CN115746763A - Modified epoxy adhesive, preparation method thereof, prepreg and flexible copper clad laminate - Google Patents
Modified epoxy adhesive, preparation method thereof, prepreg and flexible copper clad laminate Download PDFInfo
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- CN115746763A CN115746763A CN202211556092.2A CN202211556092A CN115746763A CN 115746763 A CN115746763 A CN 115746763A CN 202211556092 A CN202211556092 A CN 202211556092A CN 115746763 A CN115746763 A CN 115746763A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229920006332 epoxy adhesive Polymers 0.000 title claims abstract description 58
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 38
- 239000010949 copper Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000003822 epoxy resin Substances 0.000 claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000004814 polyurethane Substances 0.000 claims abstract description 19
- 229920002635 polyurethane Polymers 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 10
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 239000011889 copper foil Substances 0.000 claims description 21
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 18
- 238000004381 surface treatment Methods 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000002313 adhesive film Substances 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- -1 boron trifluoride amine Chemical class 0.000 claims description 8
- 229920001690 polydopamine Polymers 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 5
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 5
- 238000009832 plasma treatment Methods 0.000 claims description 5
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- 229920002799 BoPET Polymers 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920000921 polyethylene adipate Polymers 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 description 23
- 229920001721 polyimide Polymers 0.000 description 23
- 238000012360 testing method Methods 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 8
- 239000012790 adhesive layer Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000007719 peel strength test Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- 239000002131 composite material Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000010125 resin casting Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- WPEOOEIAIFABQP-UHFFFAOYSA-N hexanedioic acid;hexane-1,6-diol Chemical compound OCCCCCCO.OC(=O)CCCCC(O)=O WPEOOEIAIFABQP-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention discloses a modified epoxy adhesive and a preparation method thereof, a prepreg comprising the modified epoxy adhesive and a flexible copper clad laminate comprising the prepreg. The modified epoxy adhesive comprises the following components in parts by weight: 72.2 to 138.8 portions of polyurethane, 300 to 400 portions of epoxy resin, 75 to 100 portions of high-temperature curing agent, 240 to 320 portions of diluent and 2 to 4 portions of curing accelerator; 72.2 to 138.8 portions of polyurethane is 10 to 40 portions of diisocyanate, 60 to 90 portions of polyester polyol, 2 to 8 portions of cross-linking agent and 0.2 to 0.8 portion of catalyst. The modified epoxy adhesive greatly improves the high temperature resistance and the toughness enhancement of the modified epoxy adhesive by the polyurethane toughening epoxy resin and the matching of a high-temperature curing agent.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a modified epoxy adhesive and a preparation method thereof, a prepreg and a flexible copper clad laminate.
Background
The Flexible Copper Clad Laminate (FCCL) refers to a copper clad laminate formed by performing certain process treatment on one side or two sides of a flexible insulating material such as Polyimide (PI) or a polyester film and then laminating the copper clad laminate and a copper foil. It has the characteristics of free bending, high wiring density, light weight, thin thickness and good bending property. FCCL is a basic material in the electronic industry, is a main material for processing and manufacturing flexible printed circuit boards (FPC), and is widely applied to the fields of spaceflight, digital cameras, mobile communication, computers and the like.
The FCCL is mainly composed of three parts, namely a conductor material, an insulating film and an adhesive. Wherein, the conductor material is copper foil; the insulating film can be selected from a PI film and other flexible polyester films, and the PI film has better dimensional stability and higher high-temperature resistance, so that the PI film is widely applied to FCCL with high welding resistance requirements; the adhesive mainly includes a polyester adhesive, a polyimide adhesive, and an epoxy adhesive, wherein the epoxy adhesive is used as an adhesive for FCCL because of its advantages of high adhesive strength, good dimensional stability, excellent chemical resistance, and low curing shrinkage.
Although epoxy resin has many advantages when used as an adhesive, epoxy resin has the disadvantages of poor high temperature resistance and brittleness, so that high temperature resistance, toughening and modification are required.
Disclosure of Invention
Accordingly, there is a need for a modified epoxy adhesive with better high temperature resistance and better toughness.
In addition, a preparation method of the modified epoxy adhesive is also provided.
In addition, a prepreg comprising the modified epoxy adhesive and a flexible copper clad laminate comprising the prepreg are also necessarily provided.
A modified epoxy adhesive comprises the following components in parts by weight:
72.2 to 138.8 portions of polyurethane, 300 to 400 portions of epoxy resin, 75 to 100 portions of high-temperature curing agent, 240 to 320 portions of diluent and 2 to 4 portions of curing accelerator;
72.2 to 138.8 portions of polyurethane is 10 to 40 portions of diisocyanate, 60 to 90 portions of polyester polyol, 2 to 8 portions of cross-linking agent and 0.2 to 0.8 portion of catalyst.
In one embodiment, the high temperature curing agent is selected from at least one of dicyandiamide, 4,4' -diaminodiphenyl ether, 4,4' -diaminodiphenylmethane, and 4,4' -diaminodiphenylsulfone.
In one embodiment, the epoxy resin is selected from at least one of epoxy resin EP-51, epoxy resin EP-20, epoxy resin AG-80, and epoxy resin BNE-200.
In one embodiment, the curing accelerator is selected from at least one of imidazole, resorcinol, boron trifluoride amine, 2-ethyl-4-methylimidazole, and triethanolamine;
the diluent is at least one selected from acetone, butanone, N' -dimethylformamide and dimethyl sulfoxide.
In one embodiment, the polyester polyol is selected from at least one of polyethylene adipate, 1,6-hexanediol polycarbonate, 1,4-butanediol adipate, and 1,6-hexanediol adipate, the polyester polyol having a molecular weight of 1000 to 3000;
the diisocyanate is selected from at least one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and toluene diisocyanate;
the cross-linking agent is trimethylolpropane;
the catalyst is dibutyltin dilaurate.
The preparation method of the modified epoxy adhesive comprises the following steps:
under the atmosphere of protective gas, 10 to 40 parts of diisocyanate, 60 to 90 parts of polyester polyol and 0.2 to 0.8 part of catalyst are mixed uniformly and then are subjected to prepolymerization reaction at 60 to 90 ℃, and then 2 to 8 parts of cross-linking agent is added for continuous reaction to obtain a reaction mixture, namely polyurethane;
and heating the reaction mixture to 80-100 ℃, adding 300-400 parts of epoxy resin and 75-100 parts of high-temperature curing agent, uniformly mixing, cooling to 30-50 ℃, adding 240-320 parts of diluent to adjust viscosity, and finally adding 2-4 parts of curing accelerator to fully react to obtain the required modified epoxy adhesive.
In one embodiment, the reaction time of the prepolymerization reaction is 0.5-1.5 h, the reaction time of adding 2-8 parts of cross-linking agent for continuous reaction is 1-3 h, and the reaction time of adding 2-4 parts of curing accelerator for full reaction is 0.5-1 h;
the operation of adding and uniformly mixing 300 to 400 parts of epoxy resin and 75 to 100 parts of high-temperature curing agent is as follows: adding 300-400 parts of the epoxy resin for multiple times within 2h, and then adding 75-100 parts of the high-temperature curing agent.
A prepreg preparation process comprises the following steps: and gluing the prepared modified epoxy adhesive on the surface of a flexible film, wherein the thickness of the adhesive film is 10-50 um, and then placing the adhesive film into an oven to be dried for 2-7min at the temperature of 130-170 ℃ to obtain the prepreg.
The prepreg comprises a surface treatment flexible film and an adhesive film arranged on the surface treatment flexible film, wherein the adhesive film is made of the modified epoxy adhesive.
In one embodiment, the surface-treated flexible film is prepared by: and carrying out surface treatment on the flexible insulating film to obtain the surface-treated flexible film, wherein the surface treatment is alkali treatment, plasma treatment or polydopamine coating treatment, and the flexible insulating film is a PI film or a PET film.
The preparation process of the flexible copper-clad plate comprises the following steps: and pressing the prepared prepreg and 10-35 um copper foil on a hot press at the temperature of 150-190 ℃ and the pressure of 8-12MPa for 1-3min, and finally putting the prepreg and the copper foil into an oven at the temperature of 150-210 ℃ for curing for 1-2h to prepare the flexible copper clad laminate.
The flexible copper-clad plate comprises a copper foil and the prepreg, wherein the surface treatment flexible film, the adhesive film and the copper foil are sequentially stacked.
The modified epoxy adhesive greatly improves the high temperature resistance and toughness of the modified epoxy adhesive by the polyurethane toughening epoxy resin and the matching of a high-temperature curing agent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Wherein:
FIG. 1 is a graph showing the results of peel strength tests on flexible copper clad laminates prepared in comparative example 2, example 11 and example 7.
Fig. 2 is a graph showing the results of peel strength tests of flexible copper clad laminates prepared in examples 10, 9, 8, 7, 6 and 5.
FIG. 3 is a graph showing the results of impact strength tests on flexible copper clad laminates prepared in comparative example 1, example 10, example 9, example 8, example 7, example 6 and example 5.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The invention discloses a modified epoxy adhesive of an embodiment, which comprises the following components in parts by weight: 72.2 to 138.8 portions of polyurethane, 300 to 400 portions of epoxy resin, 75 to 100 portions of high-temperature curing agent, 240 to 320 portions of diluent and 2 to 4 portions of curing accelerator.
72.2 to 138.8 portions of polyurethane is 10 to 40 portions of diisocyanate, 60 to 90 portions of polyester polyol, 2 to 8 portions of cross-linking agent and 0.2 to 0.8 portion of catalyst.
The modified epoxy adhesive greatly improves the high temperature resistance and the toughness enhancement of the modified epoxy adhesive by polyurethane toughening epoxy resin and matching with a high-temperature curing agent.
Generally, the curing temperature of the high-temperature curing agent is 140 ℃ to 220 ℃.
In this embodiment, the high temperature curing agent is at least one selected from the group consisting of dicyandiamide, 4,4' -diaminodiphenyl ether, 4,4' -diaminodiphenylmethane, and 4,4' -diaminodiphenylsulfone.
In this embodiment, the epoxy resin is selected from at least one of epoxy resin EP-51, epoxy resin EP-20, epoxy resin AG-80, and epoxy resin BNE-200.
In the present embodiment, the curing accelerator is at least one selected from the group consisting of imidazole, resorcinol, boron trifluoride amine, 2-ethyl-4-methylimidazole, and triethanolamine.
In the present embodiment, the diluent is at least one selected from the group consisting of acetone, methyl ethyl ketone, N' -dimethylformamide, and dimethyl sulfoxide.
In this embodiment, the polyester polyol is at least one selected from the group consisting of polyethylene adipate, polycarbonate 1,6-hexanediol, polyadipic acid-1,4-butanediol, and polyadipic acid-1,6-hexanediol, and the molecular weight of the polyester polyol is 1000 to 3000.
In the present embodiment, the diisocyanate is at least one selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and toluene diisocyanate.
In this embodiment, the crosslinking agent is trimethylolpropane.
In this embodiment, the catalyst is dibutyltin dilaurate.
The invention also discloses a preparation method of the modified epoxy adhesive, which comprises the following steps:
s10, under the atmosphere of protective gas, uniformly mixing 10-40 parts of diisocyanate, 60-90 parts of polyester polyol and 0.2-0.8 part of catalyst, carrying out prepolymerization reaction at 60-90 ℃, adding 2-8 parts of cross-linking agent, and continuously reacting to obtain a reaction mixture, namely polyurethane.
By the operation of S10, a polyurethane having a crosslinked network structure can be produced.
Typically, the shielding gas may be nitrogen.
Preferably, in S10, the reaction time of the prepolymerization reaction is 0.5-1.5 h, and the reaction time of adding 2-8 parts of the crosslinking agent for continuous reaction is 1-3 h.
Preferably, in S10, adding 300 to 400 parts of epoxy resin and 75 to 100 parts of high-temperature curing agent and mixing them uniformly comprises: adding 300-400 parts of epoxy resin for multiple times within 2h, and then adding 75-100 parts of high-temperature curing agent.
S20, heating the reaction mixture to 80-100 ℃, adding 300-400 parts of epoxy resin and 75-100 parts of high-temperature curing agent, uniformly mixing, cooling to 30-50 ℃, adding 240-320 parts of diluent to adjust viscosity, and finally adding 2-4 parts of curing accelerator to fully react to obtain the required modified epoxy adhesive.
Adding 2 to 4 parts of curing accelerator and fully reacting for 0.5 to 1 hour.
By selecting a proper high-temperature curing agent and matching with a proper curing temperature, when the finally prepared modified epoxy adhesive is applied to the flexible copper clad laminate, the flexible copper clad laminate can pass a solder resistance test of 320 ℃/10 s.
The flexible copper clad laminate prepared by the modified epoxy adhesive has high peel strength which can reach 1.72Kgf/cm at most.
Compared with the traditional method, the method has the advantages that the heat-resistant group is introduced into the system through prepolymerization in an organic solvent, so that the complex steps of the welding resistance of the flexible copper-clad plate are improved, and the preparation process of the flexible copper-clad plate is simpler, energy-saving and environment-friendly.
The invention also discloses a prepreg of an embodiment, which comprises a surface treatment flexible film and an adhesive film arranged on the surface treatment flexible film, wherein the adhesive film is made of the modified epoxy adhesive.
Generally, the thickness of the adhesive film may be 10 μm to 50 μm.
Preferably, the surface-treated flexible film is prepared by: and carrying out surface treatment on the flexible insulating film to obtain the surface-treated flexible film.
The surface treatment enables the surface of the flexible insulating film to have more active groups, so that cohesive energy of an adhesive layer is damaged when the flexible copper clad laminate is peeled, and the peeling between the modified epoxy adhesive with lower peeling strength and the flexible insulating film is not carried out.
The surface treatment is alkali treatment, plasma treatment or polydopamine coating treatment, and the flexible insulating film is a PI film or a PET film.
Specifically, the alkali treatment may be: the flexible insulating film is put into 10wt% NaOH solution at 60 ℃ for treatment for 5min, so that the surface activity of the flexible insulating film is improved.
In particular, in the case of a system,the plasma treatment may be: placing the flexible insulating film into a vacuum plasma processor at N 2 Treating for 10min under atmosphere to improve surface activity.
Specifically, the polydopamine coating treatment may be: and coating a layer of polydopamine with the thickness of 5-20 mu m on the flexible insulating film, so that the surface activity of the polydopamine is improved.
In this embodiment, the prepreg may be prepared by: coating the surface of the surface treatment flexible film with a modified epoxy adhesive to form a glue film with the thickness of 10-50 mu m, and then drying at 130-170 ℃ for 2-7min to obtain the required prepreg.
The invention also discloses a flexible copper clad laminate of an embodiment, which comprises a copper foil and the prepreg, wherein the surface treatment flexible film, the adhesive film and the copper foil are sequentially laminated.
The copper foil is generally 10 to 35 μm thick.
In the embodiment, the flexible copper clad laminate can be prepared by the following operations: and (3) pressing the prepreg and the copper foil on a hot press with the temperature of 150-190 ℃ and the pressure of 8-12MPa for 1-3min, and then putting the prepreg and the copper foil into an oven with the temperature of 150-210 ℃ for curing for 1-2h to obtain the flexible copper clad laminate.
The following are specific examples
Example 1
The preparation method of the modified epoxy adhesive comprises the following steps:
(1) Under the nitrogen atmosphere, 20g of isophorone diisocyanate, 80g of polybutylene adipate and 0.5g of dibutyltin dilaurate are added into a reaction vessel, prepolymerization is carried out for 1.5h at 70 ℃, then 3.5g of trimethylolpropane is added to continue to react for 1.5h, and the obtained system is polyurethane with a cross-linked network structure.
(2) The system was heated to 90 ℃ and 350g of epoxy EP-51 were added to the system in 2h portions and stirred thoroughly. Then adding 90g of curing agent 4,4' -diaminodiphenylmethane into the system, and continuing stirring for 0.5h;
(3) And (3) cooling to 40 ℃, adding 280g of butanone during the cooling process to adjust the viscosity of the system, then adding 3.5g of 2-ethyl-4-methylimidazole into the system, and continuously stirring for 40min to obtain the modified epoxy adhesive.
The preparation steps of the flexible copper-clad plate are as follows:
(1) Putting the PI film into 10wt% of 60 ℃ NaOH solution for treatment for 5min, thereby improving the surface activity of the PI film;
(2) Coating a modified epoxy adhesive on the PI film by using a coating rod to form a 40-micron adhesive layer, and then putting the adhesive layer into a 160-DEG C drying oven to be dried for 5min until the surface is dried to obtain a prepreg;
(3) And (3) performing composite hot pressing on the copper foil with the thickness of 30 microns and the prepreg for 1.5min on a hot press with the temperature of 160 ℃ and the pressure of 12MPa, then putting the copper foil and the prepreg into an oven with the temperature of 170 ℃ for curing for 1h, then raising the temperature of the oven to 200 ℃, and curing for 20min to obtain the flexible copper-clad plate.
The impact strength test reference standard GB/T2576-2021 resin casting body performance test method cures the modified epoxy adhesive in a PTFE mould to obtain 80 multiplied by 10 multiplied by 4mm 3 The unnotched impact sample strip is subjected to impact test on a pendulum cantilever beam impact tester with the energy of 5.5J, 5 samples are tested in each group, and the average value is taken to obtain the impact strength of the modified epoxy adhesive cured sample strip.
The peel strength test refers to the standard GB/T2791-1995 adhesive T peel strength test method for flexible material to flexible material, and the effective peel length of the flexible copper-clad plate is as follows: the thickness is 200mm multiplied by 25mm, the peeling speed of the flexible copper clad laminate on a computerized tensile testing machine is 100mm/min, 5 samples are tested in each group, and the peeling strength of the flexible copper clad laminate is obtained by taking the average value.
The solder resistance test refers to the American industry standard IPC-TM-650-2.4.13, the prepared flexible copper clad laminate is cut into 20mm multiplied by 20mm test samples, dip soldering tests of 288 ℃/10s and 320 ℃/10s are respectively carried out on the samples in a soldering pot, 5 samples are tested under each temperature condition, and whether the flexible copper clad laminate has the phenomena of layering and blistering after the test of the soldering pot is observed.
The impact strength of the sample bar obtained by the method can reach 34.33KJ/m 2 Is less modified than 15.75KJ/m 2 The impact strength is improved by 118%, and the toughness of the material is obviously improved; flexible copper cladThe peel strength of the plate can reach 1.36Kgf/cm; and the solder dip resistance test at 320 ℃/10s can be passed, and the use standard of the flexible copper clad laminate is met.
Example 2
The preparation method of the modified epoxy adhesive comprises the following steps:
(1) Under the atmosphere of nitrogen, 32g of hexamethylene diisocyanate, 68g of polycarbonate 1,6-hexanediol and 0.5g of dibutyltin dilaurate are added into a reaction vessel, prepolymerization is carried out for 0.5h at 80 ℃, then 4.5g of trimethylolpropane is added, and reaction is continued for 2h, so that the obtained system is the polyurethane with the crosslinked network structure.
(2) The system is heated to 90 ℃, 150g of epoxy EP-51, 100g of epoxy EP-20 and 100g of epoxy BNE-200 are added into the system for a plurality of times in 2 hours, and the mixture is fully stirred. Then adding 75g of curing agent 4,4' -diaminodiphenyl ether into the system, and continuing stirring for 0.5h;
(3) And (3) cooling to 40 ℃, adding 80gN, N' -dimethylformamide and 200g of acetone in the cooling process to adjust the viscosity of the system, then adding 3.5g2-ethyl-4-methylimidazole in the system, and continuously stirring for 40min to obtain the modified epoxy adhesive.
The preparation method of the flexible copper-clad plate comprises the following steps:
(1) Coating a layer of polydopamine with the thickness of 10 mu m on the PI film, so that the surface activity of the polydopamine is improved;
(2) Coating a modified epoxy adhesive on the PI film by using a coating rod to form a 40-micron adhesive layer, and then putting the adhesive layer into a 160-DEG C drying oven to be dried for 7min until the surface is dried to obtain a prepreg;
(3) And (3) carrying out composite hot pressing on the copper foil with the thickness of 30 microns and the prepreg for 4min on a hot press at 170 ℃ and 12MPa, then putting the copper foil and the prepreg into an oven at 170 ℃ for curing for 1h, then raising the temperature of the oven to 200 ℃, and then curing for 20min to obtain the flexible copper clad laminate.
The sample strip prepared by the modified epoxy adhesive prepared by the method has the impact strength of 39.28KJ/m 2 Compared with unmodified impact strength, the impact strength is improved by 149 percent, and the system toughness is improved; the peel strength of the flexible copper clad laminate prepared by the adhesive can reach 1.47Kgf/cm; can pass the solder endurance test of 320 ℃/10 s.
Example 3
The preparation method of the modified epoxy adhesive comprises the following steps:
(1) Under the atmosphere of nitrogen, 20g of hexamethylene diisocyanate, 80g of polyethylene glycol adipate and 0.5g of dibutyltin dilaurate are added into a reaction vessel, prepolymerization is carried out for 1h at 70 ℃, 4.5g of trimethylolpropane is added, and reaction is continued for 1.5h, so that the obtained system is the polyurethane with the crosslinked network structure.
(2) The system was heated to 90 ℃ and 210g of epoxy EP-51 and 140g of epoxy EP-20 were added to the system several times over 2 hours, and the mixture was stirred thoroughly. Then 85g of curing agent 4,4' -diaminodiphenyl sulfone is added into the system, and the mixture is continuously stirred for 0.5h;
(3) And (3) cooling to 40 ℃, adding 60g of dimethyl sulfoxide and 220g of butanone during cooling to adjust the viscosity of the system, adding 2.8g of 2-ethyl-4-methylimidazole into the system, and continuously stirring for 40min to obtain the modified epoxy adhesive.
The preparation method of the flexible copper-clad plate comprises the following steps:
(1) Putting the PI film into a vacuum plasma processor at N 2 Treating for 10min under atmosphere to improve the surface activity;
(2) Coating a modified epoxy adhesive on the PI film by using a coating rod to form a 40-micron adhesive layer, and then putting the adhesive layer into a 160-DEG C drying oven to be dried for 4min until the surface is dried to obtain a prepreg;
(3) And carrying out composite hot pressing on the copper foil with the thickness of 30 microns and the prepreg for 3min on a hot press at 175 ℃ and 9MPa, then putting the copper foil and the prepreg into an oven at 170 ℃ for curing for 1.5h, then raising the temperature of the oven to 200 ℃, and curing for 20min to obtain the flexible copper-clad plate.
The sample strip prepared by the modified epoxy adhesive prepared by the method has the impact strength of 37.96KJ/m 2 Compared with unmodified impact strength, the impact strength is improved by 141%, and the system toughness is improved; the peel strength of the flexible copper clad laminate prepared by the adhesive can reach 1.52Kgf/cm; can pass the solder endurance test of 320 ℃/10 s.
Example 4
The preparation method of the modified epoxy adhesive comprises the following steps:
(1) Under the atmosphere of nitrogen, 25g of toluene diisocyanate, 75g of poly adipic acid-1,4-butanediol ester and 0.5g of dibutyltin dilaurate are added into a reaction vessel, prepolymerization is carried out for 1h at 70 ℃, then 6.5g of trimethylolpropane is added to continue to react for 2h, and the obtained system is the polyurethane with the cross-linked network structure.
(2) The system is heated to 90 ℃, 210g of epoxy EP-51 and 140g of epoxy BNE-200 are added into the system for a plurality of times in 2 hours, and the mixture is fully stirred. Then adding 115g of curing agent 4,4' -diaminodiphenyl sulfone into the system, and continuing stirring for 0.5h;
(3) And cooling to 40 ℃, adding 280gN, N' -dimethylformamide to adjust the viscosity of the system during cooling, then adding 3g of imidazole into the system, and continuing stirring for 40min to obtain the modified epoxy adhesive.
The preparation method of the flexible copper-clad plate comprises the following steps:
(1) Putting the PI film into a vacuum plasma processor at N 2 Treating for 10min under atmosphere to improve the surface activity;
(2) Coating a modified epoxy adhesive on the PI film by using a coating rod to form a 40-micron adhesive layer, and then putting the PI film into a 170-DEG C oven to be dried for 7.5min until the surface is dried to obtain a prepreg;
(3) And (3) performing composite hot pressing on the copper foil with the thickness of 30 microns and the prepreg for 2.5min on a hot press with the temperature of 170 ℃ and the pressure of 10MPa, then putting the copper foil and the prepreg into an oven with the temperature of 170 ℃ for curing for 1h, then raising the temperature of the oven to 190 ℃, and curing for 30min to obtain the flexible copper clad laminate.
The sample band prepared by the modified epoxy adhesive prepared by the method has the impact strength of 32.86KJ/m 2 Compared with unmodified impact strength, the impact strength is improved by 109%, and the system toughness is improved; the peel strength of the flexible copper clad laminate prepared by the adhesive can reach 1.66Kgf/cm; can pass the solder endurance test of 320 ℃/10 s.
Example 5
Substantially the same as example 4, except that 6g of trimethylolpropane was used.
Example 6
Essentially the same as example 4, except that 5g of trimethylolpropane was used.
Example 7
Substantially the same as example 4 except that trimethylolpropane is used in an amount of 4g.
Example 8
Substantially the same as example 4, except that trimethylolpropane was used in an amount of 3g.
Example 9
Substantially the same as example 4, except that 2g of trimethylolpropane was used.
Example 10
Substantially the same as example 4, except that trimethylolpropane is used in an amount of 1g.
Example 11
Essentially identical to example 4, except that trimethylolpropane was used in an amount of 4g, the PI film was subjected to an alkali treatment, namely: the PI film is put into NaOH solution with the temperature of 60 ℃ and the weight percentage of 10 percent for treatment for 5min, so that the surface activity of the PI film is improved.
Comparative example 1
Substantially the same as example 4 except that 0g of trimethylolpropane is used.
Comparative example 2
Substantially the same as example 4, except that trimethylolpropane was used in an amount of 4g and the PI film was not subjected to any surface treatment.
Test example
Peel Strength test
And respectively carrying out peel strength test on the flexible copper clad laminates prepared in the embodiments 5-11 and the comparative example 2 to obtain figures 1 and 2.
The peel strength test refers to the standard GB/T2791-1995 adhesive T peel strength test method for flexible material to flexible material, and the effective peel length of the flexible copper-clad plate is as follows: the thickness is 200mm multiplied by 25mm, the peeling speed of the flexible copper clad laminate on a computerized tensile testing machine is 100mm/min, 5 samples are tested in each group, and the peeling strength of the flexible copper clad laminate is obtained by taking the average value.
As can be seen from figure 1, the PI film can effectively improve the peel strength of the finally prepared flexible copper clad laminate by alkali treatment and plasma treatment.
As can be seen from FIG. 2, the peel strength of the finally prepared flexible copper clad laminate is increased along with the increase of the dosage of the trimethylolpropane.
Impact strength test
And (3) respectively carrying out impact strength test on the flexible copper clad laminates prepared in the examples 5-10 and the comparative example 1 to obtain a graph 3.
The impact strength test refers to GB/T2576-2021 resin casting performance test method, the modified epoxy adhesive is cured in a PTFE mould to obtain 80X 10X 4mm 3 The unnotched impact sample strip is subjected to impact test on a pendulum cantilever beam impact tester with the energy of 5.5J, 5 samples are tested in each group, and the average value is taken to obtain the impact strength of the modified epoxy adhesive cured sample strip.
As can be seen from FIG. 3, with the increase of the amount of trimethylolpropane, the impact strength of the finally prepared flexible copper clad laminate is increased first and then decreased.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the claims. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The modified epoxy adhesive is characterized by comprising the following components in parts by weight:
72.2 to 138.8 portions of polyurethane, 300 to 400 portions of epoxy resin, 75 to 100 portions of high-temperature curing agent, 240 to 320 portions of diluent and 2 to 4 portions of curing accelerator;
72.2 to 138.8 portions of polyurethane is 10 to 40 portions of diisocyanate, 60 to 90 portions of polyester polyol, 2 to 8 portions of cross-linking agent and 0.2 to 0.8 portion of catalyst.
2. The modified epoxy adhesive of claim 1, wherein the high temperature curing agent is selected from at least one of dicyandiamide, 4,4' -diaminodiphenyl ether, 4,4' -diaminodiphenylmethane, and 4,4' -diaminodiphenylsulfone.
3. The modified epoxy adhesive of claim 2, wherein the epoxy resin is at least one selected from the group consisting of epoxy resin EP-51, epoxy resin EP-20, epoxy resin AG-80, and epoxy resin BNE-200.
4. The modified epoxy adhesive of claim 3, wherein the curing accelerator is selected from at least one of imidazole, resorcinol, boron trifluoride amine, 2-ethyl-4-methylimidazole, and triethanolamine;
the diluent is at least one selected from acetone, butanone, N' -dimethylformamide and dimethyl sulfoxide.
5. The modified epoxy adhesive of any one of claims 1 to 4, wherein the polyester polyol is selected from at least one of polyethylene adipate, 1,6-hexanediol polycarbonate, 1,4-butanediol, and 1,6-hexanediol, and has a molecular weight of 1000 to 3000;
the diisocyanate is selected from at least one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and toluene diisocyanate;
the cross-linking agent is trimethylolpropane;
the catalyst is dibutyltin dilaurate.
6. A method for preparing the modified epoxy adhesive of any one of claims 1 to 5, comprising the steps of:
under the atmosphere of protective gas, 10 to 40 parts of diisocyanate, 60 to 90 parts of polyester polyol and 0.2 to 0.8 part of catalyst are mixed uniformly and then are subjected to prepolymerization reaction at 60 to 90 ℃, and then 2 to 8 parts of cross-linking agent is added for continuous reaction to obtain a reaction mixture, namely polyurethane;
and heating the reaction mixture to 80-100 ℃, adding 300-400 parts of epoxy resin and 75-100 parts of high-temperature curing agent, uniformly mixing, cooling to 30-50 ℃, adding 240-320 parts of diluent to adjust viscosity, and finally adding 2-4 parts of curing accelerator to fully react to obtain the required modified epoxy adhesive.
7. The method for preparing the modified epoxy adhesive according to claim 6, wherein the reaction time of the prepolymerization reaction is 0.5-1.5 h, the reaction time of adding 2-8 parts of the cross-linking agent for continuous reaction is 1-3 h, and the reaction time of adding 2-4 parts of the curing accelerator for full reaction is 0.5-1 h;
the operation of adding and uniformly mixing 300 to 400 parts of epoxy resin and 75 to 100 parts of high-temperature curing agent is as follows: adding 300-400 parts of the epoxy resin for multiple times within 2h, and then adding 75-100 parts of the high-temperature curing agent.
8. A prepreg, characterized by comprising a surface treatment flexible film and an adhesive film arranged on the surface treatment flexible film, wherein the adhesive film is made of the modified epoxy adhesive of any one of claims 1 to 5.
9. The prepreg according to claim 8, wherein the surface treatment flexible film is prepared by: and carrying out surface treatment on the flexible insulating film to obtain the surface-treated flexible film, wherein the surface treatment is alkali treatment, plasma treatment or polydopamine coating treatment, and the flexible insulating film is a PI film or a PET film.
10. A flexible copper clad laminate characterized by comprising a copper foil and the prepreg according to claim 8 or 9, wherein the surface-treated flexible film, the adhesive film and the copper foil are laminated in this order.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116814145A (en) * | 2023-06-05 | 2023-09-29 | 北京梦之墨科技有限公司 | Primer and preparation method and application thereof |
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| CN1670107A (en) * | 2004-03-05 | 2005-09-21 | 信越化学工业株式会社 | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same |
| CN101407708A (en) * | 2008-09-05 | 2009-04-15 | 中南大学 | High temperature resistant, high strength modified epoxy resin adhesive and preparation thereof |
| CN105297487A (en) * | 2015-11-20 | 2016-02-03 | 嘉兴洛克化学工业有限公司 | Washing resistant adhesive and preparation method thereof |
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| CN1670107A (en) * | 2004-03-05 | 2005-09-21 | 信越化学工业株式会社 | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same |
| CN101407708A (en) * | 2008-09-05 | 2009-04-15 | 中南大学 | High temperature resistant, high strength modified epoxy resin adhesive and preparation thereof |
| CN105297487A (en) * | 2015-11-20 | 2016-02-03 | 嘉兴洛克化学工业有限公司 | Washing resistant adhesive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116814145A (en) * | 2023-06-05 | 2023-09-29 | 北京梦之墨科技有限公司 | Primer and preparation method and application thereof |
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