CN116640527B - Two-component UV-curable acrylic-epoxy resin film and preparation method and application thereof - Google Patents
Two-component UV-curable acrylic-epoxy resin film and preparation method and application thereof Download PDFInfo
- Publication number
- CN116640527B CN116640527B CN202310355317.6A CN202310355317A CN116640527B CN 116640527 B CN116640527 B CN 116640527B CN 202310355317 A CN202310355317 A CN 202310355317A CN 116640527 B CN116640527 B CN 116640527B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- component
- cinnamic acid
- epoxy
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 124
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims abstract description 73
- 229930016911 cinnamic acid Natural products 0.000 claims abstract description 73
- 235000013985 cinnamic acid Nutrition 0.000 claims abstract description 73
- 239000003292 glue Substances 0.000 claims abstract description 73
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000004593 Epoxy Substances 0.000 claims abstract description 71
- 239000002313 adhesive film Substances 0.000 claims abstract description 67
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims abstract description 57
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 239000003085 diluting agent Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000007822 coupling agent Substances 0.000 claims abstract description 13
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000011889 copper foil Substances 0.000 claims description 20
- 230000035484 reaction time Effects 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 19
- 239000011231 conductive filler Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical group CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical group CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 50
- 239000000945 filler Substances 0.000 abstract description 36
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 76
- 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 description 35
- 239000007888 film coating Substances 0.000 description 32
- 238000009501 film coating Methods 0.000 description 32
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 25
- 239000000843 powder Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- -1 cinnamic acid modified bisphenol A Chemical class 0.000 description 16
- 238000001035 drying Methods 0.000 description 16
- 229920006332 epoxy adhesive Polymers 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229920001187 thermosetting polymer Polymers 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000003825 pressing Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910021487 silica fume Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 230000008054 signal transmission Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000004075 alteration Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010295 mobile communication Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- IKCQWKJZLSDDSS-UHFFFAOYSA-N 2-formyloxyethyl formate Chemical compound O=COCCOC=O IKCQWKJZLSDDSS-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- 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
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/405—Adhesives in the form of films or foils characterised by release liners characterised by the substrate of the release liner
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a double-component ultraviolet light curing acrylic acid-epoxy resin adhesive film, a preparation method and application thereof, and belongs to the technical field of polymer blending and composite materials. The preparation method comprises the steps of taking an alkaline agent as a catalyst, carrying out chemical ring opening reaction on hydroxyl-terminated epoxy resin and an epoxy diluent to obtain ring-opened epoxy resin glue solution, carrying out esterification reaction on 3-phenyl-2-acrylic acid and ring-opened epoxy resin to obtain cinnamic acid modified epoxy resin glue solution, adding an ultraviolet initiator, an epoxy curing agent, an accelerator and a leveling agent into the cinnamic acid modified epoxy resin, mixing at normal temperature and in a dark place to obtain a two-component cinnamic acid modified epoxy prepolymer glue solution, adding a coupling agent and a heat conducting filler into the two-component cinnamic acid modified epoxy prepolymer to obtain a two-component ultraviolet curing acrylic acid-epoxy resin composite glue solution, and curing under ultraviolet light to form a semi-cured two-component ultraviolet curing acrylic acid-epoxy resin glue film. The solvent-free semi-cured adhesive film is prepared.
Description
Technical Field
The invention relates to the technical field of polymer blending and composite materials, in particular to a double-component ultraviolet light curing acrylic acid-epoxy resin adhesive film, a preparation method and application.
Background
The communication technology has been developed for 40 years from generation 1 to generation 5. The 5 th generation (5G) and 6 th generation (6G) mobile communication technologies have characteristics of ultra-high signal transmission speed (10 Ghps), ultra-low delay (< 1 ms) and the like. The development of 5G and 6G mobile communication technologies has a very high degree of dependence on new materials, which depends on the close relationship between the dielectric constant and dielectric loss of the Printed Circuit Board (PCB) when signals are transmitted in the PCB. Therefore, the selection of resin-based materials with low dielectric loss and high insulation is a key to ensure efficient signal transmission.
Currently, along with the rapid upgrading and environmental protection requirements of production technology, the traditional PCB board for the solvent-type bisphenol A-type epoxy-based adhesive material has been gradually replaced by a low-dielectric epoxy resin-based adhesive film prepared by a solvent-free method. The efficiency and environmental safety are significantly improved and improved, both with respect to the configuration of the resin system and the use of the PCB substrate. The university of western union technology Li Huilu teaches that the team has achieved localization of solvent-free epoxy resin based adhesive films through research in the last decade. The formula and the process of the epoxy resin system and the semi-cured adhesive film prepared by the solvent-free method directly determine the overall technical level of the downstream PCB.
The traditional PCB board epoxy substrate is used by coating liquid epoxy resin on glass fiber cloth for pressing on the basis of a curing agent, and the peel strength between copper foil and glass fiber can be greatly tested due to the existence of the glass fiber cloth.
Disclosure of Invention
Aiming at the problems, the invention provides a double-component ultraviolet light curing acrylic acid-epoxy resin adhesive film, a preparation method and application thereof, and a solvent-free semi-cured adhesive film is prepared.
The first object of the invention is to provide a preparation method of a two-component ultraviolet curing acrylic acid-epoxy resin adhesive film, which comprises the following steps:
Step 1, taking an alkaline agent as a catalyst, and carrying out chemical ring-opening reaction on hydroxyl-terminated epoxy resin and an epoxy diluent to obtain ring-opened epoxy resin glue solution;
Step 2, adding 3-phenyl-2-acrylic acid into the ring-opened epoxy resin prepared in the step 1, and performing esterification reaction to obtain cinnamic acid modified epoxy resin glue solution;
step 3, adding an ultraviolet initiator, an epoxy curing agent, an accelerator and a leveling agent into the cinnamic acid modified epoxy resin prepared in the step 2, and uniformly mixing at normal temperature and in a dark place to obtain a double-component cinnamic acid modified epoxy prepolymer glue solution;
And 4, adding a coupling agent and a heat conducting filler into the bicomponent cinnamic acid modified epoxy prepolymer prepared in the step 3, uniformly dispersing to obtain a bicomponent ultraviolet light curing acrylic acid-epoxy resin composite glue solution, coating the glue solution on a release film, and curing the glue film under the action of ultraviolet light to obtain a semi-cured bicomponent ultraviolet light curing acrylic acid-epoxy resin glue film.
Preferably, in the step 1, the reaction temperature of the chemical ring-opening reaction is 60-75 ℃ and the reaction time is 1-2.5 hours, wherein the mass ratio of the hydroxyl-terminated epoxy resin to the epoxy diluent to the alkaline agent is 45-75:25:0.1-1.5.
Preferably, in step1, the alkaline agent is one of potassium hydroxide, barium hydroxide or sodium hydroxide.
Preferably, in the step 2, the reaction temperature of the esterification reaction is 75-90 ℃ and the reaction time is 1.5-3h, wherein the molar ratio of the carboxyl of the 3-phenyl-2 acrylic acid to the epoxy groups in the epoxy resin glue solution after ring opening is 0.15-0.55:1.
Preferably, in the step 3, the mass ratio of the ultraviolet initiator to the cinnamic acid modified epoxy resin glue solution is 0.06-0.1:1, the mass ratio of the epoxy curing agent to the cinnamic acid modified epoxy resin is 0.04-0.3:1, the mass ratio of the accelerator to the cinnamic acid modified epoxy resin is 0.01-0.05:1, and the mass ratio of the leveling agent to the cinnamic acid modified epoxy resin is 0.001-0.003:1.
Preferably, in the step 3, the ultraviolet initiator is 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide, the epoxy curing agent is bismaleimide, the accelerator is 2-ethyl-4-methylimidazole and the leveling agent is polyether modified siloxane.
Preferably, in the step 4, the mass ratio of the coupling agent to the heat-conducting filler to the bicomponent cinnamic acid modified epoxy prepolymer is 1-3:55-75:25-45.
Preferably, the heat conducting filler is a compound of silicon micropowder and aluminum oxide, and the mass ratio of the silicon micropowder to the aluminum oxide is 0.25-1:1;
the release film is a polyethylene glycol diformate film.
The second purpose of the invention is to provide the two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film prepared by the preparation method.
The third object of the invention is to provide the application of the two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film in the PCB board, which is characterized in that the two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film is bonded with a copper foil laminate and then subjected to secondary high-temperature curing to obtain the PCB board;
wherein the secondary high temperature curing temperature is 170-220 ℃, the curing time is 2h, and the press pressure is 5-10Mpa.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, cinnamic acid is copolymerized with hydroxyl-terminated bisphenol A epoxy resin, so that double bond organic molecules containing benzene rings are introduced into bisphenol A molecular chains, and the ultraviolet light accelerator and the epoxy curing agent are added to enable the cinnamic acid modified hydroxyl-terminated epoxy resin to have two functions, namely, firstly, the cinnamic acid modified hydroxyl-terminated epoxy resin can be rapidly formed into a film on a PET film under the action of ultraviolet light, and epoxy groups in the molecular chains can be secondarily cured to be bonded with copper foil at high temperature (120 ℃). Thus, the solvent-free semi-cured adhesive film can be prepared by designing the temperature range of the dual-curing system.
(2) The traditional adhesive film is characterized in that the high filling amount of the filler of the resin is achieved through the diluent, the diluent is volatilized through heating, and meanwhile, part of the epoxy resin is solidified to a certain degree to achieve a semi-solidified state, so that the defects of environmental pollution and residual solvent influence the performance. Compared with the traditional adhesive film, the low-viscosity double-component ultraviolet light curing phenyl acrylic acid-epoxy resin system and the adhesive film prepared by the invention have the characteristics of high peel strength and low dielectric loss. In the preparation process, cinnamic acid is introduced to solve the problem of film formation of a composite resin system, and the resin system has low viscosity, and double bond groups reach a semi-solidified film formation state in ultraviolet light curing, so that solvent-free production is achieved, and the filler can be filled in a high proportion.
(3) Compared with the traditional epoxy resin and phenolic resin, the cinnamic acid modified hydroxyl-terminated epoxy resin has the characteristics of good photosensitivity and high resin bonding strength under high-temperature curing, and the dual-curing system can design novel high-performance resin.
(4) Compared with the traditional solvent type epoxy and acrylic resin, the cinnamic acid modified epoxy adhesive film prepared by the invention has more excellent comprehensive performance under the action of the heat conducting filler, does not need equipment replacement, and solves the problem of solvation-free development of the high-performance polymer substrate under low cost.
(5) The molar ratio of carboxyl in cinnamic acid to epoxy groups in the epoxy resin is controlled between 0.15 and 0.55 in the preparation process, so that the epoxy groups in the semi-cured film can generate strong adhesive force with copper foil under the high-temperature curing condition. The problems that the epoxy group content is too low, the adhesion of the copper foil is reduced, the product performance is not ideal, and a semi-cured film with too high epoxy group content is sticky and is unfavorable for processing are avoided.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The hydroxyl-terminated bisphenol A type epoxy resin used in the present invention was purchased from Yu Hongchang electronic materials Co., ltd. GEBR481A80 type epoxy resin, and the linear epoxy diluent was butyl glycidyl ether diluted type (GEKR) of the Co. The cinnamic acid is available from Wu Han organic materials company.
The copper foil is purchased from Tongchuan core material limited company, the thickness is 20-50 mu m, the silicon micro powder is purchased from Siam Tianyuan chemical industry limited company, the particle size is 10-20 mu m, the aluminum oxide is purchased from Qin Royal Yinuo corporation, and the particle size is 15-20 mu m.
Example 1
The embodiment provides a preparation method of a two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film, which comprises the following steps:
step 1, weighing 0.1g of sodium hydroxide serving as a catalyst, dissolving the sodium hydroxide in 10mL of ethanol solution, adding the dissolved sodium hydroxide solution into a mixed solution of 45g of hydroxyl-terminated epoxy resin and 25g of epoxy diluent for chemical ring-opening reaction, wherein the reaction temperature is 75 ℃, and the reaction time is 2 hours, so as to obtain bisphenol A epoxy resin glue solution after ring opening;
Step 2, adding 7g of 3-phenyl-2-acrylic acid (cinnamic acid) into 45g of the bisphenol A epoxy resin glue solution prepared in the step 1 after ring opening under normal temperature, and then placing the glue solution into a heating sleeve to heat for esterification reaction, wherein the reaction temperature is 75 ℃ and the reaction time is 3 hours, so as to obtain the cinnamic acid modified bisphenol A epoxy resin glue solution;
Step 3, adding 3g of ultraviolet initiator, 15g of epoxy curing agent, 0.5g of accelerator and 0.1g of flatting agent into 45g of cinnamic acid modified bisphenol A type epoxy resin glue solution prepared in the step 2 in a light-shielding environment, and stirring for 0.5 hour at normal temperature to obtain photo-curable and thermosetting bicomponent cinnamic acid modified epoxy prepolymer glue solution;
And 4, adding 2g of coupling agent into 25g of prepared double-component cinnamic acid modified epoxy prepolymer glue solution, dispersing at high speed for 5 minutes at the rotating speed of 650 rmp/min, and rapidly adding 75g of weighed heat-conducting filler (the mass ratio of silica micropowder to alumina is 0.5:1) to fully and uniformly disperse to obtain the double-component ultraviolet light curing acrylic acid-epoxy resin compound. The two-component ultraviolet light curing acrylic acid-epoxy resin compound is coated on a release film by a film coating instrument (the coating parameters of a film coating machine are that the film coating is carried out in a dipping tank at a coating speed of 0.5 m/min, the temperature of a film coating drying channel is 90 ℃ and the length of the drying channel is 6 m), and the film is quickly cured and formed by irradiation for 30s under ultraviolet light (290 nm), wherein the irradiation is carried out at normal temperature, so that the semi-cured bisphenol A film with uniform phase distribution is obtained. The basic formulation is shown in Table 1.
TABLE 1 formulation table of two-component UV-curable acrylic-epoxy resin compound
Example 2
The embodiment provides a preparation method of a two-component ultraviolet curing acrylic-epoxy resin adhesive film, wherein a formula 5 is taken as a basic resin formula, and the heat conducting performance of the adhesive film is shown in a table 2 after the adhesive film is matched with different fillers.
Specifically:
step 1, weighing 0.3g of sodium hydroxide, dissolving in 10mL of ethanol solution, adding the dissolved sodium hydroxide solution into a mixed solution of 65g of hydroxyl-terminated epoxy resin and 25g of epoxy diluent for chemical ring-opening reaction, wherein the reaction temperature is 75 ℃, and the reaction time is 2 hours, so as to obtain bisphenol A epoxy resin glue solution after ring opening;
step 2, adding 15g of 3-phenyl-2-acrylic acid (cinnamic acid) into 65g of the bisphenol A epoxy resin glue solution subjected to ring opening in the step 1 at normal temperature, and then placing the glue solution into a heating jacket to heat for esterification reaction, wherein the reaction temperature is 75 ℃, and the reaction time is 3 hours, so as to obtain a cinnamic acid modified bisphenol A epoxy resin system;
Step 3, adding 5g of ultraviolet initiator, 5g of epoxy curing agent, 0.5g of accelerator and 0.1g of flatting agent into 65g of cinnamic acid modified bisphenol A type epoxy resin glue solution prepared in the step 2 in a light-shielding environment, and stirring for 0.5 hour at normal temperature to obtain a photo-curable and thermosetting bicomponent cinnamic acid modified epoxy prepolymer system;
And 4, adding 2g of coupling agent into 25g of prepared double-component cinnamic acid modified epoxy prepolymer glue solution, dispersing at high speed for 5 minutes at the rotating speed of 650 rmp/min, rapidly adding 75g of weighed heat conducting filler (silicon micro powder: alumina mass ratio of 1:1), and fully and uniformly dispersing to obtain the double-component ultraviolet light curing acrylic acid-epoxy resin compound.
The 50 double-component ultraviolet light curing acrylic acid-epoxy resin compound is coated on a release film by a film coating instrument (the coating parameters of a film coating machine are that the film coating is carried out in a dipping tank at a coating speed of 0.5 m/min, the temperature of a film coating drying channel is 90 ℃ and the length of the drying channel is 6 m), and the film is quickly cured and formed by irradiation for 30s under ultraviolet light (290 nm), wherein the irradiation is carried out at normal temperature, so that the semi-cured bisphenol A film with uniform phase distribution is obtained.
Then 50g of the two-component ultraviolet light curing acrylic acid-epoxy resin compound is weighed and subjected to preliminary curing on a release film (parameters of a film coater are the same as those of the embodiment 1) by adopting ultraviolet light (290 nm) irradiation at normal temperature for 30 seconds to form a uniform semi-cured bisphenol A film.
After the film is formed, hot-pressing is carried out for 2 hours at a high temperature of 180 ℃ to obtain the flexible heat-conducting adhesive film. The thermal conductivity is shown in Table 2.
Example 3
The two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film is prepared in the embodiment, and is the same as in the embodiment 2, wherein 75g of the heat conducting filler added in the step 4 consists of silicon micro powder and aluminum oxide in a mass ratio of 0.25:1.
Example 4
The two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film is prepared in the embodiment, and is the same as in the embodiment 2, wherein 75g of the heat conducting filler added in the step 4 consists of silicon micro powder and aluminum oxide in a mass ratio of 0.5:1.
Example 5
The two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film is prepared in the embodiment, and is the same as in the embodiment 2, wherein the addition amount of the two-component cinnamic acid modified epoxy prepolymer in the step 4 is 35g, the addition amount of the heat conducting filler is 65g, and the mass ratio of the silicon micro powder to the alumina is 1:1.
Example 6
The two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film is prepared in the embodiment, and is the same as in the embodiment 2, wherein the addition amount of the two-component cinnamic acid modified epoxy prepolymer in the step 4 is 35g, the addition amount of the heat conducting filler is 65g, and the mass ratio of the silicon micro powder to the alumina is 0.25:1.
Example 7
The two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film is prepared in the embodiment, and is the same as in the embodiment 2, wherein the addition amount of the two-component cinnamic acid modified epoxy prepolymer in the step 4 is 35g, the addition amount of the heat conducting filler is 65g, and the mass ratio of the silicon micro powder to the alumina is 0.5:1.
Example 8
The two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film is prepared in the embodiment, and is the same as in the embodiment 2, wherein the addition amount of the two-component cinnamic acid modified epoxy prepolymer in the step 4 is 45g, the addition amount of the heat conducting filler is 55g, and the mass ratio of the silicon micro powder to the alumina is 1:1.
Example 9
The two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film is prepared in the embodiment, and is the same as in the embodiment 2, wherein the addition amount of the two-component cinnamic acid modified epoxy prepolymer in the step 4 is 45g, the addition amount of the heat conducting filler is 55g, and the mass ratio of the silicon micro powder to the alumina is 0.25:1.
Example 10
The two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film is prepared in the embodiment, and is the same as in the embodiment 2, wherein the addition amount of the two-component cinnamic acid modified epoxy prepolymer in the step 4 is 45g, the addition amount of the heat conducting filler is 55g, and the mass ratio of the silicon micro powder to the alumina is 0.5:1.
Example 11
The two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film is prepared in the embodiment, and is the same as in the embodiment 2, wherein the addition amount of the two-component cinnamic acid modified epoxy prepolymer in the step 4 is 55g, the addition amount of the heat conducting filler is 45g, and the mass ratio of the silicon micro powder to the alumina is 1:1.
Example 12
The two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film is prepared in the embodiment, and is the same as in the embodiment 2, wherein the addition amount of the two-component cinnamic acid modified epoxy prepolymer in the step 4 is 55g, the addition amount of the heat conducting filler is 45g, and the mass ratio of the silicon micro powder to the alumina is 0.25:1.
Example 13
The two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film is prepared in the embodiment, and is the same as in the embodiment 2, wherein the addition amount of the two-component cinnamic acid modified epoxy prepolymer in the step 4 is 55g, the addition amount of the heat conducting filler is 45g, and the mass ratio of the silicon micro powder to the alumina is 0.5:1.
Comparative example 1
This comparative example prepared a two-component uv curable acrylic-epoxy adhesive film, identical to example 2, except that the amount of the heat conductive filler (silica fume) added in step 4 was 75g.
Comparative example 2
The comparative example prepared a two-component uv curable acrylic-epoxy adhesive film, identical to example 2, except that the amount of the two-component cinnamic acid-modified epoxy prepolymer added in step 4 was 35g and the amount of the thermally conductive filler (silica fume) added was 65g.
Comparative example 3
The comparative example prepared a two-component uv curable acrylic-epoxy adhesive film, identical to example 2, except that the amount of the two-component cinnamic acid-modified epoxy prepolymer added in step 4 was 45g and the amount of the thermally conductive filler (silica fume) added was 55g.
Comparative example 4
The comparative example prepared a two-component uv curable acrylic-epoxy adhesive film, identical to example 2, except that the amount of the two-component cinnamic acid-modified epoxy prepolymer added in step 4 was 55g and the amount of the thermally conductive filler (silica fume) added was 45g.
Comparative example 5
This comparative example prepared a two-component uv curable acrylic-epoxy adhesive film, identical to example 2, except that the amount of the thermally conductive filler (alumina) added in step 4 was 75g.
Comparative example 6
The comparative example prepared a two-component uv curable acrylic-epoxy adhesive film, identical to example 2, except that the amount of the two-component cinnamic acid-modified epoxy prepolymer added in step 4 was 35g and the amount of the thermally conductive filler (alumina) added was 65g.
Comparative example 7
The comparative example prepared a two-component uv curable acrylic-epoxy adhesive film, identical to example 2, except that the amount of the two-component cinnamic acid modified epoxy prepolymer added in step 4 was 45g and the amount of the heat conductive filler (alumina) added was 55g.
Comparative example 8
The comparative example prepared a two-component uv curable acrylic-epoxy adhesive film, identical to example 2, except that the amount of the two-component cinnamic acid-modified epoxy prepolymer added in step 4 was 55g and the amount of the thermally conductive filler (alumina) added was 45g.
As can be seen from table 2, the increase of the alumina content can obviously improve the overall heat conducting performance of the composite film material compared with that of the single filler, and the addition of the composite filler increases the breakdown voltage and improves the toughness of the adhesive film.
TABLE 2 influence of the proportion and amount of filler on the Heat conduction
Example 14
The embodiment provides a preparation method of a two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film, which comprises the following steps:
step 1, weighing 0.1g of sodium hydroxide serving as a catalyst, dissolving the sodium hydroxide in 10mL of ethanol solution, adding the dissolved sodium hydroxide solution into a mixed solution of 45g of hydroxyl-terminated epoxy resin and 25g of epoxy diluent for chemical ring-opening reaction, wherein the reaction temperature is 75 ℃, and the reaction time is 2 hours, so as to obtain bisphenol A epoxy resin glue solution after ring opening;
Step 2, adding 7g of 3-phenyl-2-acrylic acid (cinnamic acid) into 45g of the bisphenol A epoxy resin glue solution subjected to ring opening in the step 1 at normal temperature, and then placing the glue solution into a heating jacket to heat for esterification reaction, wherein the reaction temperature is 110 ℃, and the reaction time is 3 hours, so as to obtain the cinnamic acid modified bisphenol A epoxy resin glue solution;
Step 3, adding 3g of ultraviolet initiator, 15g of epoxy curing agent, 0.5g of accelerator and 0.1g of flatting agent into 45g of cinnamic acid modified bisphenol A type epoxy resin glue solution prepared in the step 2 in a light-shielding environment, and stirring for 0.5 hour at normal temperature to obtain photo-curable and thermosetting bicomponent cinnamic acid modified epoxy prepolymer glue solution;
And step 4, adding 2g of coupling agent into the prepared bicomponent cinnamic acid modified epoxy prepolymer glue solution, dispersing at high speed for 5 minutes at the rotating speed of 650 rmp/min, and rapidly adding 65g of weighed heat-conducting filler (silica micropowder: alumina mass ratio of 0.25:1) to fully disperse uniformly, thereby obtaining the bicomponent ultraviolet light curing acrylic acid-epoxy resin compound. The two-component ultraviolet light curing acrylic acid-epoxy resin compound is coated on a release film by a film coating instrument (the coating parameters of a film coating machine are that the film coating is carried out in a dipping tank at a coating speed of 0.5 m/min, the temperature of a film coating drying channel is 90 ℃ and the length of the drying channel is 6 m), and the film is quickly cured and formed by irradiation for 30s under ultraviolet light (290 nm), wherein the irradiation is carried out at normal temperature, so that the semi-cured bisphenol A film with uniform phase distribution is obtained.
Example 15
The two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film is prepared in the embodiment, and is the same as in the embodiment 14, wherein in the step 4, the mass ratio of the silicon micro powder to the aluminum oxide is 1:1.
Example 16
The two-component ultraviolet light curing acrylic-epoxy resin adhesive film is prepared in the embodiment, and is the same as in the embodiment 14, except that in the step 4, the mass ratio of the silicon micro powder to the aluminum oxide is 0.5:1.
Example 17
The two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film is prepared in the embodiment, and is the same as in the embodiment 14, wherein the addition amount of the heat conducting filler in the step 4 is 75g, and the mass ratio of the silica micro powder to the alumina is 1:1.
Example 18
The two-component ultraviolet light curing acrylic-epoxy resin adhesive film is prepared in the embodiment, and is the same as in the embodiment 14, except that the adding amount of the heat conducting filler in the step 4 is 75g, and the mass ratio of the silica micro powder to the alumina is 0.25:1.
Comparative example 9
This comparative example prepared a two-component uv curable acrylic-epoxy adhesive film, identical to example 14, except that the amount of the heat conductive filler (alumina) added in step 4 was 45g.
Comparative example 10
This comparative example prepared a two-component uv curable acrylic-epoxy adhesive film, identical to example 14, except that the amount of the heat conductive filler (silica fume) added in step 4 was 55g.
The properties of the ultraviolet light cured composite films (i.e., semi-cured bisphenol A films) and copper foils prepared in examples 14 to 18 and comparative examples 9 to 10, which were pressed at 190℃and 5MPa for 2 hours, were shown in Table 3.
TABLE 3 Properties of copper foil prepared with acrylic-epoxy adhesive film
As can be seen from Table 3, when the mass ratio of the hollow silica powder to the alumina is 1:1, the dielectric loss of the copper-clad plate can reach below 3 thousandths, the attenuation problem of signal transmission under high frequency (5G and 6G) is satisfied, in addition, the consumption of epoxy resin and the consumption of filler are closely related to the peeling strength, the greater the consumption of epoxy resin, the higher the peeling strength between the adhesive film and the copper foil is when the consumption of filler is 65%, and the electrical property is better.
The breakdown voltage of the adhesive film prepared by the composite filler is increased, and the dielectric loss is obviously reduced. The prepared adhesive film has better toughness. And its resistance to 288 ℃ soldering can be as long as 320 minutes, while the temperature resistance of a single filler is less than 20 minutes.
Example 19
The embodiment provides a preparation method of a two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film, which comprises the following steps:
step 1, weighing 0.2g of sodium hydroxide serving as a catalyst, dissolving the sodium hydroxide in 10mL of ethanol solution, adding the dissolved sodium hydroxide solution into a mixed solution of 50g of hydroxyl-terminated epoxy resin and 25g of epoxy diluent for chemical ring-opening reaction, wherein the reaction temperature is 65 ℃, and the reaction time is 2 hours, so as to obtain bisphenol A epoxy resin glue solution after ring opening;
Step 2, adding 10g of 3-phenyl-2-acrylic acid (cinnamic acid) into 50g of the bisphenol A epoxy resin glue solution prepared in the step 1 after ring opening under normal temperature, and then placing the glue solution into a heating sleeve to heat for esterification reaction, wherein the reaction temperature is 90 ℃ and the reaction time is 2 hours, so as to obtain the cinnamic acid modified bisphenol A epoxy resin glue solution;
Step 3, adding 5g of ultraviolet initiator, 10g of epoxy curing agent, 1g of accelerator and 0.05g of flatting agent into 50g of cinnamic acid modified bisphenol A type epoxy resin glue solution prepared in the step 2 in a light-proof environment, and stirring for 0.5 hour at normal temperature to obtain photo-curable and thermosetting bicomponent cinnamic acid modified epoxy prepolymer glue solution;
And 4, adding 2g of coupling agent into the prepared bicomponent cinnamic acid modified epoxy prepolymer glue solution, dispersing at high speed for 5 minutes at the rotating speed of 650 rmp/min, and rapidly adding 75g of weighed heat-conducting filler (the mass ratio of the silica micro powder to the alumina is 0.5:1) to fully and uniformly disperse to obtain the bicomponent ultraviolet light curing acrylic acid-epoxy resin compound. The two-component ultraviolet light curing acrylic acid-epoxy resin compound is coated on a release film by a film coating instrument (the coating parameters of a film coating machine are that the film coating is carried out in a dipping tank at a coating speed of 0.5 m/min, the temperature of a film coating drying channel is 90 ℃ and the length of the drying channel is 6 m), and the film is quickly cured and formed by irradiation for 30s under ultraviolet light (290 nm), wherein the irradiation is carried out at normal temperature, so that the semi-cured bisphenol A film with uniform phase distribution is obtained.
And pressing the prepared ultraviolet-cured composite adhesive film (namely the semi-cured bisphenol A film) and the copper foil for 2 hours at 170 ℃ and 10Mpa to obtain the insulated composite copper foil.
Example 20
The embodiment provides a preparation method of a two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film, which comprises the following steps:
Step 1, weighing 0.3g of sodium hydroxide serving as a catalyst, dissolving the sodium hydroxide in 10mL of ethanol solution, adding the dissolved sodium hydroxide solution into a mixed solution of 55g of hydroxyl-terminated epoxy resin and 25g of epoxy diluent for chemical ring-opening reaction, wherein the reaction temperature is 75 ℃, and the reaction time is 2.5 hours, so that bisphenol A epoxy resin glue solution after ring opening is obtained;
Step 2, adding 12g of 3-phenyl-2-acrylic acid (cinnamic acid) into 55g of the bisphenol A epoxy resin glue solution prepared in the step 1 after ring opening under normal temperature, and then placing the glue solution into a heating jacket to heat for esterification reaction, wherein the reaction temperature is 85 ℃, and the reaction time is 2.5 hours, so as to obtain the cinnamic acid modified bisphenol A epoxy resin glue solution;
Step 3, adding 5g of ultraviolet initiator, 5g of epoxy curing agent, 1.65g of accelerator and 0.165g of flatting agent into 55g of cinnamic acid modified bisphenol A type epoxy resin glue solution prepared in the step 2 in a light-shielding environment, and stirring for 0.5 hour at normal temperature to obtain photo-curable and thermosetting bicomponent cinnamic acid modified epoxy prepolymer glue solution;
And 4, adding 2g of coupling agent into the prepared bicomponent cinnamic acid modified epoxy prepolymer glue solution, dispersing at high speed for 5 minutes at the rotating speed of 650 rmp/min, and rapidly adding 75g of weighed heat-conducting filler (the mass ratio of the silica micro powder to the alumina is 0.5:1) to fully and uniformly disperse to obtain the bicomponent ultraviolet light curing acrylic acid-epoxy resin compound. The two-component ultraviolet light curing acrylic acid-epoxy resin compound is coated on a release film by a film coating instrument (the coating parameters of a film coating machine are that the film coating is carried out in a dipping tank at a coating speed of 0.5 m/min, the temperature of a film coating drying channel is 90 ℃ and the length of the drying channel is 6 m), and the film is quickly cured and formed by irradiation for 30s under ultraviolet light (290 nm), wherein the irradiation is carried out at normal temperature, so that the semi-cured bisphenol A film with uniform phase distribution is obtained.
And pressing the prepared ultraviolet-cured composite adhesive film (namely the semi-cured bisphenol A film) and the copper foil for 2 hours at 220 ℃ and 5Mpa to obtain the insulated composite copper foil.
Example 21
The embodiment provides a preparation method of a two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film, which comprises the following steps:
Step 1, weighing 0.3g of sodium hydroxide serving as a catalyst, dissolving the sodium hydroxide in 10mL of ethanol solution, adding the dissolved sodium hydroxide solution into a mixed solution of 60g of hydroxyl-terminated epoxy resin and 25g of epoxy diluent for chemical ring-opening reaction, wherein the reaction temperature is 70 ℃, and the reaction time is 2 hours, so as to obtain bisphenol A epoxy resin glue solution after ring opening;
Step 2, adding 12g of 3-phenyl-2-acrylic acid (cinnamic acid) into 60g of the bisphenol A epoxy resin glue solution prepared in the step 1 after ring opening under normal temperature, and then placing the glue solution into a heating jacket to heat for esterification reaction, wherein the reaction temperature is 90 ℃ and the reaction time is 1.5 hours, so as to obtain the cinnamic acid modified bisphenol A epoxy resin glue solution;
step 3, adding 2g of ultraviolet initiator, 5g of epoxy curing agent, 2.4g of accelerator and 0.12g of flatting agent into 60g of cinnamic acid modified bisphenol A type epoxy resin glue solution prepared in the step 2 in a light-shielding environment, and stirring for 0.5 hour at normal temperature to obtain photo-curable and thermosetting bicomponent cinnamic acid modified epoxy prepolymer glue solution;
And 4, adding 2g of coupling agent into the prepared bicomponent cinnamic acid modified epoxy prepolymer glue solution, dispersing at high speed for 5 minutes at the rotating speed of 650 rmp/min, and rapidly adding 75g of weighed heat-conducting filler (the mass ratio of the silica micro powder to the alumina is 0.5:1) to fully and uniformly disperse to obtain the bicomponent ultraviolet light curing acrylic acid-epoxy resin compound. The two-component ultraviolet light curing acrylic acid-epoxy resin compound is coated on a release film by a film coating instrument (the coating parameters of a film coating machine are that the film coating is carried out in a dipping tank at a coating speed of 0.5 m/min, the temperature of a film coating drying channel is 90 ℃ and the length of the drying channel is 6 m), and the film is quickly cured and formed by irradiation for 30s under ultraviolet light (290 nm), wherein the irradiation is carried out at normal temperature, so that the semi-cured bisphenol A film with uniform phase distribution is obtained.
And pressing the prepared ultraviolet-cured composite adhesive film (namely the semi-cured bisphenol A film) and the copper foil for 2 hours at 180 ℃ and 7Mpa to obtain the insulated composite copper foil.
Example 22
The embodiment provides a preparation method of a two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film, which comprises the following steps:
Step 1, weighing 0.5g of sodium hydroxide serving as a catalyst, dissolving the sodium hydroxide in 10mL of ethanol solution, adding the dissolved potassium hydroxide solution into a mixed solution of 70g of hydroxyl-terminated epoxy resin and 25g of epoxy diluent for chemical ring-opening reaction, wherein the reaction temperature is 60 ℃, and the reaction time is 1 hour, so as to obtain bisphenol A epoxy resin glue solution after ring opening;
Step 2, adding 15g of 3-phenyl-2-acrylic acid (cinnamic acid) into 70g of the bisphenol A epoxy resin glue solution prepared in the step 1 after ring opening under normal temperature, and then placing the glue solution into a heating jacket to heat for esterification reaction, wherein the reaction temperature is 75 ℃, and the reaction time is 2 hours, so as to obtain the cinnamic acid modified bisphenol A epoxy resin glue solution;
step 3, adding 2g of ultraviolet initiator, 5g of epoxy curing agent, 3.5g of accelerator and 0.20g of flatting agent into 70g of cinnamic acid modified bisphenol A type epoxy resin glue solution prepared in the step 2 in a light-shielding environment, and stirring for 1.5 hours at normal temperature to obtain photo-curable and thermosetting bicomponent cinnamic acid modified epoxy prepolymer glue solution;
And 4, adding 2g of coupling agent into the prepared bicomponent cinnamic acid modified epoxy prepolymer glue solution, dispersing at high speed for 5 minutes at the rotating speed of 650 rmp/min, and rapidly adding 75g of weighed heat-conducting filler (the mass ratio of the silica micro powder to the alumina is 0.5:1) to fully and uniformly disperse to obtain the bicomponent ultraviolet light curing acrylic acid-epoxy resin compound. The two-component ultraviolet light curing acrylic acid-epoxy resin compound is coated on a release film by a film coating instrument (the coating parameters of a film coating machine are that the film coating is carried out in a dipping tank at a coating speed of 0.5 m/min, the temperature of a film coating drying channel is 90 ℃ and the length of the drying channel is 6 m), and the film is quickly cured and formed by irradiation for 30s under ultraviolet light (290 nm), wherein the irradiation is carried out at normal temperature, so that the semi-cured bisphenol A film with uniform phase distribution is obtained.
And pressing the prepared ultraviolet-cured composite adhesive film (namely the semi-cured bisphenol A film) and the copper foil for 2 hours at 190 ℃ and 5Mpa to obtain the insulated composite copper foil.
Example 23
The embodiment provides a preparation method of a two-component ultraviolet light curing acrylic acid-epoxy resin adhesive film, which comprises the following steps:
Step 1, weighing 0.5g of sodium hydroxide serving as a catalyst, dissolving the sodium hydroxide in 10mL of ethanol solution, adding the dissolved barium hydroxide solution into a mixed solution of 75g of hydroxyl-terminated epoxy resin and 25g of epoxy diluent for chemical ring-opening reaction, wherein the reaction temperature is 65 ℃, and the reaction time is 1.5 hours, so that bisphenol A epoxy resin glue solution after ring opening is obtained;
Step 2, adding 15g of 3-phenyl-2-acrylic acid (cinnamic acid) into 75g of the bisphenol A epoxy resin glue solution prepared in the step 1 after ring opening under normal temperature, and then placing the glue solution into a heating sleeve to heat for esterification reaction, wherein the reaction temperature is 85 ℃, and the reaction time is 2 hours, so as to obtain the cinnamic acid modified bisphenol A epoxy resin glue solution;
Step 3, adding 2g of ultraviolet initiator, 5g of epoxy curing agent, 2.25g of accelerator and 0.075g of flatting agent into 75g of cinnamic acid modified bisphenol A type epoxy resin glue solution prepared in the step 2 in a light-proof environment, and stirring for 1.5 hours at normal temperature to obtain photo-curable and thermosetting bicomponent cinnamic acid modified epoxy prepolymer glue solution;
And 4, adding 2g of coupling agent into the prepared bicomponent cinnamic acid modified epoxy prepolymer glue solution, dispersing at high speed for 5 minutes at the rotating speed of 650 rmp/min, and rapidly adding 75g of weighed heat-conducting filler (the mass ratio of the silica micro powder to the alumina is 0.5:1) to fully and uniformly disperse to obtain the bicomponent ultraviolet light curing acrylic acid-epoxy resin compound. The two-component ultraviolet light curing acrylic acid-epoxy resin compound is coated on a release film by a film coating instrument (the coating parameters of a film coating machine are that the film coating is carried out in a dipping tank at a coating speed of 0.5 m/min, the temperature of a film coating drying channel is 90 ℃ and the length of the drying channel is 6 m), and the film is quickly cured and formed by irradiation for 30s under ultraviolet light (290 nm), wherein the irradiation is carried out at normal temperature, so that the semi-cured bisphenol A film with uniform phase distribution is obtained.
And pressing the prepared ultraviolet-cured composite adhesive film (namely the semi-cured bisphenol A film) and the copper foil for 2 hours at 190 ℃ and 5Mpa to obtain the insulated composite copper foil.
Compared with the insulating dielectric adhesive film prepared in the 'development of high-heat insulating dielectric adhesive film for metal substrate' published by Li Huilu et al, the invention effectively improves the breakdown voltage, reduces the dielectric loss, can be less than 3 per thousand, and can resist soldering 288 ℃ for more than 4 hours after the epoxy resin is modified.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310355317.6A CN116640527B (en) | 2023-04-06 | 2023-04-06 | Two-component UV-curable acrylic-epoxy resin film and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310355317.6A CN116640527B (en) | 2023-04-06 | 2023-04-06 | Two-component UV-curable acrylic-epoxy resin film and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116640527A CN116640527A (en) | 2023-08-25 |
| CN116640527B true CN116640527B (en) | 2025-04-04 |
Family
ID=87642452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310355317.6A Active CN116640527B (en) | 2023-04-06 | 2023-04-06 | Two-component UV-curable acrylic-epoxy resin film and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116640527B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117188160A (en) * | 2023-10-08 | 2023-12-08 | 西安康本材料有限公司 | A new type of fast light-curing sizing agent and its preparation method and sizing method |
| CN118219616B (en) * | 2024-02-27 | 2024-12-06 | 东莞市艾赛伦电子有限公司 | Aluminum substrate that can be photocured after bending |
| CN118374210B (en) * | 2024-05-07 | 2026-03-13 | 福建万安实业集团有限公司 | A high wear-resistant powder coating, its preparation method and application |
| CN119684950B (en) * | 2024-12-30 | 2025-11-04 | 苏州赛伍应用技术股份有限公司 | An epoxy resin dual-curing adhesive, its preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654607A (en) * | 2009-09-08 | 2010-02-24 | 烟台德邦科技有限公司 | High purity photo-thermal curing adhesive and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108034041B (en) * | 2017-12-25 | 2019-12-31 | 广东炎墨科技有限公司 | Alkali-soluble photocurable epoxy resin containing cinnamic acid or coumarin group, preparation method thereof, and solder resist prepared by using the same |
| KR102155180B1 (en) * | 2019-04-10 | 2020-09-11 | 주식회사 케이씨씨 | Dual cure adhesive composition |
| CN113912824B (en) * | 2021-11-29 | 2023-11-21 | 广州市白云化工实业有限公司 | Modified epoxy acrylate prepolymer, photo-thermal dual-curing conductive adhesive and preparation method thereof |
-
2023
- 2023-04-06 CN CN202310355317.6A patent/CN116640527B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654607A (en) * | 2009-09-08 | 2010-02-24 | 烟台德邦科技有限公司 | High purity photo-thermal curing adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116640527A (en) | 2023-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN116640527B (en) | Two-component UV-curable acrylic-epoxy resin film and preparation method and application thereof | |
| CN104228186B (en) | A kind of high heat conduction high-performance aluminum matrix copper-clad laminate and preparation method thereof | |
| TWI609942B (en) | Binder composition with high frequency characteristics and use thereof | |
| JP6886292B2 (en) | Ultra-low dielectric loss thermosetting resin composition and high performance laminates produced thereby | |
| TWI716967B (en) | Resin composition, prepreg, laminate, metal-clad laminate and printed circuit board | |
| CN110511533A (en) | Polyether ether ketone/tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer/chopped quartz fiber material, preparation method and application | |
| JP2012111807A (en) | Thermosetting resin composition and prepreg sheet or laminated board using the thermosetting resin composition | |
| CN106661311A (en) | Resin compositions, prepregs, metal foils with resins, metal-clad and laminated boards and printed wiring boards | |
| TWI412564B (en) | Dielectric material formula and circuit board utilizing the same | |
| CN107201185A (en) | A kind of pure glued membrane of heat cure | |
| CN119217811A (en) | A low dielectric and high heat-resistant copper-clad laminate and a preparation method thereof | |
| TW201835208A (en) | A process for the preparation of a flame retardant modified styrene-maleic anhydride resins and a composition of epoxy resins and their applying use to copper clad laminate and prepreg | |
| CN104908400B (en) | High frequency-characteristic copper-clad plate manufacturing method | |
| CN102453225A (en) | Thermosetting resin composition and application thereof in prepreg or laminated plate | |
| CN113969122B (en) | Low-dielectric thermosetting adhesive composition, preparation method thereof and flexible copper-clad plate | |
| CN115975526A (en) | A kind of low hygroscopic epoxy adhesive film and preparation method thereof | |
| TW574313B (en) | Resin composition for circuit boards | |
| CN106661198B (en) | Resin combination, prepreg, the metal foil of resin, metal-clad, printed wiring board | |
| CN114292607B (en) | Adhesive and preparation method and application thereof | |
| CN101104784A (en) | Composite laminated board high-temperature resistant adhesive and preparation method thereof | |
| CN105542161B (en) | A kind of fire-retardant cyanate ester resin and preparation method thereof | |
| CN115449211A (en) | Flexible corrosion-resistant PPO resin-based copper-clad plate and preparation method thereof | |
| CN115975093A (en) | Preparation, composition and application of a thermosetting resin of a catechol copolymer | |
| CN115073858B (en) | Bi-horse modified olefin resin glue solution and adhesive tape for high-frequency plate, and preparation method and application thereof | |
| CN102020959B (en) | Build-up adhesive with high thermal conductivity and low dissipation factor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |