CN116200160A - Non-microetching organic copper surface bonding agent and preparation method thereof - Google Patents
Non-microetching organic copper surface bonding agent and preparation method thereof Download PDFInfo
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- CN116200160A CN116200160A CN202211435178.XA CN202211435178A CN116200160A CN 116200160 A CN116200160 A CN 116200160A CN 202211435178 A CN202211435178 A CN 202211435178A CN 116200160 A CN116200160 A CN 116200160A
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- copper
- bonding agent
- polyurethane
- microetching
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- 239000010949 copper Substances 0.000 title claims abstract description 154
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 154
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 239000007767 bonding agent Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000004814 polyurethane Substances 0.000 claims abstract description 72
- 229920002635 polyurethane Polymers 0.000 claims abstract description 72
- 125000000524 functional group Chemical group 0.000 claims abstract description 32
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- -1 amidino, oxazolyl Chemical group 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 10
- 125000003368 amide group Chemical group 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
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- 125000003396 thiol group Chemical class [H]S* 0.000 claims abstract 2
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 17
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- 238000007254 oxidation reaction Methods 0.000 claims description 16
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 15
- PVNIIMVLHYAWGP-UHFFFAOYSA-N nicotinic acid Natural products OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229960005070 ascorbic acid Drugs 0.000 claims description 12
- 150000003983 crown ethers Chemical class 0.000 claims description 12
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
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- 239000011664 nicotinic acid Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 150000003949 imides Chemical class 0.000 claims description 7
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000002211 L-ascorbic acid Substances 0.000 claims description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 125000000627 niacin group Chemical group 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 235000011187 glycerol Nutrition 0.000 description 15
- 239000000758 substrate Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- 230000008646 thermal stress Effects 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- RAOWWWKNDVOQDP-UHFFFAOYSA-N copper;propane-1,2,3-triol Chemical compound [Cu].OCC(O)CO RAOWWWKNDVOQDP-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 238000000576 coating method Methods 0.000 description 3
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- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005232 molecular self-assembly Methods 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- 125000002971 oxazolyl group Chemical group 0.000 description 1
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0545—Dispersions or suspensions of nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/085—Copper
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The application relates to the technical field of bonding agents, and particularly discloses a non-microetching organic copper surface bonding agent and a preparation method thereof. The non-microetching organic copper surface bonding agent comprises any one or two of aqueous polyurethane and modified polyurethane, wherein a connecting functional group is grafted on the aqueous polyurethane and the modified polyurethane, the connecting functional group comprises any one or two of a bonding functional group and a polymerization functional group, the bonding functional group is selected from any one of carboxyl, amido, amidino, oxazolyl, sulfonic acid and mercapto, and the polymerization functional group is selected from any one of double bond, aldehyde and epoxy. The bonding agent can be used in a multilayer circuit board, and has the advantages of firm bonding, difficult microetching of copper surfaces and simple and convenient use.
Description
Technical Field
The application relates to the field of bonding agents, in particular to a non-microetching organic copper surface bonding agent and a preparation method thereof.
Background
A Printed Circuit Board (PCB) belongs to the electronic equipment manufacturing industry and is a platform for ensuring that various electronic components form an electrical interconnection. A thin copper layer is covered on one side or two sides of a polymer substrate, photoresist is covered on the copper surface, and a circuit pattern can be formed on the copper surface after exposure, development and etching, so that a circuit board with one side or two sides can be manufactured. With the development of technology, in order to increase the density of electrical interconnections, multilayer boards have been developed, but delamination between copper and a substrate between the multilayer boards is liable to occur.
In order to improve the bonding force between copper and glue, researchers have made various searches, and in the process of the searches, inner layer bonding treatment techniques such as a blackening method, a microetching method, a browning method and the like have been found. The blackening method increases the specific surface area of thin copper by oxidizing copper to cuprous, and increases the bonding firmness between copper and a base material. However, pink ring phenomenon is easy to occur in black oxidation, and the multilayer board is easy to discard. The microetching method has the defects of poor system stability, unstable etching rate, difficult control of uniformity and the like. The brown oxide method has better reliability, and generally, the brown oxide liquid comprises sulfuric acid, hydrogen peroxide and specific organic matters, an organic metal film is formed on the surface of copper, and the bonding firmness between the copper and the substrate is improved through a curing and crosslinking reaction.
For the related technology, the specific surface area of the copper surface is increased to enhance the bonding firmness between the copper and the base material, namely, the copper surface is subjected to micro etching to ensure that the copper surface has enough roughness, but the degree of micro etching is difficult to control in the process, and the signal transmission between the multilayer boards is easily influenced.
Disclosure of Invention
In order to improve the signal transmission effect between the multilayer boards, the application provides a non-microetching organic copper surface bonding agent and a preparation method thereof.
In a first aspect, the present application provides a non-microetching organic copper surface bonding agent, which adopts the following technical scheme:
the non-microetching organic copper surface bonding agent comprises any one or two of aqueous polyurethane and modified polyurethane, wherein the aqueous polyurethane and the modified polyurethane are polyurethane grafted with a connecting functional group, the connecting functional group comprises any one or two of a bonding functional group and a polymerization functional group, the bonding functional group is selected from any one of carboxyl, amido, amidino, oxazolyl, sulfonic acid and mercapto, and the polymerization functional group is selected from any one of double bond, aldehyde and epoxy.
Through adopting above-mentioned technical scheme, this application technical scheme preferably adopts waterborne polyurethane and modified polyurethane cooperation as the bonding agent, and waterborne polyurethane and modified polyurethane both have comparatively excellent bonding effect, improve the bonding effect between copper and the substrate through the cohesiveness, compare with blackening method, microetching method, brown method, need not to microetch copper, can maintain copper surface's integrality, improves signal transmission between the multiply wood.
In the technical scheme, the grafting bonding functional group or the polymerization functional group on the waterborne polyurethane and the modified polyurethane is preferably adopted, carboxyl, amido, amidine, oxazolyl, sulfonic acid and mercapto in the bonding functional group can be firmly combined with the copper surface in a coordination combination mode, double bonds, aldehyde and epoxy in the polymerization functional group can be firmly combined with the resin in a polymerization mode, and the setting of the connection functional group ensures that the copper is firmly combined with the substrate layer through chemical bonds, and the bonding effect is uniform, thereby being beneficial to signal transmission between the multilayer plates.
Preferably, the preparation method of the modified polyurethane comprises the following preparation steps: respectively taking polyurethane imide, epoxy resin and curing agent according to the mass ratio of 10:4-6:0.68, stirring and mixing to obtain the polyurethane grafted with the difunctional groups.
Through adopting above-mentioned technical scheme, preferably adopt polyurethane imide and epoxy cooperation in this application technical scheme, terminal carboxyl on the polyurethane imide reacts the ring opening with the curing agent and forms secondary amine structure, carry out the ring opening reaction with the epoxy in the epoxy again, cross-link each other, the amido and epoxy have simultaneously been obtained on the modified polyurethane, have bonding functional group and polymerization functional group on the modified polyurethane promptly simultaneously, therefore bonding agent not only can be through coordination combination with the copper surface, can also be connected through the polymerization with the substrate, realized that copper and the chemical bond of substrate firmly combine, signal transmission effect between the multiply wood has been improved.
Preferably, the nano-copper is spherical, and the particle size of the nano-copper is 50-100 nm.
Through adopting above-mentioned technical scheme, the preferred adoption has added nano copper granule in the bonding agent among this application technical scheme, at first, because nano copper's particle diameter is less, can form fine particle layer on copper surface, has effectively increased copper surface's specific surface area, when coating the substrate on copper surface, has increased substrate and copper's area of contact, has further improved copper and substrate's bonding fastness promptly. Secondly, the spherical nano copper particles are not easy to agglomerate, and the spherical structure ensures that the nano copper can be uniformly dispersed on the bonding agent, namely, the copper surface obtains a uniform and rough surface, so that the surface smoothness of a film formed by the bonding agent is maintained, and the bonding agent can obtain a uniform bonding effect.
Preferably, the nano copper is nano copper subjected to oxidation resistance treatment, and the oxidation resistance treatment comprises the following preparation steps: respectively taking 0.01-0.04mol/L copper chloride dihydrate, 0.05-0.1L glycerol solvent, 0.05-0.1mol/L polyvinylpyrrolidone and 0.02-0.06mol/L ascorbic acid, stirring and mixing the copper chloride dihydrate and 1/4 volume of glycerol solvent to obtain copper liquid; stirring and mixing polyvinylpyrrolidone, ascorbic acid and the rest glycerol solvent to obtain an oxidation solution; adding the oxidation solution into the copper solution, stirring and mixing, adjusting the pH value, placing the mixture into a reaction kettle for reaction, taking out a product, washing the product to obtain clear supernatant, and carrying out vacuum drying to obtain a dried product, thus obtaining the nano copper subjected to the antioxidation treatment.
By adopting the technical scheme, the binary solvent heating method is preferably adopted in the technical scheme, the copper chloride dihydrate is complexed in advance, then the ascorbic acid is used for reducing copper ions, glycerin copper is obtained by reaction in the process, the carbon chain skeleton of the glycerin copper is smaller and reacts with the ascorbic acid, larger steric hindrance is formed in an auxiliary way, and therefore, the formed copper particles have better dispersibility. The addition of polyvinylpyrrolidone can be used as a dispersing agent to wrap copper particles, namely, the copper particles are coated with a dispersing layer, so that the dispersing uniformity of nano copper in the bonding agent is further improved.
Secondly, the concentration ratio of the ascorbic acid to the copper chloride dihydrate is optimized in the technical scheme, the particle size of the nano copper generated under the proper concentration is uniform, the morphology is uniform, agglomeration is not easy to occur, the dispersibility is good, and the dispersion uniformity of the nano copper in the bonding agent is further improved.
In addition, the concentration ratio of polyvinylpyrrolidone to copper chloride dihydrate is optimized in the technical scheme, so that the polyvinylpyrrolidone can uniformly wrap the surface of the nano copper under the concentration, and no excessive polyvinylpyrrolidone is loaded on the surface of the nano copper, and the nano copper is independently and uniformly dispersed in the bonding agent.
Preferably, the glycerol solvent comprises glycerol and deionized water in a volume ratio of 1-2:3-4.
Through adopting above-mentioned technical scheme, optimized the volume ratio in glycerol and the deionized water among the technical scheme of this application, under suitable volume ratio, copper chloride dihydrate is comparatively even and thorough in the complexation of glycerol solution, reduction, is difficult for forming cupric oxide, cuprous oxide etc. and the nanometer copper that forms is purer and the topography is regular, is favorable to forming the nanometer copper that the dispersibility is excellent.
Preferably, part of the dried product is a dried product of surface modification treatment with a modifier, wherein the modifier comprises either or both of citric acid and oleic acid.
Through adopting above-mentioned technical scheme, the optimization carries out surface modification to the dry product, dry nano copper in this application technical scheme promptly, because nano copper's size is less, and small-size effect is more easy to make nano copper and oxygen contact and oxidation, wraps up nano copper's surface through citric acid or oleic acid cooperation polyvinylpyrrolidone, separates nano copper and oxygen to the dispersibility to nano copper has no influence, has steadily improved nano copper's oxidation resistance.
Preferably, the polyurethane nanometer copper-based polyurethane adhesive further comprises a bonding agent, wherein the bonding agent comprises crown ether or a nitrogenous heterocyclic compound, and the mass ratio of the polyurethane to the nanometer copper to the bonding agent is 10:2-4:1.
By adopting the technical scheme, crown ether or a nitrogenous heterocyclic compound is preferably adopted as a binding agent in the technical scheme, and the crown ether and the nitrogenous heterocyclic compound have more coordination sites, so that coordination combination between the bonding agent and copper can be induced, the bonding agent can be quickly combined with the surface of copper, and the bonding strength of the bonding agent and copper is further improved.
Preferably, the binding agent is a crown ether, which is an aza crown ether ligand.
By adopting the technical scheme, the aza-crown ether ligand is preferably adopted as a binding agent in the technical scheme, and has a plurality of coordination sites, so that the aza-crown ether ligand can show special stability and complexation selectivity to neutral molecules, inorganic and organic ions, heavy metal ions, transition metal ions, ammonium salts and the like, that is, carboxylic acid anions on the aza-crown ether ligand can be used as a donor and a receptor of hydrogen bonds, and can be firmly combined with the copper surface through coordination bonding, so that the combination firmness between copper and a matrix is improved.
Preferably, the crown ether is a niacin-treated crown ether.
By adopting the technical scheme, nicotinic acid is matched with the aza-crown ether ligand, the nicotinic acid is bridged, and is coordinated and combined with copper through the molecular self-assembly function with the aza-crown ether ligand to form a one-dimensional supermolecular structure, so that the connection strength between the bonding agent and the copper surface is effectively improved, namely the combination firmness between the copper and a matrix is improved.
In a second aspect, the present application provides a method for preparing a non-microetching organic copper surface bonding agent, which adopts the following technical scheme:
the preparation method of the non-microetching organic copper surface bonding agent comprises the following steps: the aqueous polyurethane and the modified polyurethane are stirred and mixed and are stood to obtain the bonding agent.
Through adopting above-mentioned technical scheme, mix waterborne polyurethane and modified polyurethane in this application technical scheme after, the processing of standing for the various components in the bonding agent can evenly cross-link and disperse, consequently can obtain excellent cohesiveness after coating to copper surface.
In summary, the present application has the following beneficial effects:
1. because the waterborne polyurethane and the modified polyurethane are matched to serve as bonding agents, the bonding firmness between copper and a substrate is improved through the excellent cohesiveness of the waterborne polyurethane and the modified polyurethane; meanwhile, functional groups are grafted on the waterborne polyurethane and the modified polyurethane, and the bonding property between copper and a base material is firmly enhanced by adopting a mode of bonding with chemical bonds such as copper coordination bonding, base material polymerization bonding and the like. The bonding agent is not easy to generate microetching on copper, can maintain the integrity of copper surface, and improves the signal transmission effect between the multilayer boards.
2. In the method, nano copper particles are preferably added into the bonding agent, so that a fine particle layer is formed on the surface of copper, and the specific surface area of the copper surface is effectively increased; the spherical nano copper particles are not easy to agglomerate, and the spherical structure ensures that the nano copper can be uniformly dispersed on the bonding agent, namely, the copper surface obtains a uniform and rough surface, so that the surface smoothness of a film formed by the bonding agent is maintained, and the bonding agent can obtain a uniform bonding effect.
3. In the method, binary solvent heating is preferably adopted to prepare nano copper, copper chloride dihydrate is complexed in advance, then ascorbic acid is used for reducing copper ions, glycerin copper is obtained through reaction in the process, a carbon chain skeleton of the glycerin copper is smaller and reacts with ascorbic acid to assist in forming larger steric hindrance, and therefore formed copper particles have better dispersibility. The addition of polyvinylpyrrolidone can be used as a dispersing agent to wrap copper particles, namely, the copper particles are coated with a dispersing layer, so that the dispersing uniformity of nano copper in the bonding agent is further improved.
Drawings
Fig. 1 is a schematic diagram showing bonding between bonding agent and copper, substrate in this application.
Detailed Description
The present application is described in further detail below with reference to examples.
In the embodiment of the present application, the selected instruments and devices are shown below, but not limited to:
medicine: the aqueous polyurethane is epoxy modified aqueous polyurethane with the model 5136 of Wuhanshi Quanxing new material technology Co., ltd.
Preparation example
Preparation of modified polyurethane
Preparation examples 1 to 3
Weighing 0.5kg of PTHF (polytetrahydrofuran ether glycol), drying in vacuum at 100 ℃ for 1h, adjusting the temperature to 50 ℃, adding 0.2852kg of MDI (diphenylmethane-4, 4-isocyanate) under nitrogen atmosphere, reacting for 4.5h at 40 ℃, adding DMF, stirring and mixing to obtain a primary solution. 0.384kg TMA (meta anhydride) is added into the primary solution, and the reaction is carried out for 1h at 50 ℃, 2h at 80 ℃ and 2h at 100 ℃ to obtain the polyurethane imide material.
Respectively weighing polyurethane imide, epoxy resin and curing agent CX-100, wherein the specific mass is shown in table 1, and stirring and mixing to obtain modified polyurethane 1-3.
TABLE 1 preparation examples 1-3 modified polyurethane compositions
Among them, it is worth mentioning that the modified polyurethane has attached thereto a bonding functional group or a polymeric functional group, including but not limited to: any one of carboxyl, amido, amidino, oxazolyl, sulfonic acid and mercapto is selected from the amide in the preparation example; the polymeric functional groups include, but are not limited to: any one of double bond, aldehyde group and epoxy group is selected as epoxy group in the preparation example.
Preparation of antioxidant treated nano copper
Preparation examples 4 to 6
Copper chloride dihydrate, glycerol solvent, polyvinylpyrrolidone and ascorbic acid were taken respectively, and the specific mass is shown in table 2. Stirring copper chloride dihydrate and 1/4 volume of glycerol solvent at 60 ℃ for 30min to obtain copper liquid; stirring polyvinylpyrrolidone, ascorbic acid and the rest glycerol solvent for 30min until the polyvinylpyrrolidone, ascorbic acid and the rest glycerol solvent are dissolved to obtain an oxidation solution; adding the oxidation solution into the copper solution, stirring and mixing, adding the solution to have the concentration of 1mol/L after the solution is clarified, adjusting the pH value to be 9, placing the solution into a reaction kettle for reaction, reacting for 4 hours at 90 ℃, taking out the product, respectively adopting absolute ethyl alcohol and deionized water for washing for 3 times, clarifying the supernatant, and carrying out vacuum drying at 50 ℃ to obtain a dried product, thus obtaining the nano copper 1-3 subjected to the antioxidation treatment.
TABLE 2 preparation examples 4-6 antioxidant treated nano copper composition
Wherein the glycerol solvent comprises glycerol and deionized water in a volume ratio of 3:2.
Preparation example 7
The difference from preparation example 5 is that: the glycerol solvent comprises glycerol and deionized water in a volume ratio of 4:1, and nano copper 4 subjected to antioxidation treatment is prepared.
Preparation example 8
Spherical superfine copper powder with the particle size of 50-80nm is adopted as nano copper.
Preparation example 9
The difference from the preparation example 2 is that: the dried product in preparation example 2 was subjected to a surface modification treatment using citric acid as a modifier, the surface modification treatment comprising the steps of: washing the dried product with dilute sulfuric acid with the volume fraction of 5% for 3 times, washing with deionized water for 3 times, dispersing into absolute ethyl alcohol, adding citric acid, performing 70% power ultrasonic treatment for 20min, performing centrifugal washing with absolute ethyl alcohol, and drying at 50 ℃ to obtain the dried product subjected to surface modification treatment, wherein the dried product is used as nano copper 5 subjected to antioxidation treatment.
Preparation example 10
The difference from preparation example 9 is that: oleic acid was used instead of citric acid in preparation example 9 to prepare nano copper 6 subjected to an oxidation-resistant treatment.
Preparation of binding agent
PREPARATION EXAMPLE 11
Crown ether was taken as binder 1.
Preparation example 12
The tetraazacyclic compound is taken as a binding agent 2.
Preparation example 13
108g of p-cresol, 282g of hexamethylenetetramine and 300g of paraformaldehyde are weighed at room temperature, dissolved in 1000mL of acetic acid, continuously stirred for 2 hours at the temperature of 80 ℃ in a water bath, cooled to room temperature, 100mL of concentrated sulfuric acid is added dropwise into the solution, oil bath is refluxed for half an hour at the temperature of 120 ℃, after the reaction is finished, the mixed solution is poured into 4000mL of distilled water to obtain a large amount of yellow flocculent precipitate, and the yellow flocculent precipitate is stood overnight and filtered to obtain a first intermediate.
3.28g of the first intermediate, 10g of perchloric acid and 2.5mL of acetic acid were taken, 300mL of methanol solution was added, stirred and refluxed, 200mL of methanol solution containing 1.76g of butanediamine was slowly added dropwise, red crystals were formed, left standing overnight, filtered, and solids were retained to obtain a second intermediate.
3.21g of the second intermediate was weighed and dissolved in 300mL of methanol solution, and NaBH was added with stirring 4 The solid was reduced at 5g and the red solution slowly turned colorless and filtered, 50mL of water was added to the filtrate and left overnight to give a large amount of white crystals which were filtered to give the aza crown ether ligand as binder 3.
PREPARATION EXAMPLE 14
The difference from preparation example 13 is that: 0.44g of aza crown ether ligand is dissolved in 150mL of methanol, 0.246g of nicotinic acid is added, and the mixture is stirred and mixed for 30min to obtain the crown ether treated by the nicotinic acid as a bonding agent 4.
Examples
Examples 1 to 7
In one aspect, the application provides a non-microetching organic copper surface bonding agent, which comprises aqueous polyurethane, modified polyurethane 1, nano copper and a bonding agent 1, wherein the specific mass is shown in table 3.
Wherein the aqueous polyurethane and the modified polyurethane are polyurethane grafted with a connecting functional group, and the aqueous polyurethane in the embodiment is epoxy aqueous polyurethane.
In another aspect, the present application provides a method for preparing a non-microetching organic copper surface bonding agent, comprising the steps of: the aqueous polyurethane and the modified polyurethane are stirred and mixed and are stood to obtain the bonding agent.
TABLE 3 examples 1-7 bonding agent compositions
Examples 8 to 9
The difference from example 2 is that: modified polyurethane 2-3 was used instead of modified polyurethane 1 in example 3 to prepare bonding agents 8-9.
Example 10
The difference from example 4 is that: instead of the spherical nano-copper in example 4, the bonding agent 10 was prepared using non-spherical nano-copper.
Examples 11 to 16
The difference from example 4 is that: the bonding agents 11 to 16 were prepared using the oxidation-resistant treated nano copper 1 to 6 instead of the spherical nano copper in example 4.
Examples 17 to 19
The difference from example 6 is that: bonding agents 17-19 were prepared using bonding agents 2-4 instead of bonding agent 1 in example 6.
Comparative example
Comparative example 1
This comparative example differs from example 3 in that only aqueous polyurethane was used as the bonding agent in this comparative example.
Performance test
(1) Peel strength: the multi-layer board was tested according to IPC-TM650 2.4.8, and the peel strength was measured using a glass strength tester and recorded in lb/inch.
(2) And (3) thermal stress performance detection: the test sample is placed in a baking oven horizontally, baked for 1h at 130 ℃, then placed in a dryer for cooling to room temperature, taken out of the dryer by pliers, coated with rosin, removed with tin surface scum, rinsed with tin for 10+/-1 s, taken out for cooling, circulated, cleaned and observed, and the number of rinsing tin without layering is recorded.
(3) And (3) cold and hot impact cycle performance detection: placing the sample in a cold and hot circulation test box, heating from room temperature to 125 ℃ at a speed of 33 ℃/min and keeping the temperature for 30min, then cooling to room temperature at a speed of 25 ℃/min and keeping the temperature for 10min, then cooling to-55 ℃ at a speed of 20 ℃/min and keeping the temperature for 30min, finally heating to room temperature at a speed of 30 ℃/min and keeping the temperature for 10min, adding time such as automatic defrosting of an instrument, taking 90min for one circulation, and recording the circulation times without layering.
(4) And (3) detecting oxidation resistance: the nano-copper subjected to the antioxidation treatment in preparation examples 4 to 10 was examined, and the nano-copper was examined by XRD diffractometer, and after 30 days, whether the nano-copper was oxidized or not was observed.
Table 4 performance tests for examples 1-19, comparative example 1
The viscosity of the bonding agent in example 3 was 300cps.
The oxidation-resistant treated nano-copper 1-6 prepared in preparation examples 4-10 were not oxidized.
The comparison of performance tests in combination with Table 2 can be found:
(1) Comparison of examples 1-3 and comparative example 1 shows that: the bonding agent prepared in examples 1-3 has improved peel strength, thermal stress and cycle number of cold and hot impact, which means that the bonding agent is firmly bonded with copper or a matrix by adopting a mode of coordination bonding or a mode of polymerization by grafting bonding functional groups or polymerization functional groups on polyurethane, namely, the bonding firmness between copper and the matrix (resin) is improved.
(2) Comparison of examples 8-9 with example 2 shows that: the bonding agent prepared in examples 5-7 has improved peel strength, thermal stress and cycle number of cold and hot impact, which means that polyurethane imide and epoxy resin are matched, amide groups and epoxy groups are obtained on modified polyurethane through ring opening, crosslinking and other reactions, and the bonding agent can be combined with the copper surface through coordination and is polymerized to connect a matrix, so that the chemical bond of copper and a substrate is firmly combined.
(3) It can be found in combination with examples 4, 10, 11-13 and 14 that: the bonding agents prepared in examples 11-13 all had improved peel strength, thermal stress, and cycle number of cold and hot impact, which indicates that the addition of spherical nano copper in the bonding agent in the present application can uniformly disperse nano copper in the bonding agent, uniformly increase the specific surface of copper, and improve the bonding force between the substrate layer and copper. The binary solvent heating method is used for preparing the nano copper, so that larger steric hindrance is formed in the reaction process, and the dispersibility of the nano copper is improved. And the coating of polyvinylpyrrolidone further improves the dispersion uniformity of nano copper in the bonding agent. Meanwhile, the proportion among the components is optimized, the proper proportion can enable the particle size of the nano copper to be 50-100nm, the particle morphology is uniform, and the possibility of agglomeration of the nano copper is reduced.
(4) The comparison of examples 15-16 and example 4 can be found: the bonding agents prepared in examples 15-16 all have improved peel strength, thermal stress and cold and hot impact cycle times, which means that citric acid or oleic acid is adopted to cooperate with polyvinylpyrrolidone to wrap the surface of the nano copper, so that the nano copper is blocked from oxygen, the dispersibility of the nano copper is unaffected, and the oxidation resistance of the nano copper is stably improved.
(5) As can be seen from a comparison of examples 5-7, examples 17-19 and example 2: the bonding agent prepared in examples 17-20 has improved peel strength, thermal stress and cold and hot impact cycle times, which means that nicotinic acid is matched with the aza-crown ether ligand, and the nicotinic acid is bridged and combined with copper through molecular self-assembly action to form a one-dimensional supermolecular structure, so that the connection strength between the bonding agent and the copper surface is effectively improved, namely the bonding firmness between copper and a matrix is improved.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. A non-microetching organic copper surface bonding agent, characterized in that: the polyurethane modified polyurethane comprises any one or two of waterborne polyurethane and modified polyurethane, wherein the waterborne polyurethane and the modified polyurethane are polyurethane grafted with a connecting functional group, the connecting functional group comprises any one or two of a bonding functional group and a polymerization functional group, the bonding functional group is selected from any one of carboxyl, amido, amidino, oxazolyl, sulfonic acid and mercapto, and the polymerization functional group is selected from any one of double bond, aldehyde and epoxy.
2. The non-microetching organic copper surface bonding agent according to claim 1, wherein the preparation method of the modified polyurethane comprises the following preparation steps: respectively taking polyurethane imide, epoxy resin and curing agent according to the mass ratio of 10:4-6:0.68, stirring and mixing to obtain the polyurethane grafted with the difunctional groups.
3. A non-microetching organic copper surface bonding agent according to claim 1, wherein: the nano copper is spherical, and the particle size of the nano copper is 50-100 nm.
4. A non-microetching organic copper surface bonding agent according to claim 3, wherein: the nano copper is nano copper subjected to antioxidation treatment, and the antioxidation treatment comprises the following preparation steps: respectively taking 0.01-0.04mol/L copper chloride dihydrate, 0.05-0.1L glycerol solvent, 0.05-0.1mol/L polyvinylpyrrolidone and 0.02-0.06mol/L ascorbic acid, stirring and mixing the copper chloride dihydrate and 1/4 volume of glycerol solvent to obtain copper liquid; stirring and mixing polyvinylpyrrolidone, ascorbic acid and the rest glycerol solvent to obtain an oxidation solution; adding the oxidation solution into the copper solution, stirring and mixing, adjusting the pH value, placing the mixture into a reaction kettle for reaction, taking out a product, washing the product to obtain clear supernatant, and carrying out vacuum drying to obtain a dried product, thus obtaining the nano copper subjected to the antioxidation treatment.
5. A non-microetching organic copper surface bonding agent according to claim 4, wherein: the glycerol solvent comprises glycerol and deionized water in a volume ratio of 3-4:1-2.
6. A non-microetching organic copper surface bonding agent according to claim 4, wherein: the dry product is a dry product of surface modification treatment of a modifier, and the modifier comprises any one or two of citric acid and oleic acid.
7. A non-microetching organic copper surface bonding agent according to claim 1, wherein: the polyurethane nano-copper-based adhesive also comprises a bonding agent, wherein the bonding agent comprises crown ether or a nitrogenous heterocyclic compound, and the mass ratio of the polyurethane to the nano-copper to the bonding agent is 10:2-4:1.
8. A non-microetching organic copper surface bonding agent according to claim 7, wherein: the binding agent is a crown ether, which is an aza crown ether ligand.
9. A non-microetching organic copper surface bonding agent according to claim 8, wherein: the crown ether is a nicotinic acid-treated crown ether.
10. A method of preparing a non-microetching organic copper surface bonding agent according to any one of claims 1 to 9, comprising the steps of: the aqueous polyurethane and the modified polyurethane are stirred and mixed and are stood to obtain the bonding agent.
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| CN109266284A (en) * | 2018-09-05 | 2019-01-25 | 广东生益科技股份有限公司 | A kind of halogen-free resin composition, cover film prepared therefrom and copper-clad plate and printed circuit board |
| CN113286835A (en) * | 2019-01-29 | 2021-08-20 | 东洋纺株式会社 | Adhesive composition containing dimer alcohol copolymerized polyimide polyurethane resin |
| CN114016094A (en) * | 2021-09-29 | 2022-02-08 | 深圳市励高表面处理材料有限公司 | Leveling agent and preparation method thereof |
| CN115188523A (en) * | 2022-08-10 | 2022-10-14 | 芯体素(杭州)科技发展有限公司 | Low-temperature copper paste suitable for high-precision 3D printing and preparation method and application thereof |
| CN115584185A (en) * | 2022-10-25 | 2023-01-10 | 深圳市利红金科技有限公司 | Weldable tin-copper slurry and preparation method and application thereof |
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