phenylate amine epoxy resin, MDI, bisphenol A and ethyl triphenyl phosphine acetate, and diluting by cyclohexanone, wherein the MDI modified phenylate amine epoxy resin in the MDI modified phenylate amine epoxy resin solution has a chemical structure simple formula shown as follows:
furthermore, the mass percentage content of the solid of the MDI modified phenylate 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 phenylate amine epoxy resin is as follows:
a preparation method of MDI modified epoxy resin solution for a copper-clad plate glue solution fluidity improver is characterized by comprising the following steps: the method comprises the following steps:
s1: adding 90-100 parts by mass of phenylate amine epoxy resin and 70-80 parts by mass of cyclohexanone into a reactor, heating the reactor to 97-103 ℃, and stirring for 0.5 hour;
s2: adding 0.02-0.1 part by mass of ethyl triphenyl phosphine 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 ℃, 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 the reactor, and uniformly stirring to obtain the MDI modified phenylate amine epoxy resin solution with the solid content of 57 +/-2% by mass.
The MDI modified epoxy resin solution composition for the copper-clad plate glue solution fluidity improver has the innovation points that: comprises the following components: 20-30 parts by mass of MDI modified phenylate amine epoxy resin solution with the solid content of 57 +/-2%, 50-60 parts by mass of naphthoquinone phosphorus-containing epoxy resin, 30-40 parts by mass of XY-8800 anthracene epoxy resin, 40-50 parts by mass of ODA benzoxazine, 5-8 parts by mass of 2-ethyl-4-methylimidazole and 40-50 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 diphenyl ether amine epoxy resin with good heat resistance and MDI are adopted to generate an oxazolidinone structure with high heat resistance under the action of high temperature and catalyst ethyl triphenyl phosphine acetate, and simultaneously, the MDI with double functional groups reacts with an epoxy group, so that the length of an epoxy main chain is prolonged, the cross-linking density is reduced, the toughness of the resin is improved, the copper-clad plate is not cracked and powder falls when the copper-clad plate is applied to drilling, finally, the resin is further extended by bisphenol A, the number average molecular weight of the resin is controlled to be 8000-12000, and the fluidity of the glue solution of the composition for the copper-clad plate can be well controlled;
MDI modified phenylate amine epoxy resin, anthracene epoxy resin with high heat resistance, low dielectric and low dielectric loss structure, naphthoquinone phosphorus-containing epoxy resin with heat resistance, phosphorus-containing 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 are adopted to prepare the composition of resin for the copper-clad plate, and the resin composition with high heat resistance, halogen-free flame retardance, low dielectric loss, high toughness and glue running prevention 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 and no cracking and powder falling when drilling is applied, the flame retardance is UL94-V0, the glue flow amount of a pressing plate (the mass of the glue flow loss when the pressing plate is pressed accounts for the mass of the total glue) is less than 0.2 percent, and the performance requirement of the resin for the high-end copper-clad plate is met.
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the scope of the embodiments described herein.
The MDI modified epoxy resin solution for the copper-clad plate glue solution fluidity improver is prepared by the reaction of phenylate amine epoxy resin, MDI, bisphenol A, ethyl triphenyl phosphine acetate and cyclohexanone, wherein the MDI is 4, 4' -diisocyanate diphenylmethane.
The MDI modified epoxy resin in the MDI modified epoxy resin solution has the chemical structure simple formula as shown in the specification:
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: adding 90-100 parts by mass of phenylate type amine epoxy resin and 70-80 parts by mass of cyclohexanone into a reactor, wherein the chemical structural formula of the phenylate type amine epoxy resin is shown in the specification
The reactor is heated to 97-103 ℃ and stirred for 0.5 hour.
S2: adding 0.02-0.1 part by mass of ethyl triphenyl phosphine acetate into a reactor, wherein the chemical structural formula of the ethyl triphenyl phosphine acetate is shown in the specification
And dropwise adding 15-20 parts by mass of MDI liquid into the reactor, wherein the MDI liquid has the chemical structural formula
Dripping for 1-2 hours, stirring, heating the reactor to 140-150 ℃, 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 the reactor, and uniformly stirring to obtain the MDI modified phenylate amine epoxy resin solution with the solid content of 57 +/-2% by mass.
Examples 1-1 to 1-8, using different amounts and process conditions, are shown in table 1,
table 1: the formula amount (unit: kg) of the MDI modified phenylate amine epoxy resin solution for preparing the copper-clad plate glue solution fluidity improver and the process condition table are as follows:
TABLE 1
In table 1, temperature a is the temperature-rising temperature of the reactor in step S1, temperature B is the temperature-rising temperature of the reactor in step S2, time a is the reaction time of the reactor in step S2, temperature C is the temperature-rising temperature of the reactor in step S3, and time B is the reaction time of the reactor in step S3.
The MDI modified phenylate amine epoxy resin solution composition for the copper-clad plate glue solution fluidity improver comprises the following components: 20-30 parts by mass of MDI modified phenylate amine epoxy resin solution with the solid content of 57 +/-2%, 50-60 parts by mass of naphthoquinone phosphorus-containing epoxy resin, 30-40 parts by mass of XY-8800 anthracene epoxy resin, 40-50 parts by mass of ODA benzoxazine, 5-8 parts by mass of 2-ethyl-4-methylimidazole and 40-50 parts by mass of butanone,
the structural formula of the naphthoquinone type phosphorus-containing epoxy resin is as follows:
the structural formula of 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, using different amounts and process conditions, are specified in table 2,
table 2: the formula table (unit: mass portion) of the MDI modified phenylate amine epoxy resin solution composition for preparing the copper-clad plate glue solution fluidity improver is as follows:
TABLE 2
1-1 to 1-8 in Table 2 are the MDI modified phenylene ether amine epoxy resin solutions prepared in the above examples.
Table 3 shows the comparison of the copper-clad plate performance results of the MDI modified phenylate amine epoxy resin solution composition for the copper-clad plate glue solution fluidity improver in the embodiments 2-1 to 2-8:
TABLE 3
As can be seen from the comparison of the data in Table 3, the MDI modified phenylate 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 copper-clad plate has good toughness and no cracking and powder dropping when drilling is applied, the flame retardance is UL94-V0, the glue flow rate of the pressing plate (the mass of glue flow loss during pressing plate accounts for less than 0.2 percent of the mass of the total glue solution), and the resin performance requirement for high-end copper-clad plates is met.
Example 3:
adding 90 parts by mass of phenylate type amine epoxy resin and 70 parts by mass of cyclohexanone into a reactor, and heating the reactor to 100 ℃; adding 0.02 part by mass of ethyl triphenyl phosphine acetate into the reactor, dripping 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; and finally, adding 30 parts by mass of cyclohexanone into the reactor, and uniformly stirring to obtain the MDI modified phenylate amine epoxy resin solution with the solid content of 57 +/-2 percent by mass, wherein the solution has the viscosity of 12000mpas and is light yellow liquid.
Example 4:
adding 100 parts by mass of phenylate type amine epoxy resin and 80 parts by mass of cyclohexanone into a reactor, and heating to 100 ℃; then adding 0.1 part by mass of ethyl triphenyl phosphine acetate into the reactor, dripping 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 the reactor, heating to 170 ℃, stirring, and reacting for 6 hours; and finally, adding 40 parts by mass of cyclohexanone into the reactor, and uniformly stirring to obtain the MDI modified phenylate amine epoxy resin solution with the solid content of 57 +/-2 percent by mass, wherein the solution has the viscosity of 13000mpas and is light yellow liquid.
Example 5:
adding 95 parts by mass of phenylate type amine epoxy resin and 75 parts by mass of cyclohexanone into a reactor, and heating to 100 ℃; then 0.06 part by mass of ethyl triphenyl phosphine acetate is added into the reactor, 18 parts by mass of MDI liquid is dripped into the reactor, the mixture is stirred, the temperature is raised to 150 ℃, and the reaction is carried out for 4 hours; adding 35 parts by mass of bisphenol A into the reactor, heating to 180 ℃, stirring, and reacting for 6 hours; and finally, adding 35 parts by mass of cyclohexanone into the reactor, and uniformly stirring to obtain the MDI modified phenylate amine epoxy resin solution with the solid content of 57 +/-2 percent by mass, wherein the viscosity of the solution is 11000mpas, and the solution is a light yellow liquid.
Example 6:
adding 98 parts by mass of phenylate type amine epoxy resin and 77 parts by mass of cyclohexanone into a reactor, and heating to 100 ℃; adding 0.08 part by mass of ethyl triphenyl phosphine acetate into the reactor, dropwise adding 19 parts by mass of MDI liquid, stirring, heating to 145 ℃, and reacting for 3 hours; adding 38 parts by mass of bisphenol A into the reactor, heating to 175 ℃, stirring, and reacting for 6 hours; and finally, adding 37 parts by mass of cyclohexanone into the reactor, and uniformly stirring to obtain the MDI modified phenylate amine epoxy resin solution with the solid content of 57 +/-2 percent by mass, wherein the solution has the viscosity of 14000mpas and is light yellow liquid.
Example 7:
adding 93 parts by mass of phenylate type amine epoxy resin and 74 parts by mass of cyclohexanone into a reactor, and heating to 100 ℃; then adding 0.04 parts by mass of ethyl triphenyl phosphine acetate into the 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; and finally, adding 32 parts by mass of cyclohexanone into the reactor, and uniformly stirring to obtain the MDI modified phenylate amine epoxy resin solution with the solid content of 57 +/-2% by mass, wherein the solution has the viscosity of 13500mpas and is a light yellow liquid.
From examples 1-1 to 1-8 and examples 3-7, it is known that a high toughness and improved flowability MDI modified epoxy resin for copper clad laminate with excellent comprehensive properties is provided by using a diphenyl ether amine epoxy resin, MDI (4, 4' -diisocyanate diphenylmethane), bisphenol A and cyclohexanone to generate a high heat resistant MDI modified epoxy resin solution with an oxazolidinone structure under the action of high temperature and a catalyst ethyl triphenyl phosphine acetate, and then extending the chain with bisphenol A.
Example 8:
the composition is prepared by uniformly mixing and stirring 20 parts by mass of MDI modified phenylate amine epoxy resin solution with the mass percentage content of solids of 57 +/-2%, 50 parts by mass of naphthoquinone phosphorus epoxy resin, 30 parts by mass of XY-8800 anthracene epoxy resin, 40 parts by mass of ODA 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 the Tg of the obtained product is as follows: 232 ℃; dielectric constant: 3.40; dielectric loss: 0.018; the glue flow of the pressing plate is as follows: 0.15 percent, smooth drilling surface, good toughness of the copper clad laminate during drilling, no cracking and powder falling and flame retardance: UL 94-V0.
Example 9:
the composition is prepared by uniformly mixing and stirring 30 parts by mass of MDI modified phenylate amine epoxy resin solution with the mass percentage content of solids of 57 +/-2%, 60 parts by mass of naphthoquinone phosphorus epoxy resin, 40 parts by mass of XY-8800 anthracene epoxy resin, 50 parts by mass of ODA benzoxazine, 8 parts by mass of 2-ethyl-4-methylimidazole and 50 parts by mass of butanone, and curing by a 7628 glass fiber cloth pressing plate to obtain the product with the Tg: 236 ℃; dielectric constant: 3.32 of; dielectric loss: 0.016; the glue flow of the pressing plate is as follows: 0.14 percent, smooth drilling surface, good toughness of the copper clad laminate during drilling, no cracking and powder falling and flame retardance: UL 94-V0.
Example 10:
the composition is prepared by uniformly mixing and stirring 25 parts by mass of MDI modified phenylate amine epoxy resin solution with the solid content of 57 +/-2 percent, 55 parts by mass of naphthoquinone phosphorus epoxy resin, 36 parts by mass of XY-8800 anthracene epoxy resin, 44 parts by mass of ODA benzoxazine, 6 parts by mass of 2-ethyl-4-methylimidazole and 45 parts by mass of butanone, and curing by a 7628 glass fiber cloth pressing plate to obtain the product with the Tg: 242 ℃; dielectric constant: 3.30; dielectric loss: 0.010; the glue flow of the pressing plate is as follows: 0.16 percent, smooth drilling surface, good toughness of the copper clad laminate during drilling, no cracking and powder falling and flame retardance: UL 94-V0.
Example 11:
the composition is prepared by uniformly mixing and stirring 28 parts by mass of MDI modified phenylate amine epoxy resin solution with the mass percentage content of solids of 57 +/-2%, 57 parts by mass of naphthoquinone phosphorus epoxy resin, 36 parts by mass of XY-8800 anthracene epoxy resin, 47 parts by mass of ODA benzoxazine, 7 parts by mass of 2-ethyl-4-methylimidazole and 48 parts by mass of butanone, and curing by a 7628 glass fiber cloth pressing plate to obtain the product with the Tg: 242 ℃; dielectric constant: 3.28; dielectric loss: 0.011; the glue flow of the pressing plate is as follows: 0.10 percent, smooth drilling surface, good toughness of the copper clad laminate during drilling, no cracking and powder falling and flame retardance: UL 94-V0.
Example 12:
the composition is prepared by uniformly mixing and stirring 23 parts by mass of MDI modified phenylate amine epoxy resin solution with the mass percentage content of solids of 57 +/-2%, 52 parts by mass of naphthoquinone phosphorus epoxy resin, 33 parts by mass of XY-8800 anthracene epoxy resin, 42 parts by mass of ODA benzoxazine, 5.5 parts by mass of 2-ethyl-4-methylimidazole and 41 parts by mass of butanone, and curing a 7628 glass fiber cloth pressing plate to obtain the product with the Tg: 233 ℃; dielectric constant: 3.31; dielectric loss: 0.014; the glue flow of the pressing plate is as follows: 0.17 percent, smooth drilling surface, good toughness of the copper clad laminate during drilling, no cracking and powder falling and flame retardance: UL 94-V0.
In examples 8 to 12, the MDI modified phenylene ether type amine epoxy resin having a solid content of 57 ± 2% by mass was the MDI modified phenylene ether type amine epoxy resin having a solid content of 57 ± 2% by mass in the above examples 1 to 8, and the specific preparation steps were the same and will not be described again.
From examples 2-1 to 2-8 and 8-12, it is known that a resin composition for copper clad laminate, which is prepared from MDI modified phenyl ether type amine epoxy resin for copper clad laminate glue solution fluidity improver, XY-8800 anthracene type epoxy resin with high heat resistance, low dielectric and low loss structure, naphthoquinone type phosphorus epoxy resin with phosphorus flame retardant structure, ODA type benzoxazine resin with high heat resistance, low dielectric and low loss structure, a small amount of curing accelerator and butanone as solvent, provides a resin composition with high heat resistance, halogen-free flame retardance, low dielectric loss, high toughness and glue running resistance.
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 copper-clad plate has good toughness, no cracking and powder falling, flame retardance UL94-V0 and less than 0.2% of the flow amount of a pressing plate when drilling is applied, and the resin performance requirement for a 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 finally determined solid amount by mass blending of the added cyclohexanone is calculated according to the mass of the non-volatile matter;
namely: the definition of the MDI modified phenylate amine epoxy resin solution for the copper-clad plate glue solution fluidity improver with the solid content of 57 +/-2 percent is as follows: the mass percentage of non-volatile matter in the total mass of 1g of the sample after 1 hour of baking in an oven at 160 ℃ was 57. + -.2%.
In the above embodiment: the percentages used, not specifically indicated, are percentages by weight or known to those skilled in the art; the proportions used, not specifically noted, are mass (weight) proportions; the parts by weight may each be grams or kilograms.
In the above embodiment: the process parameters (temperature, time, etc.) and the numerical values of the components in each step are in the range, and any point can be applicable.
The present invention and the technical contents not specifically described in the above examples are the same as those of the prior art, and the raw materials are all commercially available products.
It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. An MDI modified epoxy resin solution for a copper-clad plate glue solution fluidity improver is characterized in that: the MDI modified phenylate amine epoxy resin solution is prepared by reacting phenylate amine epoxy resin, MDI, bisphenol A and ethyl triphenyl phosphine acetate, and diluting by cyclohexanone, wherein the MDI modified phenylate amine epoxy resin in the MDI modified phenylate amine epoxy resin solution has a chemical structure simple formula shown as follows:
2. the MDI modified epoxy resin solution for the copper-clad plate glue solution fluidity improver according to claim 1, which is characterized in that: the mass percentage content of the solid of the MDI modified phenylamine epoxy resin solution is 57 +/-2%, the viscosity is 10000-15000 mpas, and the number average molecular weight is 8000-12000.
3. The MDI modified epoxy resin solution for the copper-clad plate glue solution fluidity improver according to claim 1, which is characterized in that: the chemical structural formula of the phenylate amine epoxy resin is as follows:
4. a method for preparing MDI modified epoxy resin solution for the copper-clad plate glue solution fluidity improver according to claim 1, which is characterized in that: the method comprises the following steps:
s1: adding 90-100 parts by mass of phenylate amine epoxy resin and 70-80 parts by mass of cyclohexanone into a reactor, heating the reactor to 97-103 ℃, and stirring for 0.5 hour;
s2: adding 0.02-0.1 part by mass of ethyl triphenyl phosphine 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 ℃, 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 the reactor, and uniformly stirring to obtain the MDI modified phenylate amine epoxy resin solution with the solid content of 57 +/-2% by mass.
5. An MDI modified epoxy resin solution composition for a copper-clad plate glue solution fluidity improver is characterized in that: comprises the following components: 20-30 parts by mass of MDI modified phenylate amine epoxy resin solution with the solid content of 57 +/-2%, 50-60 parts by mass of naphthoquinone phosphorus-containing epoxy resin, 30-40 parts by mass of XY-8800 anthracene epoxy resin, 40-50 parts by mass of ODA benzoxazine, 5-8 parts by mass of 2-ethyl-4-methylimidazole and 40-50 parts by mass of butanone.
6. The MDI modified epoxy resin solution for the copper-clad plate glue solution fluidity improver according to claim 5, which is characterized in that: the structural formula of the naphthoquinone type phosphorus-containing epoxy resin is as follows:
7. the MDI modified epoxy resin solution for the copper-clad plate glue solution fluidity improver according to claim 5, which is characterized in that: the structural formula of the XY-8800 anthracene epoxy resin is as follows:
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| 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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| 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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