CN109608811A - A kind of preparation method of flame-resistant electronic composite substrate - Google Patents
A kind of preparation method of flame-resistant electronic composite substrate Download PDFInfo
- Publication number
- CN109608811A CN109608811A CN201811299261.2A CN201811299261A CN109608811A CN 109608811 A CN109608811 A CN 109608811A CN 201811299261 A CN201811299261 A CN 201811299261A CN 109608811 A CN109608811 A CN 109608811A
- Authority
- CN
- China
- Prior art keywords
- flame
- composite substrate
- preparation
- copper foil
- resistant electronic
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of preparation methods of flame-resistant electronic composite substrate, the material has the matrix of a kind of low-k and low loss factors, for making the laminate and prepreg of high-frequency high-speed application field, which includes butadiene, styrene, butadienestyrene copolymer or styrene butadiene styrene.One key property of invention using laminate made from the thermosetting polymer is that the content of lower fiberglass fabric has excellent comprehensive performance relative to the range of high granular filler, comprising excellent thermal reliability (reducing CTE Z axis or thickness direction), improve electrically energy (fissipation factor) and extremely low water imbibition, the substrate suitable for high-frequency high-speed application.
Description
Technical field
The present invention relates to a kind of preparation methods of flame-retardant thermoset electronics composite substrate, can be used for high-frequency high-speed communication
The preparation of zone material.
Background technique
In recent years due to antenna, transmission signal speed is fast and undistorted in high frequency for base station and satellite communication requirement, especially
Be high frequency and under the conditions of high temperature and humidity signal transmission capabilities performance it is consistent under normality, so the substrate to frequency applications mentions
New requirement is gone out.
Generally, epoxide polymer with frequency increase, especially 5GHz or more when, loss of signal is increasing,
And as the temperature rises, loss of signal also can be increasing, when the frequency of antenna and base station is higher and higher, the epoxy of general category
Polymer has been unable to meet requirement, so putting forward new requirements to polymer used in substrate.
In addition, there are two class demands in market for such constant low-loss high frequency substrate, one kind is to require signal velocity
Fastly, that is, low-k is required, another kind of is to require high dielectric constant, can satisfy the demand of encapsulation volume miniaturization.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of preparation method of thermosetting property electronics composite substrate, systems
Standby composite substrate fissipation factor is low, and drifts about under the conditions of high frequency and high temperature and humidity without obvious, while heat-resist, stripping
Low from intensity height, water absorption rate, especially anti-flammability is splendid, and antenna and base station etc. is suitble to require the application of high frequency.
The present invention adopts the following technical scheme that:
A kind of preparation method of flame-resistant electronic composite substrate, includes the following steps；
(1) alkene organic matter is dissolved in solvent, is added with stirring filler, curing agent, fire retardant is then added, stirs
To resin liquid；The alkene organic matter includes butadiene, styrene, polybutadiene, polystyrene, Butadiene/Styrene copolymerization
One or more of object；
(2) by reinforcing material impregnating resin liquid, prepreg is obtained；
(3) prepreg is heated, prepreg is obtained；
(4) plural number prepreg is overlapped, respectively covers a copper foil up and down, hot pressing obtains electronics composite substrate；
The copper foil is 1 ounce copper foil or half ounce copper foil；The copper tumor height of 1 ounce copper foil is 8~12 microns；
The copper tumor height of half ounce copper foil is 6~10 microns；The copper foil rough surface is through supervinyi coupling agent treatment.
In the present invention, the filler includes silica, titanium dioxide, barium titanate, boron nitride, aluminium oxide, glass fibre
One of or more than one mixture；The reinforcing material is fibrous glass cloth.
In the present invention, the curing agent includes cumyl peroxide, peroxidized t-butyl perbenzoate, (the 2- second of 2,5- bis-
Base hexanoyl peroxide) -2,5- dimethylhexane, lithium rhodanate, three (2- carboxyethyl) phosphines, connection one of boric acid neopentyl glycol ester or
It is several.
In the present invention, alkene organic matter, reinforcing material, filler, curing agent mass ratio be (5~40): (10~30):
(10~70): (1~5)；The solid content of resin liquid is 75~85%, and generally 60% or so, the present invention uses existing resin liquid
High solids content had not only improved resin utilization efficiency, but also improved dielectric properties, also avoided the decline of peel strength.
In the present invention, the partial size of the filler is 30~50 microns.
In the present invention, the dosage of the fire retardant be alkene organic matter, filler, curing agent gross mass 8~15%.
In the present invention, the fire retardant is brominated or phosphorous fire retardant.
In the present invention, the temperature of heating is 60~140 DEG C, and the time is 1~5 minute.
In the present invention, the temperature of hot pressing is 150~300 DEG C, and the time is 10~55 minutes, pressure 25kg/cm2~
70kg/cm2。
In the present invention, the vinyl coupling agent is vinyl trichlorosilane, vinyl trimethylsilane, three second of vinyl
Oxysilane, vinyl three (methoxy ethoxy) silane, three tert-butoxy silane of vinyl, vinyl triacetoxy silicon
One or more of alkane, vinyltrimethoxysilane, vinyl methyl dimethoxysilane.
Flame-resistant electronic composite substrate of the invention is used to make the circuit board of high-frequency high-speed application field, and alkene is organic
Object includes one or more of butadiene, styrene, polybutadiene, polystyrene, butadiene/styrene copolymers；Wherein
Butadiene/styrene copolymers include butadiene-styrene copolymer or styrene-butadiene-styrene etc.；Dioxy
SiClx includes that crystalline sillica, amorphous silica, preparing spherical SiO 2, fumed silica etc. are a kind of or more
Kind；The fire retardant further included is brominated or phosphorous fire retardant, for example brominated fire retardant is deca-BDE, ten bromines
Diphenylethane or the double tetrabromo phthalimides of ethylene, phosphonium flame retardant are three (2,6- 3,5-dimethylphenyl) phosphorus, 10- (2,5-
Dihydroxy phenyl) miscellaneous -10- phosphine phenanthrene -10- oxide of -9,10- dihydro-9-oxy, 2,6- 3,5-dimethylphenyl phosphorus base benzene.
The present invention has the advantage that
Invention olefin organic matter can be butadiene, styrene, butadienestyrene copolymer, styrene butadiene benzene
Any one or more mixtures of ethylene copolymer, because containing the preferable phenyl ring of rigidity and Gao Yi in resinous molecular structure
Amount vinyl content provides required a large amount of unsaturated ethylene alkenyls when solidification crosslinking, crosslink density when solidification can be improved, to mention
(Kraton is public by the excellent high temperature resistance and rigidity of high material, alkene organic matter such as D1101 (Kraton company) and FG1901
Department).
Granular filler of the invention is crystalline sillica, amorphous silica, preparing spherical SiO 2, gas phase dioxy
The one or more such as SiClx, titanium dioxide, barium titanate, boron nitride, aluminium oxide, glass fibre, granular filler play raising glue
Liquid solid content improves dimension stability, reduces the purpose of CTE；Preferential granular filler is silica, and wherein partial size is
30~50 microns, adoptable silica filler such as FB-35 (Denka company), 525 (Sibelco companies).
Fibrous glass cloth of the invention plays the dimensional stability for improving substrate, reduces the work of Material shrinkage in solidification process
With the specification of fibrous glass cloth is as follows:
| Fabric | Cloth thickness (mm) | Supplier |
| 7628 | 0.18 | Shanghai it is macro and |
| 2116 | 0.094 | Shanghai it is macro and |
| 1080 | 0.056 | Shanghai it is macro and |
| 106 | 0.04 | Shanghai it is macro and |
The flame retardant property of electronics composite material can be improved in fire retardant of the invention；Curing agent plays the work for accelerating reaction
With, when composition of the invention is heated, curing agent decomposition is generated free radicals, and the strand for causing polymer crosslinks,
Curing agent be cumyl peroxide, peroxidized t-butyl perbenzoate, 2,5- bis- (2- ethyihexanoylperoxy) -2,5- dimethyl oneself
One or more of alkane, lithium rhodanate, three (2- carboxyethyl) phosphines, connection boric acid neopentyl glycol ester, and the elements such as phosphorus, boron, sulphur
Certain fire retarding effect can also be provided.
Resin not instead of epoxylite employed in thermosetting property electronics composite material of the invention uses low dielectric
Double bond quasi polymer material, while packing technique of arranging in pairs or groups can be made low loss factors substrate, and it is heat-resisting, water-fast, fire-retardant,
Removing etc. is had excellent performance.
Most important, the present invention overcomes low (residual copper ratio height, the influences if being higher than 5 microns of existing copper foil copper tumor height
Electric signal), the defect of vinyl coupling agent treatment (causing existing resin system peel strength low) can not be used, limit 1 ounce of copper
The copper tumor height of foil is 8~12 microns；The copper tumor height of half ounce copper foil is 6~10 microns；Copper foil rough surface is through supervinyi
Coupling agent treatment, obtained substrate residual copper ratio is very low, peel strength is high.
Specific embodiment
Embodiment 1
The block copolymer (D1101) of the styrene of 100 parts by weight and butadiene is dissolved in toluene, is added with stirring 85 weights
Measure the silica (525) of part, the curing agent DCP of 6.5 parts by weight, 22 parts by weight fire retardant SAYTEX8010, stir to get
Resin liquid (solid content 80%) impregnates the above resin liquid using 80 parts by weight, 1080 fibrous glass cloth and obtains prepreg.Then
Prepreg is made after drying removal solvent.8 prepregs are overlapped, copper foil are covered in its two sides, through excessively high in press
Warm it is cured after flame-resistant electronic composite substrate is made.
In the present embodiment, the partial size of filler is 30~40 microns；Copper foil is 1 ounce copper foil, the copper tumor height of copper foil is 9~
10 microns；Copper foil rough surface is handled through supervinyi coupling agent vinyl trimethylsilane；In rolled copper foil or electrolytic copper foil
The copper tumor for preparing on one side form rough surface, then with vinyl coupling agent treatment, obtain copper foil of the invention；Prior art preparation
Copper tumor height is low and uses epoxy group coupling agent treatment, and in order to avoid residual copper ratio is high and improves peel strength, invention is then first
It is secondary to use high-copper tumor, vinyl coupling agent, it had not only improved peel strength but also had controlled residual copper.
The temperature of above-mentioned drying is 80 DEG C, and the time is 5 minutes, and the temperature of hot pressing is 280 DEG C, and the time is 45 minutes, pressure
For 60kg/cm2；Its physical data is as shown in table 1.
Embodiment 2
The block copolymer (D1101) of the styrene of 100 parts by weight and butadiene is dissolved in toluene, is added with stirring 240
The silica (525) of parts by weight, the curing agent DCP of 7.5 parts by weight, 28 parts by weight fire retardant SAYTEX8010, stir
To resin liquid (solid content 80%), the above resin liquid is impregnated using 125 parts by weight, 1080 fibrous glass cloth and then dries removal
Prepreg is made after solvent, then 8 prepregs are overlapped, covers copper foil in its two sides, high temperature hot pressing is passed through in press
Flame-resistant electronic composite substrate is made after solidification；The temperature of drying is 100 DEG C, and the time is 3 minutes, and the temperature of hot pressing is 250
DEG C, the time is 50 minutes, pressure 70kg/cm2；Its physical data is as shown in table 1.
In the present embodiment, the partial size of filler is 40~50 microns；Copper foil is 1 ounce copper foil, and copper tumor height is 10~11 micro-
Rice；Copper foil rough surface is handled through supervinyi coupling agent vinyl trimethylsilane.
Embodiment 3
The block copolymer (D1101) of the styrene of 90 parts by weight and butadiene is dissolved in toluene, is added with stirring 45 weights
Measure the silica (525) of part, curing agent (lithium rhodanate, the connection boric acid neopentyl glycol of mass ratio 1: 0.2 of 5.6 parts by weight
Ester), the fire retardants 2 of 12 parts by weight, 6- 3,5-dimethylphenyl phosphorus base benzene stirs to get resin liquid (solid content 80%), uses 78
Then 1080 fibrous glass cloth of parts by weight, which impregnates above resin liquid, dries prepreg is made after removal solvent, then by 8 Zhang Bangu
Change piece overlapping, covers copper foil in its two sides, flame-resistant electronic composite substrate is made after high temperature hot pressing solidifies in press；
The temperature of drying is 130 DEG C, and the time is 2 minutes, and the temperature of hot pressing is 290 DEG C, and the time is 42 minutes, pressure 60kg/cm2；
Its physical data is as shown in table 1.
In the present embodiment, the partial size of filler is 30~35 microns；Copper foil is 1 ounce copper foil, and copper tumor height is 9~10 micro-
Rice；Copper foil rough surface is handled through supervinyi coupling agent vinyl trimethylsilane.
Embodiment 4
The block copolymer (D1101) of the styrene of 100 parts by weight and butadiene is dissolved in toluene, is added with stirring 85 weights
Measure the silica (525) of part, curing agent (lithium rhodanate of mass ratio 1: 0.8, three (2- carboxyethyls) of 6.5 parts by weight
Phosphine), the fire retardant SAYTEX8010 of 18 parts by weight, stir to get resin liquid (solid content 80%), use 80 parts by weight 1080
Fibrous glass cloth, which impregnates then the above resin liquid dries removal solvent after, is made prepreg, then 8 prepregs are overlapped,
Its two sides covers copper foil, and flame-resistant electronic composite substrate is made after high temperature hot pressing solidifies in press；The temperature of drying
It is 80 DEG C, the time is 5 minutes, and the temperature of hot pressing is 280 DEG C, and the time is 45 minutes, pressure 60kg/cm2；Its physical data is such as
Shown in table 1.
In the present embodiment, the partial size of filler is 40~50 microns；Copper foil is half ounce copper foil, and copper tumor height is 8~9 micro-
Rice；Copper foil rough surface is handled through supervinyi coupling agent vinyl methyl dimethoxysilane.
Embodiment 5
The butadiene of the styrene of 60 parts by weight and 40 parts by weight is dissolved in toluene, is added with stirring the dioxy of 85 parts by weight
SiClx (525), the curing agent (lithium rhodanate of mass ratio 1: 0.8, three (2- carboxyethyl) phosphines) of 7.5 parts by weight, 25 parts by weight
Fire retardant SAYTEX8010, stir to get resin liquid (solid content 80%), use 80 parts by weight, 1080 fibrous glass cloth soak
Prepreg is made after then drying removal solvent in the above resin liquid of stain, then 8 prepregs are overlapped, and covers copper in its two sides
Flame-resistant electronic composite substrate is made in foil in press after high temperature hot pressing solidifies；The temperature of drying is 80 DEG C, and the time is
5 minutes, the temperature of hot pressing was 280 DEG C, and the time is 45 minutes, pressure 60kg/cm2；Its physical data is as shown in table 1.
In the present embodiment, the partial size of filler is 30~40 microns；Copper foil is half ounce copper foil, and copper tumor height is 7~8 micro-
Rice；Copper foil rough surface is handled through supervinyi coupling agent vinyl methyl dimethoxysilane.
Comparative example 1
Manufacture craft is same as Example 1, and using existing 1 ounce copper foil, physical data is as shown in table 1.
Comparative example 2
Manufacture craft is same as Example 1, and the block for replacing styrene and butadiene using existing epoxy-resin systems is total
Polymers D1101 and curing agent DCP；Its physical data is as shown in table 1.
Comparative example 3
Manufacture craft is same as Example 1, using ladder heating and hot pressing, be heated to be+90 DEG C/2 minutes 60 DEG C/1 minute+
120 DEG C/1 minute, hot pressing was 150 DEG C/10 minutes/50kg/cm2+ 180 DEG C/25 minutes/60kg/cm2+250℃/20/70kg/
cm2+ 300 DEG C/5 minutes/70kg/cm2；Its physical data is as shown in table 1.
All of above raw material is all commercial products, and obtained properties of product test method is conventional method, and embodiment 100 is small
When boiling water absorption rate less than 0.015%, comparative example 1 be 0.014%, comparative example 2 be 0.092%, comparative example 3 be 0.032%；?
On the basis of embodiment 1, silica is replaced with into the fillers such as boron nitride, aluminium oxide, performance is close；If using existing epoxy
Base coupling agent treatment copper foil, then peel strength is less than 4.4.
1 embodiment of table and comparative example properties of product
Described in Physical Property Analysis as above, compared with general composite material, flame-resistant electronic composite substrate of the invention is gathered around
There are more excellent dielectric constant and fissipation factor, high-frequency high-speed performance is fine, fully meets the demand in the following market 5G.
Claims (10)
1. a kind of preparation method of flame-resistant electronic composite substrate, which is characterized in that include the following steps；
(1) alkene organic matter is dissolved in solvent, is added with stirring filler, curing agent, fire retardant is then added, stir to get tree
Rouge liquid；The alkene organic matter include butadiene, styrene, polybutadiene, polystyrene, in butadiene/styrene copolymers
One or more；
(2) by reinforcing material impregnating resin liquid, prepreg is obtained；
(3) prepreg is heated, prepreg is obtained；
(4) plural number prepreg is overlapped, respectively covers a copper foil up and down, hot pressing obtains electronics composite substrate；
The copper foil is 1 ounce copper foil or half ounce copper foil；The copper tumor height of 1 ounce copper foil is 8~12 microns；It is described
The copper tumor height of half ounce copper foil is 6~10 microns；The copper foil rough surface is through supervinyi coupling agent treatment.
2. the preparation method of flame-resistant electronic composite substrate according to claim 1, it is characterised in that: the filler includes
One of silica, titanium dioxide, barium titanate, boron nitride, aluminium oxide, glass fibre or more than one mixture；Institute
Stating reinforcing material is fibrous glass cloth.
3. the preparation method of flame-resistant electronic composite substrate according to claim 1, it is characterised in that: the curing agent packet
Include cumyl peroxide, peroxidized t-butyl perbenzoate, 2,5- bis- (2- ethyihexanoylperoxy) -2,5- dimethylhexane, sulphur
One or more of cyanic acid lithium, three (2- carboxyethyl) phosphines, connection boric acid neopentyl glycol ester.
4. the preparation method of flame-resistant electronic composite substrate according to claim 1, it is characterised in that: alkene organic matter,
Reinforcing material, filler, curing agent mass ratio be (5~40): (10~30): (10~70): (1~5)；The solid content of resin liquid
It is 75~85%.
5. the preparation method of flame-resistant electronic composite substrate according to claim 1, it is characterised in that: the grain of the filler
Diameter is 30~50 microns.
6. the preparation method of flame-resistant electronic composite substrate according to claim 1, it is characterised in that: the fire retardant
Dosage be alkene organic matter, filler, curing agent gross mass 8~15%.
7. the preparation method of flame-resistant electronic composite substrate according to claim 1, it is characterised in that: the fire retardant is
Brominated or phosphorous fire retardant.
8. the preparation method of flame-resistant electronic composite substrate according to claim 1, it is characterised in that: the temperature of heating is
60~140 DEG C, the time is 1~5 minute.
9. the preparation method of flame-resistant electronic composite substrate according to claim 1, it is characterised in that: the temperature of hot pressing is
150~300 DEG C, the time is 10~55 minutes, pressure 25kg/cm2~70kg/cm2。
10. the preparation method of flame-resistant electronic composite substrate according to claim 1, it is characterised in that: the vinyl
Coupling agent is vinyl trichlorosilane, vinyl trimethylsilane, vinyltriethoxysilane, (the methoxyl group second of vinyl three
Oxygroup) silane, three tert-butoxy silane of vinyl, vinyltriacetoxy silane, vinyltrimethoxysilane, vinyl
One or more of methyl dimethoxysilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811299261.2A CN109608811A (en) | 2018-10-11 | 2018-10-11 | A kind of preparation method of flame-resistant electronic composite substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811299261.2A CN109608811A (en) | 2018-10-11 | 2018-10-11 | A kind of preparation method of flame-resistant electronic composite substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109608811A true CN109608811A (en) | 2019-04-12 |
Family
ID=66002720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811299261.2A Pending CN109608811A (en) | 2018-10-11 | 2018-10-11 | A kind of preparation method of flame-resistant electronic composite substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109608811A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5571609A (en) * | 1994-10-13 | 1996-11-05 | Rogers Corporation | Polybutadiene and polyisoprene based thermosetting compositions and method of manufacture thereof |
| US5679230A (en) * | 1995-08-21 | 1997-10-21 | Oak-Mitsui, Inc. | Copper foil for printed circuit boards |
| CN102161823A (en) * | 2010-07-14 | 2011-08-24 | 广东生益科技股份有限公司 | Composite material, high-frequency circuit substrate therefrom and manufacture method thereof |
-
2018
- 2018-10-11 CN CN201811299261.2A patent/CN109608811A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5571609A (en) * | 1994-10-13 | 1996-11-05 | Rogers Corporation | Polybutadiene and polyisoprene based thermosetting compositions and method of manufacture thereof |
| US5679230A (en) * | 1995-08-21 | 1997-10-21 | Oak-Mitsui, Inc. | Copper foil for printed circuit boards |
| CN102161823A (en) * | 2010-07-14 | 2011-08-24 | 广东生益科技股份有限公司 | Composite material, high-frequency circuit substrate therefrom and manufacture method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 胡旭日等: "无添加剂体系中电解铜箔的多步粗化", 《电镀与涂饰》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104845363B (en) | A kind of halogen-free resin composition and application thereof | |
| CN102161823B (en) | Composite material, high-frequency circuit substrate therefrom and manufacture method thereof | |
| CN108219371B (en) | Epoxy resin composition, prepreg, laminate, and printed wiring board | |
| TW201617380A (en) | Low dielectric polyester composite having phosphorous and method of manufacturing the same | |
| CN103980708A (en) | Halogen-free flame-retardant thermosetting resin composition of integrated circuit, prepreg and laminate | |
| WO2001042360A1 (en) | Flame-retardant epoxy resin composition and laminate made with the same | |
| CN106589748B (en) | A kind of resin combination of the copper clad foil substrate for high-frequency high-speed field and its application | |
| JP6540259B2 (en) | Epoxy resin composition for heat conductive material, cured product thereof and electronic member | |
| WO2015101232A1 (en) | Halogen-free epoxy resin composition and use thereof | |
| CN103965624A (en) | Halogen-free resin composition, and prepreg and laminated board prepared from same | |
| CN103980704A (en) | Halogen-free resin composition for high-frequency and high-speed substrate as well as prepreg and laminated plate | |
| CN102850766B (en) | Halogen-free resin composition, prepreg and laminated board made from the same | |
| CN104109347A (en) | Halogen-free thermosetting resin composition, prepreg and laminated plate | |
| CN104177530A (en) | Active ester resin and thermosetting resin composition thereof | |
| US20140342161A1 (en) | Epoxy Resin Composition and Prepreg and Copper Clad Laminate Manufactured by Using the Same | |
| CN109777123A (en) | Resin combination, preliminary-dip piece used for printed circuit and metal-coated laminated board | |
| CN109705284A (en) | A kind of polyphenyl ether resin composition of low-k and its prepreg of production | |
| WO2014040261A1 (en) | Epoxy resin compound, and, prepreg and clad copper laminate manufactured using the compound | |
| CN109749396A (en) | A kind of polyphenyl ether resin composition and its application | |
| CN111393594A (en) | Active ester resin and resin composition thereof | |
| CN105348742A (en) | Thermosetting resin composition containing melamine type benzoxazine resin, prepreg and laminated board | |
| CN109504020A (en) | A kind of flame-resistant electronic composite substrate | |
| CN103980667A (en) | Thermosetting resin composition of integrated circuit, prepreg and laminate | |
| CN114921059A (en) | Novel phosphorus-containing epoxy resin composition and copper-clad plate prepared from same | |
| CN103342894A (en) | Thermosetting resin composition as well as prepreg and laminate prepared from same |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20191220 Address after: 519060, Zhuhai District, Guangdong Province, Hong Wan Road, hung Wan Road, No. 10, communications building on the first floor A District Applicant after: ZHUHAI GUONENG COMPOSITE MATERIAL TECHNOLOGY CO.,LTD. Address before: 215011 Jiangsu Province, Suzhou City District Xuguan Xingxian Road No. 315 room 650 Applicant before: SUZHOU YIKETAI ELECTRONIC MATERIAL Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| DD01 | Delivery of document by public notice |
Addressee: Wang Ling Document name: Rejection decision |
|
| DD01 | Delivery of document by public notice | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190412 |
|
| RJ01 | Rejection of invention patent application after publication |