CN109504038A - A kind of Halogen-free high heat-resistant resin combination for HDI copper-clad plate - Google Patents
A kind of Halogen-free high heat-resistant resin combination for HDI copper-clad plate Download PDFInfo
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- CN109504038A CN109504038A CN201811511136.3A CN201811511136A CN109504038A CN 109504038 A CN109504038 A CN 109504038A CN 201811511136 A CN201811511136 A CN 201811511136A CN 109504038 A CN109504038 A CN 109504038A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The present invention discloses a kind of Halogen-free high heat-resistant resin combination for HDI copper-clad plate, and by organic solid content based on 100 parts by weight (PHR), composition includes following main component: (a) polyfunctional epoxy resin 30-60PHR；(b) toughened resin 20-40PHR；(c) phosphorous epoxy resin 10-30PHR；(d) phosphorus curing agent 30-60PHR；(e) other curing agent 10-30PHR；(f) 30~150PHR of inorganic filler；(g) 0.01~1PHR of curing accelerator；(h) 0.01~1PHR of silane coupling agent；(i) solvent is appropriate.Rigidity and flexibility resin are had both in this resin combination, made copper-clad laminate has good processability, while having both excellent dimensional stability, high-fire resistance, good dielectric properties, low-expansion coefficient, and flame retardant rating is UL94 V-0 grades.
Description
Technical field
The present invention relates to copper-clad laminate field technologies, refer in particular to a kind of Halogen-free high heat-resistant for HDI copper-clad plate
Property resin combination.
Background technique
Along with advancing by leaps and bounds for the information industries such as electronic computer, mobile phone and electronics industry, each electronic product
It constantly incorporates in the work and life of people, has pushed the innovation of PCB (printed circuit board) production technology, also pushed PCB base
The development of material (copper-clad plate).
Used in traditional printed circuit board largely the material containing halogen containing flame-retardant it is fire-retardant etc. to reach UL94V-0
Grade, but this kind of material burning when generate a large amount of cigarette case it is toxic and have corrosive gas.WEE and RoHs is promulgated from European Union
After application of two instruction limitation halogen flames in electronics industry, PCB manufacturer also requires copper-clad plate manufacturer to develop Halogen
Copper-clad plate material.Exploitation halogen-free environmental copper-clad plate material has become inexorable trend.
As electronic product is constantly to thin, light, short, small and high speed information demand, PCB is in circuit design and processing procedure skill
Increasingly complexity progresses greatly in art, gradually toward thin wire, thin space, highly integrated, multiple stratification development.The appearance of build-up multi layer board, is opened
The new era of a HDI multi-layer board manufacturing technology is created.Therefore, for meet HDI it is highly integrated, it is multiple pressing etc. special process processing procedure
There are increasingly higher demands in demand, PCB manufacturer to the performance etc. of substrate.Produce the HDI wiring board requirement copper-clad plate of high multilayer
Must have good dimensional stability and heat resistance；To meet high speed information propagation, signal integrity and authenticity, it is desirable that cover
Copper sheet has low-k (Dk) and low-dielectric loss tangent value (Df)；In addition to this it should also have excellent machining
The properties such as property, resistance to Ion transfer, endurance.Common FR-4 epoxy systems copper-clad plate is because having biggish thermal expansion coefficient
And dimensional stability needed for HDI wiring board can not being met in PCB production process, while heat resistance, dielectricity are also difficult to reach
To requirement.And though the properties such as special resin such as polyflon, polyphenylene oxide resin are good, it is at high price, and
Processing technology is special, and the development in the field HDI is restricted.Therefore, a high-performance is developed, moderate cost meets HDI system
The copper-clad plate of journey has become the urgent market demand.
Summary of the invention
Copper is covered for HDI in view of this, in view of the deficiencies of the prior art, the present invention aims to provide one kind
The Halogen-free high heat-resistant resin combination of plate is suitable for production HDI with prepreg made of this resin combination and copper-clad plate
(high density interconnection) wiring board.
To achieve the above object, the present invention is using following technical solution:
A kind of Halogen-free high heat-resistant resin combination for HDI copper-clad plate presses 100 parts by weight with organic solid content
(PHR) it counts, composition includes following main component:
(a) polyfunctional epoxy resin 30-60PHR；
(b) toughened resin 20-40PHR；
(c) phosphorous epoxy resin 10-30PHR；
(d) phosphorus curing agent 30-60PHR；
(e) other curing agent 10-30PHR；
(f) 30~150PHR of inorganic filler；
(g) 0.01~1PHR of curing accelerator；
(h) 0.01~1PHR of silane coupling agent；
(i) solvent is appropriate.
As a preferred embodiment, the polyfunctional epoxy resin include trifunctional epoxy resin, tetrafunctional epoxy resin,
Dicyclopentadiene phenol type epoxy resin, bisphenol A type epoxy resin, biphenyl epoxy resin one or more, structural formula point
Not are as follows:
As a preferred embodiment, the toughened resin is diisocyanate (diisocyanate) modified asphalt mixtures modified by epoxy resin
Rouge；Diisocyanate includes isophorone diisocyanate (IPDI), '-diphenylmethane diisocyanate (MDI), toluene diisocyanate
Acid esters (TDI), lysine diisocyanate (LDI), dicyclohexyl methyl hydride diisocyanate (HMDI)；Wherein, preferable toughening
Resin is MDI modified epoxy, structural formula are as follows:
Wherein, n is any positive integer；
R1For
R2For,
As a preferred embodiment, the phosphorous epoxy resin is the modification with DOPO structure or DOPO derivant structure
Epoxy resin.
As a preferred embodiment, the phosphorus curing agent is the phenolic aldehyde tree with DOPO structure or DOPO derivant structure
Rouge.
As a preferred embodiment, other described curing agent are bisphenol A phenolic resin, linear phenolic resin, dicyandiamide, two
One or more of aminodiphenyl sulfone, diaminodiphenylmethane.
As a preferred embodiment, the inorganic filler is aluminium hydroxide, fusion silica, crystal type titanium dioxide
One or more of silicon, alumino-silicate, kaolin, talcum powder, boehmite.
As a preferred embodiment, the curing accelerator is mainly imidazoles promotor, including 2- ethyl -4- methyl miaow
One or more of azoles, 2-methylimidazole, 2- phenylimidazole, 2- undecyl imidazole, boric acid.
As a preferred embodiment, the solvent is acetone, butanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, hexamethylene
One of ketone is a variety of.
The present invention has obvious advantages and beneficial effects compared with the existing technology, specifically, by above-mentioned technical proposal
Known to:
One, higher crosslink density can be obtained in the polyfunctional epoxy resin contained in the present composition after solidification, because
This with low thermal expansion coefficient, higher glass transition temperature and good thermal stability, while with contain in the composition
Some inorganic fillers cooperate with jointly, it is possible to provide excellent dimensional stability.
Two, the toughened resin itself contained in the present composition has the structure of high degree of symmetry, and polarity is lower, thus makes
Material is while with low hydroscopicity with lower and stable dielectric constant and dielectric loss tangent value.The resin is being handed over
The long linear structure for remaining its distinctive cyclic structure and ehter bond, aliphatic chain after connection solidifies on main chain, compared with ordinary epoxy resin
With more excellent flexibility, damage can be reduced in substrate process, and excellent machining is provided to composition
Property.
Three, the phosphorous epoxy resin and phosphorus curing agent contained in the present composition has excellent flame-retarding characteristic, together
When the composition in inorganic filler include fire-retardant filler, the two plays synergistic effect jointly, provides for the composition good fire-retardant
Performance.
Four, inorganic filler contained in the present composition is the lower filler of hardness, is substantially reducing composition
The coefficient of expansion while improve the processing performance of the composition, can also be promoted flame retardancy and reduces cost.
Five, the more traditional copper-clad plate of copper-clad plate made by invention resin composition have excellent dimensional stability,
Machining property and good heat resistance and anti-flammability, are completely suitable for high density interconnection laminated plates.
Specific embodiment
Present invention discloses a kind of Halogen-free high heat-resistant resin combinations for HDI copper-clad plate, are pressed with organic solid content
100 parts by weight (PHR) meter, composition include following main component:
(a) polyfunctional epoxy resin 30-60PHR；
(b) toughened resin 20-40PHR；
(c) phosphorous epoxy resin 10-30PHR；
(d) phosphorus curing agent 30-60PHR；
(e) other curing agent 10-30PHR；
(f) 30~150PHR of inorganic filler；
(g) 0.01~1PHR of curing accelerator；
(h) 0.01~1PHR of silane coupling agent；
(i) solvent is appropriate.
The polyfunctional epoxy resin includes trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene phenol type
Epoxy resin, bisphenol A type epoxy resin, biphenyl epoxy resin one or more, structural formula is respectively as follows:
The toughened resin is diisocyanate (diisocyanate) modified epoxy resin；Diisocyanate includes different
Isophorone diisocyanate (IPDI), '-diphenylmethane diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI), lysine two are different
Cyanate (LDI), dicyclohexyl methyl hydride diisocyanate (HMDI)；Wherein, preferable toughened resin is MDI modified epoxy tree
Rouge, structural formula are as follows:
Wherein, n is any positive integer；
R1For
R2For,
The phosphorous epoxy resin is the modified epoxy with DOPO structure or DOPO derivant structure.
The phosphorus curing agent is the phenolic resin with DOPO structure or DOPO derivant structure.
Other described curing agent are bisphenol A phenolic resin, linear phenolic resin, dicyandiamide, diaminodiphenylsulfone, diamino
One or more of diphenyl-methane.
The inorganic filler be aluminium hydroxide, fusion silica, crystalline sillica, alumino-silicate, kaolin,
One or more of talcum powder, boehmite.
The curing accelerator is mainly imidazoles promotor, including 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-
One or more of phenylimidazole, 2- undecyl imidazole, boric acid.
The solvent be one of acetone, butanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, cyclohexanone or a variety of,
Solvent only uses during the preparation process, as needed appropriate addition, and the amount of addition is unlimited, and final product of the invention does not contain
Solvent.
With multiple embodiments, invention is further described in detail below:
Main component code name is as follows:
(A) epoxy resin:
A1: tetrafunctional epoxy resin；
A2: bisphenol A type epoxy resin；
A3:MDI modified epoxy；
A4: phosphorous epoxy resin.
(B) curing agent:
B1: phosphorus curing agent；
B2: phenolic resin；
B3: diaminodiphenylmethane.
(C) inorganic filler:
C1: aluminium hydroxide；
C2: silica.
(D) curing accelerator:
D1:2- ethyl -4-methylimidazole；
D2: boric acid.
(E) coupling agent:
E: silane coupling agent.
Above-mentioned resin is mixed in following table 1 ratio, is then coated on reinforcing material E-Glass, it is roasting at 171 DEG C
3-5min is toasted in case and obtains prepreg, and respectively covering a 1OZ copper foil up and down with 6 prepregs is folded structure, is put into laminating machine
Middle pressing obtains laminate, carries out characteristic evaluation with this laminate.
The formula (parts by weight) of 1 composition of table
| Code name | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| A1 | 10 | 20 | 15 | 20 | 15 | |
| A2 | 20 | 15 | 10 | 20 | 30 | 20 |
| A3 | 30 | 30 | 40 | 30 | 40 | |
| A4 | 10 | 10 | 10 | 20 | 20 | |
| B1 | 20 | 20 | 20 | 10 | 10 | 20 |
| B2 | 10 | 5 | 20 | 20 | ||
| B3 | 5 | 5 | ||||
| C1 | 15 | 15 | 15 | 15 | 15 | 15 |
| C2 | 45 | 45 | 45 | 45 | 45 | 45 |
| D1 | 1 | 1 | 1 | 1 | 1 | 1 |
| D2 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
2 characteristic evaluation of table
The test method of the above characteristic is as follows:
(1) it peel strength: provides to test according to IPC-TM-650 2.4.9.
(2) PCT+Dip: the boiling 1h in 121 DEG C of 105KPa pressure cookers immerses in 288 DEG C of tin furnaces, when record plate bursting is layered
Between.
(3) Float (Cu): being placed on the tin of 288 DEG C of tin furnaces containing copper base, records plate bursting separation time；
(4) glass transition temperature (Tg): according to differential scanning calorimetry (DSC), according to IPC-TM-650 2.4.25 institute
Defined DSC method is measured.
(5) it thermally stratified layer time (T-288): is measured according to IPC-TM-650 2.4.24.1 method.
(6) thermal expansion coefficient Z axis CTE (TMA): according to the HDI testing of materials of defined in IPC-TM-650 2.4.24.5
Method is measured.
(7) dielectric constant (Dk) and dielectric loss tangent value (Df): the dielectric constant under 10GHz is tested according to SPDR method
With dielectric loss tangent value.
Design focal point of the invention is: one, the polyfunctional epoxy resin contained in the present composition, can after solidification
Higher crosslink density is obtained, therefore there is low thermal expansion coefficient, higher glass transition temperature and good thermostabilization
Property, while being cooperateed with jointly with the inorganic filler contained in the composition, it is possible to provide excellent dimensional stability.
Two, the toughened resin itself contained in the present composition has the structure of high degree of symmetry, and polarity is lower, thus makes
Material is while with low hydroscopicity with lower and stable dielectric constant and dielectric loss tangent value.The resin is being handed over
The long linear structure for remaining its distinctive cyclic structure and ehter bond, aliphatic chain after connection solidifies on main chain, compared with ordinary epoxy resin
With more excellent flexibility, damage can be reduced in substrate process, and excellent machining is provided to composition
Property.
Three, the phosphorous epoxy resin and phosphorus curing agent contained in the present composition has excellent flame-retarding characteristic, together
When the composition in inorganic filler include fire-retardant filler, the two plays synergistic effect jointly, provides for the composition good fire-retardant
Performance.
Four, inorganic filler contained in the present composition is the lower filler of hardness, is substantially reducing composition
The coefficient of expansion while improve the processing performance of the composition, can also be promoted flame retardancy and reduces cost.
Five, the more traditional copper-clad plate of copper-clad plate made by invention resin composition have excellent dimensional stability,
Machining property and good heat resistance and anti-flammability, are completely suitable for high density interconnection laminated plates.
The above described is only a preferred embodiment of the present invention, be not intended to limit the scope of the present invention,
Therefore any subtle modifications, equivalent variations and modifications to the above embodiments according to the technical essence of the invention, still
Belong in the range of technical solution of the present invention.
Claims (9)
1. a kind of Halogen-free high heat-resistant resin combination for HDI copper-clad plate, it is characterised in that: press 100 with organic solid content
Parts by weight (PHR) meter, composition include following main component:
(a) polyfunctional epoxy resin 30-60PHR；
(b) toughened resin 20-40PHR；
(c) phosphorous epoxy resin 10-30PHR；
(d) phosphorus curing agent 30-60PHR；
(e) other curing agent 10-30PHR；
(f) 30~150PHR of inorganic filler；
(g) 0.01~1PHR of curing accelerator；
(h) 0.01~1PHR of silane coupling agent；
(i) solvent is appropriate.
2. a kind of Halogen-free high heat-resistant resin combination for HDI copper-clad plate according to claim 1, feature exist
In: the polyfunctional epoxy resin includes trifunctional epoxy resin, tetrafunctional epoxy resin, dicyclopentadiene phenol type epoxy tree
Rouge, bisphenol A type epoxy resin, biphenyl epoxy resin one or more, structural formula is respectively as follows:
3. a kind of Halogen-free high heat-resistant resin combination for HDI copper-clad plate according to claim 1, feature exist
In: the toughened resin is diisocyanate (di isocyanate) modified epoxy resin；Diisocyanate includes different Fo Er
Ketone diisocyanate (IPDI), '-diphenylmethane diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI), lysine diisocyanate
Ester (LDI), dicyclohexyl methyl hydride diisocyanate (HMDI)；Wherein, preferable toughened resin is MDI modified epoxy,
Structural formula are as follows:
Wherein, n is any positive integer；
R1For—CH2—；
R2For,
4. a kind of Halogen-free high heat-resistant resin combination for HDI copper-clad plate according to claim 1, feature exist
In: the phosphorous epoxy resin is the modified epoxy with DOPO structure or DOPO derivant structure.
5. a kind of Halogen-free high heat-resistant resin combination for HDI copper-clad plate according to claim 1, feature exist
In: the phosphorus curing agent is the phenolic resin with DOPO structure or DOPO derivant structure.
6. a kind of Halogen-free high heat-resistant resin combination for HDI copper-clad plate according to claim 1, feature exist
In: other described curing agent are bisphenol A phenolic resin, linear phenolic resin, dicyandiamide, diaminodiphenylsulfone, diamino hexichol
One or more of methane.
7. a kind of Halogen-free high heat-resistant resin combination for HDI copper-clad plate according to claim 1, feature exist
In: the inorganic filler is aluminium hydroxide, fusion silica, crystalline sillica, alumino-silicate, kaolin, talcum
One or more of powder, boehmite.
8. a kind of Halogen-free high heat-resistant resin combination for HDI copper-clad plate according to claim 1, feature exist
In: the curing accelerator is mainly imidazoles promotor, including 2-ethyl-4-methylimidazole, 2-methylimidazole, 2- phenyl miaow
One or more of azoles, 2- undecyl imidazole, boric acid.
9. a kind of Halogen-free high heat-resistant resin combination for HDI copper-clad plate according to claim 1, feature exist
In: the solvent be one of acetone, butanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, cyclohexanone or a variety of.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283428A (en) * | 2019-07-15 | 2019-09-27 | 山东金宝电子股份有限公司 | A kind of copper-clad plate halogen-free resin composition and preparation method thereof |
| CN110421931A (en) * | 2019-08-30 | 2019-11-08 | 重庆德凯实业股份有限公司 | Cover copper foil glass fabric laminates and preparation method thereof |
| CN110481119A (en) * | 2019-08-30 | 2019-11-22 | 重庆德凯实业股份有限公司 | Halogen-free type covers copper foil glass fabric laminates |
| CN110655757A (en) * | 2019-09-27 | 2020-01-07 | 青岛欧普瑞新材料有限公司 | Halogen-free resin composition and preparation method thereof, prepreg and preparation method thereof, and laminated board and preparation method thereof |
| CN111114047A (en) * | 2019-12-30 | 2020-05-08 | 江苏联鑫电子工业有限公司 | Halogen-free phosphorus-containing phenolic cured copper-clad plate and preparation method thereof |
| CN111234734A (en) * | 2020-02-27 | 2020-06-05 | 招远春鹏电子科技有限公司 | Environment-friendly glue solution for flexible copper-clad plate and preparation method thereof |
| CN111704786A (en) * | 2020-06-19 | 2020-09-25 | 林州致远电子科技有限公司 | Glue solution for halogen-free high-Tg medium-loss copper-clad plate and preparation method and application thereof |
| CN111704785A (en) * | 2020-06-19 | 2020-09-25 | 林州致远电子科技有限公司 | Glue solution for halogen-free high-CTI copper-clad plate and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283428A (en) * | 2019-07-15 | 2019-09-27 | 山东金宝电子股份有限公司 | A kind of copper-clad plate halogen-free resin composition and preparation method thereof |
| CN110421931A (en) * | 2019-08-30 | 2019-11-08 | 重庆德凯实业股份有限公司 | Cover copper foil glass fabric laminates and preparation method thereof |
| CN110481119A (en) * | 2019-08-30 | 2019-11-22 | 重庆德凯实业股份有限公司 | Halogen-free type covers copper foil glass fabric laminates |
| CN110481119B (en) * | 2019-08-30 | 2022-03-25 | 重庆德凯实业股份有限公司 | Halogen-free copper foil-clad fiberglass cloth laminated board |
| CN110655757A (en) * | 2019-09-27 | 2020-01-07 | 青岛欧普瑞新材料有限公司 | Halogen-free resin composition and preparation method thereof, prepreg and preparation method thereof, and laminated board and preparation method thereof |
| CN110655757B (en) * | 2019-09-27 | 2022-06-28 | 青岛欧普瑞新材料有限公司 | Halogen-free resin composition and preparation method thereof, prepreg and preparation method thereof, and laminated board and preparation method thereof |
| CN111114047A (en) * | 2019-12-30 | 2020-05-08 | 江苏联鑫电子工业有限公司 | Halogen-free phosphorus-containing phenolic cured copper-clad plate and preparation method thereof |
| CN111234734A (en) * | 2020-02-27 | 2020-06-05 | 招远春鹏电子科技有限公司 | Environment-friendly glue solution for flexible copper-clad plate and preparation method thereof |
| CN111704786A (en) * | 2020-06-19 | 2020-09-25 | 林州致远电子科技有限公司 | Glue solution for halogen-free high-Tg medium-loss copper-clad plate and preparation method and application thereof |
| CN111704785A (en) * | 2020-06-19 | 2020-09-25 | 林州致远电子科技有限公司 | Glue solution for halogen-free high-CTI copper-clad plate and preparation method and application thereof |
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Application publication date: 20190322 |